TW200538754A

TW200538754A - Method for producing a multilayer body

Info

Publication number: TW200538754A
Application number: TW094108473A
Authority: TW
Inventors: Hiroomi Shimomura; Mitsunobu Doimoto; Yasunobu Suzuki; Tetsuya Yamamura; Yuichi Eriyama; Takayoshi Tanabe; Hideaki Takase
Original assignee: Jsr Corp
Priority date: 2004-03-18
Filing date: 2005-03-18
Publication date: 2005-12-01
Also published as: WO2005090473A1; KR20070003944A; JPWO2005090473A1; JP4715746B2

Abstract

The present invention discloses a method for producing a multilayer body having a base and a conductive layer (antistatic layer) and multilayer structure arranged on the base. The method for producing a multilayer body is characterized in that the conductive layer (antistatic layer) is formed by vapor-phase polymerization of at least one monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene, 3,4-ethylenedioxythiophene and derivatives of those, then a liquid curable resin composition containing a fluorine-containing polymer (A), a thermosetting compound (B), a curing catalyst c, metal oxide particles (D), a highly volatile solvent (E-1) and a less volatile solvent (E-2) is applied thereto for forming a coating and the solvent is evaporated from the coating, so that this single coating is formed into two or more layers. Also disclosed is a multilayer body produced by such a method.

Description

200538754 (1) 九、發明說明【發明所屬之技術領域】本發明係有關層合物之製造方法，及藉由其而得之層合物者。尤其是有關可由1之塗膜形成2以上之層的層合物之製造方法者。【先前技術】 p 目前，隨著多重媒體之發達，可觀察到在各種顯示裝置中之種種發展。各種顯示裝置之中，尤其是以攜帶用爲中心之室外使用者，其辨識性之提升越發重要；需要者要求在大型顯示裝置中亦能更輕鬆觀賞，但此事依然成爲技術課題而未決。已往，提升顯示裝置之辨識性的方法之一，係將由低折射率材料構成之防反射膜被覆於顯示裝置的基材而進行 ;形成防反射膜之方法有，例如藉由蒸鍍法形成氟化合物 φ 之薄膜的方法。然而，近年來對以液晶顯示裝置爲中心、低成本、且大型之顯示裝置，亦尋求可形成防反射膜之技術。不過，在藉由蒸鍍法時，對大面積之基板形成高效率且均勻的防反射膜相當困難，並且必要真空裝置之故，難以降低成本。由於如此之情況，開始檢討將折射率低之氟系聚合物溶解於有機溶劑調製成液狀的組成物，以其塗佈於基板表面形成防反射膜之方法；例如有在基板表面塗佈氟化烷基矽烷之提案（例如參照專利文獻1及2 )。又，有塗佈具有 200538754 (2) 特定結構之氟系聚合物的方法之提案（例如參照專利文獻 3 ) ° 另一方面，亦有以防靜電層中使用導電性高分子之層合物做爲防反射膜者（例如參照專利文獻4 )。專利文獻1 :特開昭6 1 -40 845號公報專利文獻2:特公平6-9 8 703號公報專利文獻3 :特開平6- 1 1 5 023號公報專利文獻4:特開2003 -3 00267號公報此等已往之防反射膜，大部份係在基材上形成導電層 (防靜電層）、不同折射率之層、硬塗層等之層合物。已往之製造方法中，重覆在基材上將各層分別塗佈的步驟。本發明係以如上所述之狀況爲背景者，其目的爲提供藉由一次之塗佈步驟能形成2以上之層的層合物之製造方法，及藉由其而得之層合物。又，本發明之另一目的爲提供效率良好形成導電層之層合物的製造方法及藉由其而得之層合物。進而，本發明之又一目的爲提供具有對基材之密著性優越、耐擦傷性高、防反射效果良好的層合物之製造方法及藉由其而得之層合物。【發明內容】 [發明之揭示] 依本發明能提供下述之層合物的製造方法及藉由其而得之層合物。 [1] 一種層合物之製造方法，其係具有基材，與在其上 200538754 (3) 之導電層及多層結構的層合物之製造方法；其特徵爲藉由將至少一種選自吡咯、噻吩、呋喃、硒吩、3，4 -伸乙二氧基噻吩及此等之衍生物所成群的單體進行氣相聚合’形成導電層；以含有下述成份（A) 、( B ) 、( C ) 、( D )、（ E-1 )及（E_2 )之液狀硬化性樹脂組成物進行塗佈，形成塗膜； p 藉由使溶劑自此1之塗膜蒸發，形成2以上之層； (液狀硬化性樹脂組成物） (A )含氟聚合物 (B )熱固性化合物 (C )硬化催化劑 (D ) —種或兩種以上之數平均粒徑爲lOOnm以下的金屬氧化物粒子（以下稱爲「（ D )金屬氧化物粒子」） φ ( E-1 ) —種或兩種以上之對（A )含氟聚合物的溶解性高之溶劑（以下稱爲「（ E-1 )快速揮發溶劑」） (E-2 ) —種或兩種以上之對（D )金屬氧化物粒子的分散穩定性高，且與（E-1 )快速揮發溶劑具有相溶相之溶劑（以下稱爲「（ E-2 )緩慢揮發溶劑」）；而且，（E -1 )快速揮發溶劑之相對蒸發速度大於（ E-2 )緩慢揮發溶劑之相對蒸發速度。 [2]—種層合物之製造方法’其係具有基材，與在其上之導電層及多層結構的層合物之製造方法；其特徵爲藉由 (4) 200538754 將至少一種選自吡咯、噻吩、呋喃、硒吩、3，4 -伸乙二氧基噻吩及此等之衍生物所成群的單體進行氣相聚合’形成導電層；以含有下述成份（A) 、( B ) 、( C ) 、( 〇 )、( E-1 ) 、（ E-2 )及（F )之液狀硬化性樹脂組成物進行塗佈，形成塗膜；藉由使溶劑自此1之塗膜蒸發，形成2以上之層； (液狀硬化性樹脂組成物） (A )含氟聚合物 (B )熱固性化合物 (C )硬化催化劑 (D) —種或兩種以上之數平均粒徑爲lOOnm以下的金屬氧化物粒子（以下稱爲「（ D )金屬氧化物粒子」） (E-1) —種或兩種以上之對（A)含氟聚合物的溶解 φ 性高之溶劑（以下稱爲「（ E-1 )快速揮發溶劑」） (E - 2 ) —種或兩種以上之對（D )金屬氧化物粒子的分散穩定性高，且與（E-1 )快速揮發溶劑具有相溶相之溶劑（以下稱爲「（ E-2 )緩慢揮發溶劑」）； (F )活性能量線硬化性化合物；而且，（E -1 )快速揮發溶劑之相對蒸發速度大於（ E-2 )緩慢揮發溶劑之相對蒸發速度。 [3]如上述[1]或[2]記載之層合物的製造方法，其中該 (A)含氟聚合物爲分子內具有羥基之含氟聚$物j。 200538754 1 (5) [4] 如上述[2]記載之層合物的製造方法，其中液狀硬化性樹脂組成物之固形份1 0 0質量％中，含有該（B )成份 5〜8 0質量％。 [5] 如上述[1]記載之層合物的製造方法，其中該（C) 硬化催化劑爲熱酸產生劑。 [6] 如上述[2]記載之層合物的製造方法，其中液狀硬化性樹脂組成物之固形份1 00質量％中，含有該（C )成份 | 0.1-20 質量％。 [7] 如上述[1]記載之層合物的製造方法，其中該（D ) 金屬氧化物粒子之折射率爲1.50以上。 [8] 如上述[1]記載之層合物的製造方法，其中該（D ) 金屬氧化物粒子係以一種或兩種以選自氧化鈦、氧化鉻、含銻之氧化錫、含磷之氧化錫、含錫之氧化銦、氧化鋁、氧化鈽、氧化鋅、含鋁之氧化鋅、氧化錫、含銻之氧化鋅及含銦之氧化鋅的金屬氧化物爲主成份之粒子。 φ [9]如上述[1]記載之層合物的製造方法，其中該（D ) 金屬氧化物粒子係以氧化鈦爲主成份之粒子。 [10]如上述[2]記載之層合物的製造方法，其中該（D )金屬氧化物粒子係以一種或兩種以上選自氧化鈦、氧化鉻、含銻之氧化錫、含錫之氧化銦、二氧化矽、氧化鋁、氧化鈽、氧化鋅、含鋁之氧化鋅、氧化錫、含銻之氧化鋅及含銦之氧化鋅的金屬氧化物爲主成份之粒子。 [1 1]如上述[1]或[2]記載之層合物的製造方法，其中該 (D )金屬氧化物粒子爲具有多層結構之金屬氧化物粒子 -9- 200538754 v (6) [12] 如上述[2]記載之層合物的製造方法，其中該（D )金屬氧化物粒子與具有聚合性不飽和基之有機化合物連結。 [13] 如上述[1]或[2]記載之層合物的製造方法，其中該 (E-1 )快速揮發溶劑爲一種或兩種以上之對（D )金屬氧化物粒子的分散穩定性低之溶劑；（E - 2 )緩慢揮發溶劑爲一種或兩種以上之對（A)含氟聚合物的溶解性低之溶劑。 [14] 如上述[1]或[2]記載之層合物的製造方法，其中該 2以上之層的各層爲金屬氧化物粒子高密度存在之層、或金屬氧化物粒子貫質上不存在之層，至少一層爲金屬氧化物粒子高密度存在之層。 [15] 如上述[1]或[2]記載之層合物的製造方法，其中該 2以上之層爲兩層。 [1 6 ]如上述[1 ]記載之層合物的製造方法，其中更藉由將該2以上之層加熱而硬化。 [17] 如上述[2]記載之層合物的製造方法，其中更藉由將該2以上之層加熱及/或藉由照射放射線而硬化。 [18] 如上述[1]或[2]記載之層合物的製造方法，其中層合物爲光學用零件。 [19] 如上述[1]或[2] g己載之層合物的製造方法，甘中層合物爲防反射膜。 [20] 如上述[15]記載之層合物的製造方法，其中該層 -10- 200538754 v (7) 合物係在基材上，自靠近基材側起依順序至少層合防靜電層、高折射率層及低折射率層之防反射膜；該導電層係防靜電層；該[1 5 ] 載之兩層係由筒折射率層及低折射率層所成〇 [21] 如上述[20]記載之層合物的製造方法，其中低折射率層於5 89nm之折射率爲1.20〜1.55 ;高折射率層於 g 589nm之折射率爲1.50〜2.20，比低折射率層之折射率高。 [22] 如上述[15]記載之層合物的製造方法，其中該層合物係在基材上，自靠近基材側起依順序至少層合防靜電層、中折射率層、高折射率層及低折射率層之防反射膜；該導電層爲防靜電層；該[1 5 ]記載之兩層係由高折射率層及低折射率層所成〇 [23] 如上述[22]記載之層合物的製造方法，其中低折 φ 射率層於5 8 9nm之折射率爲1 .20〜1 .55 ;中折射率層於 5 89nm之折射率爲1.50〜1.90，比低折射率層之折射率高；高折射率層於5 89nm之折射率爲1.51〜2.20，比中折射率層之折射率高。 [24] 如上述[20]記載之層合物的製造方法，其中更在基材上形成硬塗層。 [25] —種層合物，其特徵爲藉由如上述[1]或[2]記載之層合物之製造方法製造而得。本發明之層合物的製造方法，可由塗佈組成物而得之1 -11 - 200538754 v. (8) 的塗膜形成2以上之層，能簡化具有多層結構之層合物的製造步驟。又，本發明之層合物的製造方法，能效率良好形成導電層。因此，本發明之層合物的製造方法，極適合使用於形成防反射膜、透鏡、選擇穿透膜濾光片等光學材料。進而，本發明之層合物，利用氟含量高，甚適合使用於對耐候性要求之基板的塗料、耐候薄膜、塗覆、其他等。並且，該層合物藉由在最外層（自基材起最遠之層）設置 g 低折射率層，可賦予良好之防反射效果。又，依本發明可獲得對基材之密著性優越、耐擦傷性高的層合物。因此，本發明之層合物極適合使用爲防反射膜，藉由使用於各種顯示裝置能提升其辨識性。 [用以實施發明之最佳型態] 本發明係，具有基材，與在其上之導電層及多層結構的層合物之製造方法，及藉由其而得之層合物。具體而言 φ ，本發明之製造方法係在基材或基材上形成之層（以下稱爲基底層）之上，將單體進行氣相聚合而形成導電層。，大塗佈如後述之所定的液狀硬化性樹脂組成物，藉由自此塗佈之組成物使溶劑蒸發（以下亦稱「乾燥」），形成2以上之層。還有，乾燥後並非於完全無溶劑之狀態亦可，在能獲得做爲硬化膜之特性的範圍溶劑殘餘亦可。較佳爲在基底層之上形成導電層後，於其上方形成2以上之層。又，本發明中，可實施兩次以上由1之塗膜形成2以上之層。首先，就導電層之氣相聚合說明如下。 -12- 200538754 . Ο) 藉由氣相聚合形成導電層，可採用例如特_ 82 1 0 5號公報記載之方法等製造，具體而言，可自聚合形成。即，在基底層上以數μιη單位塗佈氧化劑體於氣體狀態與氧化劑塗膜接觸進行聚合，在基材導電性聚合物膜。此時爲提升黏著力，亦可倂用溶聚胺基甲酸乙酯、聚氯乙烯、聚乙烯醇、甲基纖維殼素等高分子。 φ 本發明中，在塗佈氧化劑之基底層上使單體氣，形成由導電性聚合物所成之導電層，此時之反應〇〜1 40 °C爲佳。更詳細說明聚合方法如下，本發明定於其方法。具體而言，首先第一階段，在基底層之表面以位塗佈0.5〜1 0重量°/。的氧化劑。氧化劑可單獨或組選自例如CuCl2、甲苯磺酸鐵（III )、過氯酸鐵（ FeCl2及Cu(C104)2 · 6H20所成群之化合物。此時之 φ 件隨使用的基底層種類而異，例如可使用選自甲醇醇、乙基溶纖劑、乙醇、環己烷、丙酮、乙酸乙酯及甲乙酮之有機溶劑。此等可單獨或兩種以上混合例如由甲醇、2 - 丁醇及乙基溶纖劑所構成之有機转 :2 : 1、6 : 2 : 2、5 : 3 : 2等比例混合使用。塗佈之基底層，考量氧化劑之分解以80 °C以下之熱風乾燥。其次第二階段，在以氧化劑塗佈之基底層上，自卩比略、噻吩、咲喃、硒吩、3，4 -伸乙二氧基噻吩 ^ 2003- 導電性，使單上形成劑，與素、甲相聚合溫度以並不限數μιη單合使用 III )、溶劑條 :、2-丁、甲苯使用， I劑以7 氧化劑乾燥機與將選及其衍 -13- (10) 200538754 生物所成群之單體氣化接觸，於基底層之表面進行聚合反應。此時使單體氣化之方法有在密閉之小室內將單體以 0〜14 0 °c蒸餾的方法，與藉化學蒸鍍（CVD )之方法等。此時以調整溫度條件與反應時間爲佳，聚合反應在1 〇秒〜40分鐘之範圍進行，一般而言因應單體之種類而改變，進行膜厚及表面電阻値等可達目標値爲止。其次，第三階段，在聚合完成後進行爲去除未反應之 φ 單體及氧化劑的洗淨步驟。此時使用之溶劑，通常使用甲醇等醇類，隨情況而異亦可使用水洗淨。如上所述之一聯串的步驟，可採用階段式或連續式進行，自單體的聚合至形成導電膜能以一貫之操作步驟處理。所得導電性聚合物薄膜，對基底層之密著性良好，對醇類溶劑之耐性亦充分。導電層之膜厚以1〜2000nm爲佳。膜厚低於liim時，容易產生針孔等，難以形成膜，又表面電阻亦增大，防靜電性有 φ 劣化之虞；又，膜厚超過200nm時，雖表面電阻良好，但透明性、色調顯著劣化，有難以做爲防反射膜使用之情況。從透明性、色調、表面電阻之平衡的觀點而言，較佳之膜厚爲5〜300nm。又，導電層之表面電阻通常爲1〇2〜ι〇8Ω/□。其次，就形成2以上之層的方法說明如下。於此所謂「2以上之層」，亦有指同時含有金屬氧化物粒子高密度存在之層」、與「金屬氧化物粒子實質上不存在之層」的情況，或指僅由「金屬氧化物粒子高密度存在 -14- (11) 200538754 麋之層」所成的2以上之層的情況。採用圖式，就「2以上之層的各層，爲金屬氧化物粒子高密度存在之層，或金屬氧化物粒子實質上不存之層，至少一層爲金屬氧化物粒子高密度存在之層」說明如下。圖 1 A係，2以上之層爲「金屬氧化物粒子高密度存在之層1」與「金屬氧化物粒子實質上不存在之層3」的2層之情況；圖1B係，2以之層爲「金屬氧化物粒子高密度存在之層1、 H 1 a」的2層之情況；圖1 c係，2以上之層爲「金屬氧化物粒子高密度存在之層1、la」與「金屬氧化物粒子實質上不存在之層3」的3層之情況；圖1 D係，2以上之層爲「金屬氧化物粒子高密度存在之層1、1 a」與「金屬氧化物粒子實質上不存之層3」的3層之情況；圖1 E係，2以上之層爲「金屬氧化物粒子高密度存在之層1 b」與「金屬氧化物粒子實質上不存在之層3」的2層之情況。液狀硬化性樹脂組成物含有兩種以上之金屬氧化物粒 φ 子時，如圖1 B、1 C、1 D所示，「金屬氧化物粒子高密度存在之層」形成2種類以上。進而，「金屬氧化物粒子高密度存在之層」的「金屬氧化物粒子」爲至少一種，即一種或兩種以上的「金屬氧化物粒子」之意。液狀硬化性樹脂組成物含有2種以上之金屬氧化物粒子時，「金屬氧化物粒子高密度存在之層」爲由2種以上之金屬氧化物粒子所構成爲佳（例如圖1 E )。圖 1E中，「金屬氧化物粒子高密度存在之層lb」爲由粒子X與粒子Y所構成。粒子Y比「金屬氧化物粒子高密度存在之層 -15- 200538754 奢 (12) 1 b」的厚度大之故，突出於「金屬氧化物粒子實質上不存在之層3」，此突出部份亦包含於「金屬氧化物粒子高密度存在之層lb」。還有’圖1A〜1E中，「金屬氧化物粒子實質上不存在之層3」通常不存在金屬氧化物粒子，在不損及本發明之效果的範圍含有少許亦可。又，「金屬氧化物粒子高密度存在之層1、1 a、1 b」亦同樣的含有金屬氧化物粒子以外之其他 | 物質亦可。液狀硬化性樹脂組成物之塗佈法，可使用眾所周的塗佈方法，尤其可使浸漬法、塗佈機法、印刷法等各種方法。乾燥，通常以室溫〜150 °C左右加熱1〜60分鐘而實施。在不含後述之（F )活性能量線硬化性化合物爲必要成份的第一型態的液狀硬化性樹脂組成物的情況，較佳爲藉由將此等2以上之層加熱而硬化。又，在含有該（F )成份爲必要成份之第二型態的液狀硬化性樹脂組成物之情況，較 φ 佳爲藉由加熱及/或藉由照射放射線而硬化。具體的硬化條件如後述。本發明中，將單體氣相聚合，進而液狀硬化性樹脂組成物以溶液狀塗佈於各種基材，將所得塗膜乾燥/硬化，可獲得層合物。例如基材爲透明基材時，藉由在最外層設置低折射率層，可形成優越之防反射膜。防反射膜之具體的結構，通常爲依順序將基材及低折射率膜，或基材、高折射率膜及低折射率膜層合者；進而本發明中，在基材、高折射率層及低折射率層之間設置由 16- 200538754 (13) 導電層所成的防靜電層。其他，在基材高折射率層及低折射率層之間介有其他之層亦可，例如可設置防靜電層、硬塗層、中折射率層、局折射率層、低折射率層的組合等之層。圖2爲在基材1 0上依順序層合防靜電層2 0、高折射率層 40及低折射率層50之防反射膜。此防反射膜中，高折射率層40相當於金屬氧化物粒子 g 高密度存在之層，低折射率層5 0相當於金屬氧化物粒子實質上不存在之層。依本發明，可藉由氣相聚合形成防靜電層20、高折射率層40與低折射率層50可由1之塗膜形成。圖3爲在基材10上，依順序層合硬塗層30、防靜電層20 、高折射率層40及低折射率層50之防反射膜。此防反射膜中、高折射率層40相當於金屬氧化物粒子高密度存在之層、低折射率層5 0相當於金屬氧化物粒子實 φ 質上不存在之層。依本發明，可藉由氣相聚合形成防靜電層20、高折射率層40及低折射率層50可由1之塗膜形成。圖4爲在基材10上，依順序層合防靜電層20、硬塗層30 、高折射率層40及低折射率層50之防反射膜。此防反射膜中，高折射率層4 0相當於金屬氧化物粒子高密度存在之層，低折射率層50相當於金屬氧化物粒子實質上不存在之層。依本發明，可藉由氣相聚合形成防靜電層2 0、高折射 -17- 200538754 會 (14) 率層4 0及低折射率層5 0可由1之塗膜形成。圖5爲在基材1 0上，依順序層合硬塗層3 0、防靜電層2 0 、中折射率層60、高折射率層40及低折射率層50之防反射膜。此防反射膜中，高折射率層40相當於金屬氧化物粒子高密度存在之層，低折射率層5 0相當於金屬氧化物粒子實質上不存在之層。或，中折射率層60及高折射率層40的任 φ 一種均相當於金屬氧化物粒子高密度存在之層、或中折射率層60相當於金屬氧化物粒子高密度存在之層，高折射率層4 0相當於金屬氧化物粒子實質上不存在之層。依本發明，可藉由氣相聚合形成防靜電層20、中折射率層60及高折射率層40、或高折射率層40與低折射率層50 ，可由1之塗膜形成。較佳爲高折射率層40與低折射率層50 由1之塗膜形成。圖6爲在基材10上，依順序層合防靜電層20、硬塗層30 φ 、中折射率層60、高折射率層40及低折射率層50之防反射膜。此防反射膜中，高折射率層40相當於金屬氧化物粒子高密度存在之層，低折射率層50相當於金屬氧化物粒子實質上不存在之層。或，中折射率層60及高折射率層40的任一種均相當於金屬氧化物粒子高密度存在之層、或中折射率層60相當於金屬氧化物粒子高密度存在之層，高折射率層40相當於金屬氧化物粒子實質上不存在之層。依本發明，可藉由氣相聚合形成防靜電層20、中折射 -18- 200538754 % (15) 率層60與高折射率層40、或高折射率層40與低折射率層50 ，可由1之塗膜形成。較佳爲高折射率層40與低折射率層50 由1之塗膜形成。圖7爲在基材10上，依順序層合防靜電層20、中折射率層60、高折射率層40及低折射率層50之防反射膜。此防反射膜中，高折射率層40相當於金屬氧化物粒子高密度存在之層，低折射率層50相當於金屬氧化物粒子實 φ 質上不存在之層。或，中折射率層60相當於金屬氧化物粒子高密度存在之層，高折射率層40相當於金屬氧化物粒子實質上不存在之層。依本發明，可藉由氣相聚合形成防靜電層20、中折射率層60與高折射率層40、或高折射率層40低折射率50，可由1之塗膜形成。較佳爲高折射率層40與低折射率層50由1 之塗膜形成。其次，就上述之防反射膜的各層說明如下。 (1 )基材透明基材之具體例有，例如三乙醯基纖維素、聚對苯二甲酸乙二醇酯樹脂（東麗股份有限公司製，魯米拉等）、玻璃、聚碳酸酯樹脂、丙烯酸、苯乙烯樹脂、烯丙酸酯樹脂、冰片烯系樹脂（J S R股份有限公司製之阿東，日本節甕股份有限公司製之節歐內庫斯等）、甲基丙烯酸甲酯/苯乙烯共聚物樹脂、聚烯烴樹脂等各種透明塑料板或薄膜等等。較佳爲三乙醯基纖維素、聚對苯二甲酸乙二醇酯樹脂（東麗股 -19- 200538754 ^ (16) 份有限公司製之魯米拉等）、冰片烯系樹脂（JSR股份有限公司製之阿東等）。 (2 )低折射率層所謂低折射率層，係指於波長589nm的折射率爲 1.20〜1.55之層。低折射率層中所使用之材料，只要爲能獲得目標之特 p 性者沒有特別的限制，有例如含有含氟聚合物之硬化性組成物、丙烯酸單體、含氟丙烯酸單體、含環氧基化合物、含有含氧環氧基化合物等之硬化物等等。又，爲提升低折射率層之強度，配合二氧化矽微粒等亦可。 (3 )高折射率層所謂高折射率層，係指於波長589nm的折射率爲 1.50〜2.20之層〇 φ 可配合爲形成高折射率層之高折射率的無機粒子，例如金屬氧化物粒子。金屬氧化物粒子之具體例有，含銻之氧化錫（ΑΤΟ )粒子、含磷之氧化錫（ΡΤΟ )粒子、含錫之氧化銦（ΙΤΟ )粒子）、氧化鋅（ΖηΟ )粒子、含銻之氧化鋅粒子、含鋁之氧化鋅粒子、氧化鉻（Zr02 )粒子、氧化鈦（Ti02 )粒子、二氧化矽被覆之Ti 02粒子、Al203/Zr02被覆之Ti02粒子、二氧化鈽（Ce02 )粒子等等。較佳爲含銻氧化錫（ΑΤΟ )粒子、含錫氧化銦（ΙΤΟ )粒子、含鋁氧化鋅粒子、Al203/Zr02 -20- 200538754 (17) 被覆之Ti〇2粒子等。此等金屬氧化物粒子可一種單獨或兩種以上組合使用。又’咼折射率層亦可具有硬塗層或防靜電層之功能。 (4)中折射率層在將具有三種以上的折射率之層組合時，通常將於波長 5 8 9nm之折射率爲1.50〜1.90，具有比低折射率層高、比高 φ 折射率層低的折射率之層稱爲中折射率層。中折射率層之折射率較佳爲1.50〜1.80，以1.50〜1.75更佳。爲形成中折射率層，可配合高折射率之無機粒子，例如金屬氧化物粒子。金屬氧化物粒子之具體例有，含銻氧化錫（ΑΤΟ )粒子、含磷氧化錫（ΡΤΟ )粒子、含錫氧化銦（ΙΤΟ )粒子、氧化鋅（ΖηΟ )粒子、含銻氧化鋅粒子、含鋁氧化鋅粒子、氧化锆（Zr02 )粒子、氧化鈦（Ti02 )粒子、二氧化矽被覆 φ Ti02粒子、Al203/Zr02被覆Ti02粒子、二氧化鈽（Ce02 )粒子等等。較佳爲含銻氧化錫（ΑΤΟ )粒子、含錫氧化銦（ ΙΤΟ )粒子、含鋁氧化鋅粒子、氧化鉻（Zr〇2 )粒子等。此等金屬氧化物粒子可一種單獨或兩種以上組合使用。又，中折射率層亦可具有硬塗層或防靜電層之功能。藉由低折射率層與高折射率層組合可降低反射率，進而藉由將低折射率層、高折射率層、中折射率層組合可降低反射率同時能減少閃光及帶藍之色調。 -21 - (18) 200538754 ♦ (5 )硬塗層硬塗層之具體例，以由Si〇2、環氧系樹脂 '丙烯酸系樹脂、二聚氰胺系樹脂等材料所構成爲佳。又，此等樹脂中配合二氧化矽粒子亦可。硬塗層具有提局層合物之機械強度的效果。 (6 )防靜電層 •防靜電層係如上所述之氣相聚合的導電層。防靜電層可賦予層合物導電性，能防止由於靜電成之塵埃等的附黏。此等層僅形成一層亦可’或形成兩層以上相異之層亦可〇又’低、中、局折射率層之膜厚通常分別爲6〇〜I50nm ，硬塗層之膜厚通常爲1〜2 0 μιη，防靜電層之膜厚通常爲 5 〜3 Onm 〇 φ 本發明中，層合物之導電層及其他之任意連續的2以上之層採用本發明的製造方法形成；不依本發明之製造方法’層之製造方法可藉由眾所周知的塗佈與硬化、蒸鍍、濺鍍等方法製造。又’發明中，以由液狀硬化性樹脂組成物所成之層，以硬化形成具有優越光學特性與耐久性的硬化膜，尤其以加熱賦予熱經歷爲佳。當然，於常溫放置時與經歷之時間同時進行硬化反應亦能形成目標的硬化膜，但實際上加熱硬化能縮短所需時間更具效果。又，藉由添加熱酸產生劑做爲硬化 •22- 200538754 秦 (19) 催化劑’ Μ能促進硬化反應。此硬化催化劑沒有特別的限制’可使用一般尿素樹脂、三聚氰胺樹脂做爲硬化劑使用之各種酸類或其鹽類，尤其以使用銨鹽更佳。硬化反應之加熱條件可適當選擇，加熱溫度必要爲塗佈對象之基材的耐熱界限溫度以下。依本發明能以氣相聚合形成導電層之故，可製造均勻的導電層。又，能由1之塗膜形成2以上之層，可簡化層合 φ 物之製造步驟。又’藉由金屬氧化物粒子之偏在化，能提升層合物之耐擦傷性。本發明之層合物，除防反射膜以外，亦適合使用於例如透鏡、選擇穿透膜濾光片等光學用零件。其次，就本發明使用之液狀硬化性樹脂組成物，說明如下。本發明中使用之液狀硬化性樹脂組成物有，含有以下 φ 述成份（A) 、( Β ) 、( C ) 、( D ) 、（Ε-1)及（Ε-2 )爲必要成份之第一型態，與含有以此等之外尙有（F ) 爲必要成份的第二型態。 (A )含氟聚合物 (B )熱固性化合物 (C )硬化催化劑 (D)數平均粒徑爲l〇〇nm以下的金屬氧化物粒子 (E-1 ) —種或兩種以上之對（A )含氟聚合物的溶解性高之溶劑（以下稱爲「（ E-1 )快速揮發溶劑」） -23- 200538754 (20) (Ed ) —種或兩種以上之對（D )金屬氧化物粒子的分散穩定性高，且與（丨）快速揮發溶劑具有相溶性之溶劑（以下稱爲「（ E_2 )緩慢揮發溶劑」）； (F )活性能量線硬化性化合物，就此等成份說明如下。 (A)含氟聚合物 g Q氣聚合物，係分子內具有碳-氟鍵之聚合物、氟含量爲3 0重量％以上。含氟聚合物只要爲分子中具有羥基之含氟聚合物（以下稱爲「含羥基含氟聚合物」、或簡稱「含氟聚合物」），均適合使用。於此氟含量係藉由茜素配位劑法測定之値。較佳之含有羥基的含氟聚合物之例有，含有10〜50莫耳 %之來自含羥基的單體之結構單位所成，在主鏈中具有聚矽氧烷段節者等等。含有羥基之含氟聚合物，較佳爲氟含量在 φ 30重量％以上，以40〜60重量％更佳·藉由凝膠滲透色譜法，以四氫呋喃爲展開溶劑時之聚苯乙烯換算的數平均分子量爲 5000以上，以1000 0〜500000者更佳。如此之含有羥基的含氟聚合物，係主鏈上具有下述一般式（1 )表示之聚矽氧烷段節的烯烴系聚合物。含有羥基之含氟聚合物中’該聚矽氧烷段節之比例通常爲0.1〜20莫耳％ ⑴ R1 —Si"〇_ R2 -24- (21) 200538754 式中，R 1及R2爲相同或相異均可之氫原子、院基、鹵化院基或芳基。該含氟聚合物可藉由將（a )含氟烯烴化合物[以下稱「（a)成份」]、（b)可與此（a)成份共聚合之含有經基的單體化合物[以下稱「（b)成份」]、及（c)含有氮基之聚矽氧烷化合物[以下稱「（ c )成份」]、以及因應需 φ 求之（d )反應性乳化劑[以下稱「（ d )成份」]、及/或（ e)可與該（a)成份共聚合之（b)成份以外的單體化合物反應而得。 (a )成份之含氟烯烴化合物爲，具有至少一個聚合性之不飽和雙鍵、與至少一個氟原子之化合物，其具體例有例如（1)四氟乙烯、六氟丙烯、3，3,3-三氟丙烯等氟烯烴類； (2)全氟（烷基乙烯基醚）類或者全氟（烷氧基烷基乙烯基醚類）；（3)全氟（甲基乙烯基醚）、全氟（乙基乙烯 φ 基醚）、全氟（丙基乙烯基醚）、全氟（丁基乙烯基醚）、全集（異丁基乙儲基醚）等全氟（院基乙稀基醚）類； (4)全氟（丙氧基丙基乙烯基醚）等全氟（烷氧基烷基乙烯基醚）類；其他等等。此等化合物可單獨使用或兩種以上倂用。其中以六氟丙烯、全氟（烷基乙烯基醚）或全氟 (烷氧基烷基乙烯基醚）較佳，進而以將此等組合使用更佳。 (b )成份之含有羥基的單體化合物有例如（丨）2 —羥基乙基乙烯基醚、3 -羥基丙基乙烯基醚、2 -羥基丙基乙烯 -25- (22) 200538754 基醚、4-羥基丁基乙烯基醚、3-羥基丁基乙烯基醚、5-羥基戊基乙烯基醚、6-羥基己基乙烯基醚等含有羥基之乙烯基醚類；（2 ) 2-羥基乙基烯丙基醚、4-羥基丁基烯丙基醚、丙三醇單烯丙基醚等含有羥基之烯丙基醚類；（3)烯丙醇；（4)羥基乙基（甲基）丙烯酸酯；其他；等等。此等化合物可單獨使用，或兩種以上倂用。以含有羥基之烷基乙烯基醚類較佳。 (c )成份之含有偶氮基的聚矽氧烷，係含有一 N = N-所示之容易熱裂解的偶氮基，同時具有該一般式（1)所示之聚矽氧烷段節的化合物，例如藉由特開平6-93 1 00號公報上記載之方法製造而得者。（c)成份之具體例有下述一般式 (2 )表示的化合物等。 HO·200538754 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for manufacturing a laminate and a laminate obtained therefrom. In particular, it relates to a method for producing a laminate in which two or more layers can be formed from a coating film of one. [Previous technology] p. At present, with the development of multiple media, various developments in various display devices can be observed. Among various display devices, especially for outdoor users whose focus is on portable use, the improvement of visibility is becoming more and more important; those who require it can also watch more easily in large display devices, but this issue remains a technical issue and remains unresolved. In the past, one of the methods for improving the visibility of a display device is to coat an anti-reflection film made of a low-refractive-index material on the base material of the display device. There are methods for forming an anti-reflection film, such as forming fluorine by evaporation. Method for thin film of compound φ. However, in recent years, a technique for forming an anti-reflection film has been sought for a low-cost, large-scale display device centered on a liquid crystal display device. However, when an evaporation method is used, it is difficult to form an efficient and uniform anti-reflection film on a large-area substrate, and it is difficult to reduce costs because a vacuum device is necessary. Because of this situation, we have begun to review the method of dissolving a fluorine-containing polymer with a low refractive index in an organic solvent to prepare a liquid composition, and then coating it on the substrate surface to form an anti-reflection film. For example, there is a method of coating fluorine on the substrate surface. Proposed alkylated silane (for example, refer to Patent Documents 1 and 2). In addition, there is a proposal for a method for coating a fluorine-based polymer having a specific structure of 200538754 (2) (for example, refer to Patent Document 3) ° On the other hand, there is also a method of using a laminate of a conductive polymer in an antistatic layer. An anti-reflection film (for example, refer to Patent Document 4). Patent Document 1: Japanese Patent Application Laid-Open No. 6 1 -40 845 Patent Document 2: Japanese Patent Application No. 6-9 8 703 Patent Patent 3: Japanese Patent Application Laid-Open No. 6-1 15 023 Patent Document 4: Japanese Patent Application Laid-Open No. 2003 -3 The conventional anti-reflection films of the 00267 gazette are mostly a laminate of a conductive layer (antistatic layer), a layer with a different refractive index, a hard coat layer, and the like formed on a substrate. In the conventional manufacturing method, the step of coating each layer on the substrate is repeated. The present invention is based on the situation described above, and an object thereof is to provide a method for producing a laminate capable of forming two or more layers in one coating step, and a laminate obtained therefrom. Another object of the present invention is to provide a method for producing a laminate for forming a conductive layer with high efficiency and a laminate obtained by the method. Furthermore, another object of the present invention is to provide a method for producing a laminate having excellent adhesiveness to a substrate, high abrasion resistance, and good antireflection effect, and a laminate obtained by using the same. [Disclosure of the invention] [Disclosure of the invention] According to the present invention, the following method for producing a laminate and a laminate obtained therefrom can be provided. [1] A method for producing a laminate, which is a method for producing a laminate having a substrate, a conductive layer and a multilayer structure thereon 200538754 (3); characterized in that at least one kind is selected from pyrrole by Monomers of thiophene, furan, selenophene, 3,4-ethylenedioxythiophene and their derivatives are polymerized in a gas phase to form a conductive layer; containing the following components (A), (B ), (C), (D), (E-1), and (E_2) are applied as a liquid hardening resin composition to form a coating film; p is formed by evaporating the solvent from the coating film of 1 to form 2 The above layers; (liquid curable resin composition) (A) fluoropolymer (B) thermosetting compound (C) curing catalyst (D)-one or two or more metal oxides having an average particle diameter of 100 nm or less Particles (hereinafter referred to as "(D) metal oxide particles") φ (E-1)-one or two or more types of solvents with high solubility for (A) fluoropolymers (hereinafter referred to as "(E -1) fast volatilizing solvent ") (E-2) — one or two or more pairs of (D) metal oxide particles have high dispersion stability and are compatible with (E- 1) Fast-evaporating solvent A solvent with a compatible phase (hereinafter referred to as "(E-2) slow-evaporating solvent"); and, the relative evaporation rate of the (E-1) fast-evaporating solvent is greater than (E-2) the slow-evaporating solvent Relative evaporation rate. [2] A method for producing a laminate, which is a method for producing a laminate having a substrate, a conductive layer thereon, and a multilayer structure; characterized in that at least one selected from (4) 200538754 Pyrrole, thiophene, furan, selenophene, 3,4-ethylenedioxythiophene, and a group of these monomers are subjected to gas-phase polymerization to form a conductive layer; the following components (A), ( B), (C), (0), (E-1), (E-2), and (F) liquid hardenable resin compositions are applied to form a coating film; The coating film evaporates to form a layer of 2 or more; (liquid curable resin composition) (A) fluoropolymer (B) thermosetting compound (C) curing catalyst (D) — one or two or more average particle diameters Metal oxide particles below 100 nm (hereinafter referred to as "(D) metal oxide particles") (E-1)-one or two or more pairs of (A) fluorinated polymers which are highly soluble in φ Hereinafter referred to as "(E-1) fast volatilizing solvent") (E-2)-one or two or more pairs of (D) metal oxide particles having high dispersion stability, and (E-1) fast volatilizing solvent A solvent having a compatible phase (hereinafter referred to as "(E-2) slow volatilizing solvent"); (F) active energy ray hardening compound; and (E-1) fast volatilizing solvent The relative evaporation rate is greater than (E-2) the relative evaporation rate of slowly volatile solvents. [3] The method for producing a laminate according to the above [1] or [2], wherein the (A) fluorine-containing polymer is a fluorine-containing polymer j having a hydroxyl group in a molecule. 200538754 1 (5) [4] The method for producing a laminate according to the above [2], wherein the solid content of the liquid curable resin composition is 100% by mass, and the component (B) is contained in an amount of 5 to 80. quality%. [5] The method for producing a laminate according to the above [1], wherein the (C) curing catalyst is a thermal acid generator. [6] The method for producing a laminate as described in the above [2], wherein the solid content of the liquid hardening resin composition is 100% by mass, and the (C) component is contained in | 0. 1-20% by mass. [7] The method for producing a laminate as described in [1] above, wherein the refractive index of the (D) metal oxide particles is 1. above 50. [8] The method for producing a laminate according to the above [1], wherein the (D) metal oxide particles are one or two selected from titanium oxide, chromium oxide, antimony-containing tin oxide, and phosphorus-containing Particles consisting mainly of metal oxides of tin oxide, tin-containing indium oxide, aluminum oxide, hafnium oxide, zinc oxide, zinc oxide containing aluminum, tin oxide, zinc oxide containing antimony, and zinc oxide containing indium. φ [9] The method for producing a laminate according to the above [1], wherein the (D) metal oxide particles are particles containing titanium oxide as a main component. [10] The method for producing a laminate according to the above [2], wherein the (D) metal oxide particles are selected from one or two or more kinds selected from titanium oxide, chromium oxide, antimony-containing tin oxide, and tin-containing Indium oxide, silicon dioxide, aluminum oxide, hafnium oxide, zinc oxide, aluminum oxide-containing zinc oxide, tin oxide, antimony-containing zinc oxide, and indium-containing zinc oxide metal oxide-based particles. [1 1] The method for producing a laminate according to the above [1] or [2], wherein the (D) metal oxide particle is a metal oxide particle having a multilayer structure-9- 200538754 v (6) [12 ] The method for producing a laminate according to the above [2], wherein the (D) metal oxide particles are connected to an organic compound having a polymerizable unsaturated group. [13] The method for producing a laminate according to the above [1] or [2], wherein the (E-1) rapidly volatile solvent is one or two or more kinds of dispersion stability of (D) metal oxide particles Low solvent; (E-2) Slow volatilizing solvent is one or two or more solvents with low solubility in (A) fluoropolymer. [14] The method for producing a laminate according to the above [1] or [2], wherein each layer of the two or more layers is a layer in which metal oxide particles are present at a high density, or metal oxide particles are not present in a solid state. At least one layer is a layer in which metal oxide particles exist at a high density. [15] The method for producing a laminate according to the above [1] or [2], wherein the two or more layers are two layers. [16] The method for producing a laminate according to the above [1], wherein the two or more layers are further hardened by heating. [17] The method for producing a laminate according to the above [2], wherein the two or more layers are further hardened by heating and / or irradiating radiation. [18] The method for producing a laminate according to the above [1] or [2], wherein the laminate is an optical component. [19] As described in the above [1] or [2] g of the laminated method for producing a laminate, the Ganzhong laminate is an anti-reflection film. [20] The method for producing a laminate according to the above [15], wherein the layer is -10- 200538754 v (7) The compound is on a substrate, and at least an antistatic layer is laminated in order from the side near the substrate. Anti-reflection film of high refractive index layer and low refractive index layer; The conductive layer is an antistatic layer; The two layers carried by [1 5] are formed by the cylindrical refractive index layer and the low refractive index layer. [21] Such as [20] The method for producing a laminate according to the above [20], wherein the refractive index of the low refractive index layer at 5 89 nm is 1. 20 ~ 1. 55; the refractive index of the high refractive index layer at g 589nm is 1. 50 ~ 2. 20, higher refractive index than the low refractive index layer. [22] The method for producing a laminate according to the above [15], wherein the laminate is on a substrate, and at least an antistatic layer, a medium refractive index layer, and a high refractive layer are laminated in order from the side near the substrate. The anti-reflection film of the refractive index layer and the low refractive index layer; the conductive layer is an antistatic layer; the two layers described in [1 5] are made of a high refractive index layer and a low refractive index layer. [23] As described above [22] ] The manufacturing method of the laminate described in which the refractive index of the low-refractive φ emissivity layer is 1 at 589 nm. 20 ~ 1. 55; the refractive index of the medium refractive index layer is 1. 50 ~ 1. 90, higher than the refractive index of the low refractive index layer; the refractive index of the high refractive index layer at 5 89nm is 1. 51 ~ 2. 20, higher than the refractive index of the medium refractive index layer. [24] The method for producing a laminate according to the above [20], wherein a hard coat layer is further formed on the substrate. [25] A laminate characterized by being produced by the method for producing a laminate as described in [1] or [2] above. The method for producing the laminate of the present invention can be obtained by coating the composition 1-11-200538754 v. The coating film of (8) is formed into two or more layers, which can simplify the manufacturing process of a laminate having a multilayer structure. The method for producing a laminate of the present invention can form a conductive layer with good efficiency. Therefore, the method for manufacturing the laminate of the present invention is extremely suitable for forming optical materials such as antireflection films, lenses, and selective transmission film filters. Furthermore, the laminate of the present invention has a high fluorine content and is very suitable for use in coatings, weather-resistant films, coatings, and the like for substrates requiring weather resistance. In addition, by providing the g low-refractive index layer in the outermost layer (the layer furthest from the substrate), this laminate can provide a good antireflection effect. Further, according to the present invention, a laminate having excellent adhesion to a substrate and high abrasion resistance can be obtained. Therefore, the laminate of the present invention is very suitable for use as an anti-reflection film, and its visibility can be improved by using it in various display devices. [The best form for implementing the invention] The present invention is a method for manufacturing a laminate having a substrate, a conductive layer and a multilayer structure thereon, and a laminate obtained therefrom. Specifically, φ, the manufacturing method of the present invention is to form a conductive layer by vapor-phase polymerization of a monomer on a base material or a layer formed on the base material (hereinafter referred to as a base layer). The liquid hardenable resin composition as described later is applied in a large amount, and the solvent is evaporated by the composition applied therefrom (hereinafter also referred to as "drying") to form a layer of 2 or more. In addition, the solvent may not be left in a completely solvent-free state after drying, and the solvent may be left in a range in which the characteristics as a cured film can be obtained. It is preferable that after the conductive layer is formed on the base layer, a layer of 2 or more is formed thereon. Further, in the present invention, two or more layers can be formed from a coating film of one or more times. First, the gas phase polymerization of the conductive layer will be described as follows. -12- 200538754. 〇) The conductive layer is formed by gas phase polymerization, and can be produced by, for example, the method described in Japanese Patent No. 82105, and specifically, can be formed by polymerization. That is, the base layer is coated with an oxidant in units of several µm, and the polymer is brought into contact with the oxidant coating film in a gaseous state to be polymerized to form a conductive polymer film on the base material. In this case, in order to improve the adhesion, polymers such as polyurethane, polyvinyl chloride, polyvinyl alcohol, and methylcellulose can also be used. φ In the present invention, a monomer gas is formed on the base layer coated with an oxidizing agent to form a conductive layer made of a conductive polymer, and the reaction at this time is preferably 0 to 1 40 ° C. The polymerization method will be described in more detail as follows, and the present invention is defined by the method. Specifically, in the first stage, the surface of the base layer is coated with a bit of 0. 5 to 10 weight ° /. Oxidant. The oxidizing agent may be selected from a group of compounds such as CuCl2, iron (III) tosylate, iron perchlorate (FeCl2 and Cu (C104) 2 · 6H20). The φ member at this time depends on the type of the base layer used. For example, an organic solvent selected from the group consisting of methanol alcohol, ethyl cellosolve, ethanol, cyclohexane, acetone, ethyl acetate, and methyl ethyl ketone can be used. These can be used alone or in combination of two or more, such as methanol, 2-butanol Organic conversion composed of ethyl and cellosolve: 2: 1, 6: 2: 2, 5: 3: 2, etc. Mix and use in proportion. The coated base layer is dried by hot air below 80 ° C in consideration of the decomposition of the oxidant. Secondly, in the second stage, on the base layer coated with an oxidizing agent, the ratio of thiopyridine, thiophene, sulfan, selenophene, 3,4-ethylenedioxythiophene ^ 2003- conductive, so that the formation agent The temperature of polymerization with the prime and formazan phases can be used in combination with an unlimited number of μm III), solvent strips: 2-butane, toluene, I agent with 7 oxidant dryer and will choose its derivative-13- (10) 200538754 Monomers of living organisms are gasified and contacted, and the polymerization reaction is performed on the surface of the base layer. At this time, the method of vaporizing the monomer includes a method of distilling the monomer at 0 to 14 ° C in a closed chamber, and a method of chemical vapor deposition (CVD). At this time, it is better to adjust the temperature conditions and reaction time. The polymerization reaction is performed in the range of 10 seconds to 40 minutes. Generally, it changes according to the type of monomer, and the film thickness and surface resistance 値 can reach the target 値. Secondly, in the third stage, after the polymerization is completed, a washing step is performed to remove unreacted φ monomers and oxidants. As the solvent used at this time, alcohols such as methanol are usually used, and they may be washed with water depending on the situation. One of the steps described above can be performed in a stepwise or continuous manner. From the polymerization of the monomers to the formation of a conductive film, it can be processed in a consistent operation step. The obtained conductive polymer film had good adhesion to the base layer and sufficient resistance to alcohol solvents. The film thickness of the conductive layer is preferably 1 to 2000 nm. When the film thickness is less than liim, it is easy to produce pinholes, etc., and it is difficult to form a film. The surface resistance is also increased, and the antistatic property may be degraded. When the film thickness exceeds 200 nm, although the surface resistance is good, the transparency, The color tone is significantly deteriorated, and it may be difficult to use it as an antireflection film. From the viewpoint of the balance of transparency, hue, and surface resistance, a preferable film thickness is 5 to 300 nm. In addition, the surface resistance of the conductive layer is usually from 10 to 80 Ω / □. Next, a method of forming two or more layers is described below. The "layer above 2" as used herein also refers to a layer containing both metal oxide particles with a high density, and a layer that does not substantially exist with metal oxide particles, or only refers to a layer consisting of "metal oxide There are cases where the particle density is higher than -14- (11) 200538754. Using the diagram, the description of "each layer of 2 or more layers is a layer with a high density of metal oxide particles, or a layer with substantially no metal oxide particles, and at least one layer is a layer with high density of metal oxide particles" as follows. Fig. 1 A series, the layers above 2 are the two layers of "Layer 1 with high density of metal oxide particles" and "Layer 3 with substantially no metal oxide particles"; Fig. 1B, layer 2 and above It is the case of two layers of "layer 1, metal oxide particles with high density 1, H 1 a"; Fig. 1c, 2 or more layers are "layer 1, metal oxide particles with high density, 1" and "metal" In the case of 3 layers of "layer 3 where oxide particles do not exist substantially"; Fig. 1 D series, layers above 2 are "layers 1 and 1 a where metal oxide particles are present at a high density" and "metal oxide particles are substantially The case of 3 layers that do not exist "; Figure 1 E series, the layers above 2 are the" layer 1 b where metal oxide particles exist at a high density "and the" layer 3 where metal oxide particles do not exist substantially " In the case of 2 floors. When the liquid curable resin composition contains two or more kinds of metal oxide particles φ, as shown in Figs. 1B, 1C, and 1D, "a layer in which metal oxide particles exist at a high density" forms two or more types. Furthermore, the "metal oxide particles" of the "layer where metal oxide particles exist at a high density" means at least one, that is, one or two or more "metal oxide particles". When the liquid curable resin composition contains two or more kinds of metal oxide particles, the "layer having high density of metal oxide particles" is preferably composed of two or more kinds of metal oxide particles (for example, Fig. 1E). In FIG. 1E, "the layer lb in which metal oxide particles exist at a high density" is composed of particles X and Y. Particle Y is thicker than "Layer 3 with high density of metal oxide particles-15- 200538754 Luxury (12) 1 b", which protrudes from "Layer 3 with essentially no metal oxide particles", this protruding part It is also included in "the layer lb in which metal oxide particles exist at a high density". Further, in Figs. 1A to 1E, "Layer 3 in which metal oxide particles are substantially absent" does not normally have metal oxide particles, and may contain a small amount as long as the effect of the present invention is not impaired. In addition, the "layers 1, 1 a, and 1 b in which metal oxide particles exist at a high density" may also contain other substances other than metal oxide particles. As the method for applying the liquid curable resin composition, various coating methods can be used, and in particular, various methods such as a dipping method, a coater method, and a printing method can be used. Drying is usually carried out by heating at room temperature to 150 ° C for 1 to 60 minutes. When the first-type liquid curable resin composition containing no (F) active energy ray-curable compound as an essential component described later is not contained, it is preferred that the two or more layers be cured by heating. In the case where the liquid-type curable resin composition containing the second type of the (F) component is an essential component, it is more preferable than φ to be hardened by heating and / or by irradiation of radiation. Specific hardening conditions are described later. In the present invention, a monomer is vapor-phase polymerized, and a liquid curable resin composition is applied as a solution to various substrates, and the obtained coating film is dried / cured to obtain a laminate. For example, when the base material is a transparent base material, an excellent anti-reflection film can be formed by providing a low refractive index layer on the outermost layer. The specific structure of the anti-reflection film is usually a substrate and a low refractive index film, or a substrate, a high refractive index film, and a low refractive index layer. An antistatic layer made of 16-200538754 (13) conductive layer is provided between the layer and the low refractive index layer. In addition, other layers may be interposed between the high refractive index layer and the low refractive index layer of the substrate. For example, an antistatic layer, a hard coat layer, a medium refractive index layer, a local refractive index layer, and a low refractive index layer Layers of composition and so on. FIG. 2 is an anti-reflection film in which an antistatic layer 20, a high refractive index layer 40, and a low refractive index layer 50 are laminated on a substrate 10 in this order. In this anti-reflection film, the high refractive index layer 40 corresponds to a layer in which the metal oxide particles g exist at a high density, and the low refractive index layer 50 corresponds to a layer in which the metal oxide particles do not actually exist. According to the present invention, the antistatic layer 20, the high-refractive index layer 40, and the low-refractive index layer 50 can be formed by a coating film of 1 by gas phase polymerization. FIG. 3 is an anti-reflection film in which a hard coat layer 30, an antistatic layer 20, a high refractive index layer 40, and a low refractive index layer 50 are laminated on a substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which the metal oxide particles do not exist substantially. According to the present invention, the antistatic layer 20, the high-refractive index layer 40, and the low-refractive index layer 50 can be formed by a coating film of 1 by vapor-phase polymerization. FIG. 4 is an anti-reflection film in which the antistatic layer 20, the hard coat layer 30, the high refractive index layer 40, and the low refractive index layer 50 are laminated on the substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles do not substantially exist. According to the present invention, the antistatic layer 20, the high refractive index -17- 200538754 can be formed by gas phase polymerization (14) the rate layer 40 and the low refractive index layer 50 can be formed by a coating film of 1. Fig. 5 is an anti-reflection film in which a hard coat layer 30, an antistatic layer 20, a middle refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated on a substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles do not actually exist. Or, any one of the medium refractive index layer 60 and the high refractive index layer 40 corresponds to a layer in which metal oxide particles exist at a high density, or the medium refractive index layer 60 corresponds to a layer in which metal oxide particles exist at a high density and has a high refractive index. The rate layer 40 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the antistatic layer 20, the intermediate refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index layer 50 can be formed by vapor phase polymerization, and can be formed of a coating film of 1. The high refractive index layer 40 and the low refractive index layer 50 are preferably formed of a coating film of 1. Fig. 6 is an antireflection film in which an antistatic layer 20, a hard coat layer 30φ, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated on the substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles are present at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles do not actually exist. Or, any one of the medium refractive index layer 60 and the high refractive index layer 40 corresponds to a layer with a high density of metal oxide particles, or the medium refractive index layer 60 corresponds to a layer with a high density of metal oxide particles, and has a high refractive index. The layer 40 corresponds to a layer in which metal oxide particles are not substantially present. According to the present invention, the antistatic layer 20, intermediate refractive -18-200538754% (15) rate layer 60 and high refractive index layer 40, or high refractive index layer 40 and low refractive index layer 50 can be formed by gas phase polymerization. A coating film of 1 was formed. The high refractive index layer 40 and the low refractive index layer 50 are preferably formed of a coating film of 1. Fig. 7 shows an anti-reflection film in which an antistatic layer 20, a medium refractive index layer 60, a high refractive index layer 40, and a low refractive index layer 50 are laminated on a substrate 10 in this order. In this antireflection film, the high refractive index layer 40 corresponds to a layer in which metal oxide particles exist at a high density, and the low refractive index layer 50 corresponds to a layer in which metal oxide particles do not actually exist. Alternatively, the middle refractive index layer 60 corresponds to a layer in which metal oxide particles exist at a high density, and the high refractive index layer 40 corresponds to a layer in which metal oxide particles do not substantially exist. According to the present invention, the antistatic layer 20, the intermediate refractive index layer 60 and the high refractive index layer 40, or the high refractive index layer 40 and the low refractive index 50 can be formed by vapor phase polymerization, and can be formed of a coating film of 1. The high refractive index layer 40 and the low refractive index layer 50 are preferably formed of a coating film of 1. Next, each layer of the above-mentioned antireflection film is described as follows. (1) Specific examples of the transparent substrate include, for example, triethyl cellulose, polyethylene terephthalate resin (manufactured by Toray Corporation, Lumila, etc.), glass, and polycarbonate. Resin, acrylic acid, styrene resin, allyl ester resin, norbornene-based resin (Ato made by JSR Co., Ltd., Kaneko Co., Ltd. made by Japan Jiefang Co., Ltd., etc.), methyl methacrylate / benzene Various transparent plastic plates or films such as ethylene copolymer resin and polyolefin resin. Preferred are triethylfluorinated cellulose, polyethylene terephthalate resin (Toray 19-19200538754 ^ (16) parts of Lumila, etc.), norbornene resin (JSR shares Adon, etc.). (2) Low-refractive index layer The so-called low-refractive index layer refers to a refractive index of 1 at a wavelength of 589 nm. 20 ~ 1. 55 floors. The material used in the low-refractive-index layer is not particularly limited as long as it can obtain the desired properties, and there are, for example, a curable composition containing a fluorine-containing polymer, an acrylic monomer, a fluorine-containing acrylic monomer, and a ring-containing material. Oxygen compounds, hardened products containing oxygen-containing epoxy compounds, etc. In order to increase the strength of the low-refractive-index layer, silica particles and the like may be added. (3) High refractive index layer The so-called high refractive index layer refers to a refractive index of 1 at a wavelength of 589 nm. 50 ~ 2. The layer 20 of 0 can be used as a high refractive index inorganic particle forming a high refractive index layer, such as a metal oxide particle. Specific examples of the metal oxide particles include antimony-containing tin oxide (ATO) particles, phosphorus-containing tin oxide (PTO) particles, tin-containing indium oxide (ITO) particles), zinc oxide (ZηO) particles, and antimony-containing Zinc oxide particles, aluminum-containing zinc oxide particles, chromium oxide (Zr02) particles, titanium oxide (Ti02) particles, silicon dioxide-coated Ti 02 particles, Al203 / Zr02-coated Ti02 particles, thorium dioxide (Ce02) particles, etc. Wait. Preferred are antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, aluminum-containing zinc oxide particles, Al203 / Zr02 -20- 200538754 (17) coated Ti02 particles, and the like. These metal oxide particles may be used alone or in combination of two or more. The "咼" refractive index layer may also function as a hard coat layer or an antistatic layer. (4) Medium refractive index layer When a layer having three or more refractive indexes is combined, the refractive index at a wavelength of 5 8 9 nm is usually 1. 50 ~ 1. 90. A layer having a higher refractive index than a low refractive index layer and a lower refractive index than a φ refractive index layer is referred to as a medium refractive index layer. The refractive index of the middle refractive index layer is preferably 1. 50 ~ 1. 80 to 1. 50 ~ 1. 75 is better. In order to form the medium refractive index layer, inorganic particles having a high refractive index, such as metal oxide particles, can be blended. Specific examples of the metal oxide particles include antimony-containing tin oxide (ATO) particles, phosphorus-containing tin oxide (PTO) particles, tin-containing indium oxide (ΙΤΟ) particles, zinc oxide (ZηΟ) particles, antimony-containing zinc oxide particles, Zinc alumina particles, zirconia (Zr02) particles, titanium oxide (Ti02) particles, silicon dioxide-coated φ Ti02 particles, Al203 / Zr02-coated Ti02 particles, hafnium dioxide (Ce02) particles, and the like. Preferred are antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, aluminum-containing zinc oxide particles, chromium oxide (ZrO2) particles, and the like. These metal oxide particles may be used singly or in combination of two or more. The middle refractive index layer may also function as a hard coat layer or an antistatic layer. The combination of a low-refractive index layer and a high-refractive index layer can reduce the reflectance, and the combination of a low-refractive index layer, a high-refractive index layer, and a middle-refractive index layer can reduce the reflectivity and reduce the flicker and bluish tint. -21-(18) 200538754 ♦ (5) Hard coating layer A specific example of the hard coating layer is preferably composed of a material such as Si02, epoxy resin, acrylic resin, melamine resin, and the like. It is also possible to mix silica particles with these resins. The hard coat layer has the effect of improving the mechanical strength of the laminate. (6) Antistatic layer • The antistatic layer is a gas-phase polymerized conductive layer as described above. The antistatic layer imparts conductivity to the laminate and prevents adhesion of dust and the like caused by static electricity. These layers may form only one layer, or two or more different layers may be formed. Also, the film thicknesses of the low, medium, and local refractive index layers are usually 60 to 50 nm, and the film thickness of the hard coating layer is usually 1 ~ 2 0 μιη, the film thickness of the antistatic layer is usually 5 ~ 3 Onm 0φ In the present invention, the conductive layer of the laminate and any other continuous layers of 2 or more are formed by the manufacturing method of the present invention; The manufacturing method of the invention can be manufactured by a well-known method such as coating and hardening, vapor deposition, sputtering, or the like. In the invention, a layer made of a liquid curable resin composition is cured to form a cured film having excellent optical characteristics and durability, and it is particularly preferable to impart heat history by heating. Of course, when the hardening reaction is carried out at the same time as the elapsed time at room temperature, the target hardened film can be formed, but in fact, heat hardening can shorten the required time and is more effective. In addition, the addition of a thermal acid generator as hardening • 22- 200538754 Qin (19) Catalyst ‘M can promote the hardening reaction. The hardening catalyst is not particularly limited. Various kinds of acids or salts thereof used in general urea resins and melamine resins as hardeners can be used, and especially ammonium salts are more preferable. The heating conditions for the curing reaction can be appropriately selected, and the heating temperature must be below the heat-resistant limit temperature of the substrate to be coated. Since a conductive layer can be formed by gas phase polymerization according to the present invention, a uniform conductive layer can be manufactured. In addition, two or more layers can be formed from the coating film of one, and the manufacturing steps of laminating φ can be simplified. Furthermore, by the bias of the metal oxide particles, the scratch resistance of the laminate can be improved. In addition to the antireflection film, the laminate of the present invention is also suitable for use in optical parts such as lenses and selective transmission film filters. Next, the liquid curable resin composition used in the present invention will be described below. The liquid curable resin composition used in the present invention includes the following components (A), (B), (C), (D), (E-1), and (E-2) as the necessary components. The first form is similar to the second form containing (F) as an essential component. (A) Fluoropolymer (B) Thermosetting compound (C) Hardening catalyst (D) Number of metal oxide particles (E-1) having an average particle diameter of 100 nm or less-One or two or more pairs (A ) Solvents with high solubility of fluoropolymers (hereinafter referred to as "(E-1) fast volatilizing solvents") -23- 200538754 (20) (Ed)-one or two or more kinds of (D) metal oxides Particles with high dispersion stability and solvents compatible with (丨) fast volatilizing solvents (hereinafter referred to as "(E_2) slow volatilizing solvents"); (F) active energy ray hardening compounds. These components are described below. (A) Fluoropolymer g Q polymer is a polymer having a carbon-fluorine bond in the molecule, and the fluorine content is 30% by weight or more. As long as the fluorine-containing polymer is a fluorine-containing polymer having a hydroxyl group in the molecule (hereinafter referred to as "hydroxy-containing fluorine-containing polymer", or simply "fluoro-containing polymer"), it is suitable for use. Here, the fluorine content is determined by the method of alizarin complexing agent. Examples of preferred fluoropolymers containing a hydroxyl group are those containing 10 to 50 mole% of structural units derived from a hydroxyl-containing monomer, those having a polysiloxane segment in the main chain, and the like. The fluorine-containing polymer containing a hydroxyl group, preferably having a fluorine content of φ 30% by weight or more, more preferably 40 to 60% by weight. • Polystyrene-equivalent number by gel permeation chromatography using tetrahydrofuran as a developing solvent The average molecular weight is above 5,000, and more preferably between 100,000 and 500,000. Such a hydroxyl-containing fluoropolymer is an olefin-based polymer having a polysiloxane segment represented by the following general formula (1) in the main chain. The ratio of the polysiloxane segment in the fluoropolymer containing a hydroxyl group is usually 0. 1 to 20 mole% ⑴ R1 —Si " 〇_ R2 -24- (21) 200538754 In the formula, R 1 and R 2 are the same or different hydrogen atom, radical, halogenated radical or aryl. This fluoropolymer can be obtained by (a) a fluorinated olefin compound [hereinafter referred to as "(a) component"], (b) a monomer compound containing a radical that can be copolymerized with this (a) component [hereinafter referred to as "(B) ingredients"], and (c) nitrogen-containing polysiloxane compounds [hereinafter referred to as "(c) ingredients"], and (d) reactive emulsifiers [hereinafter referred to as "( d) ingredients "], and / or (e) can be obtained by reacting with monomer compounds other than (b) ingredients copolymerized with the (a) ingredients. (a) The fluorine-containing olefin compound of the component is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom, and specific examples thereof include (1) tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-Fluoroolefins such as trifluoropropylene; (2) Perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether); (3) Perfluoro (methyl vinyl ether) , Perfluoro (ethyl vinyl φ-based ether), Perfluoro (propyl vinyl ether), Perfluoro (butyl vinyl ether), Complete Collection (isobutyl ethyl ether) (4) Perfluoro (propoxypropyl vinyl ether) and other perfluoro (alkoxyalkyl vinyl ether); others and so on. These compounds may be used alone or in combination of two or more. Among them, hexafluoropropylene, perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) is preferred, and further combinations of these are more preferred. (b) The hydroxy-containing monomer compound of the component includes, for example, (丨) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl-25- (22) 200538754 based ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether and other vinyl ethers containing hydroxyl groups; (2) 2-hydroxyethyl Allyl ethers containing hydroxyl groups such as allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether; (3) allyl alcohol; (4) hydroxyethyl (methyl ) Acrylate; others; etc. These compounds may be used alone or in combination of two or more. Hydroxy-containing alkyl vinyl ethers are preferred. (c) The siloxane-containing polysiloxane containing the component contains an azo group represented by N = N-, which is easy to be thermally cracked, and has a polysiloxane segment shown by the general formula (1). The compound obtained is produced, for example, by the method described in JP-A-6-93100. Specific examples of the component (c) include compounds represented by the following general formula (2). HO ·

ch3 ch3 ch3ch3 OC(CH2)2C-N=N-C-(CH2)2CONH(CH2)3Si(〇Si)y(CH2)3NH^Hch3 ch3 ch3ch3 OC (CH2) 2C-N = N-C- (CH2) 2CONH (CH2) 3Si (〇Si) y (CH2) 3NH ^ H

CNCN

CN CH3CH3CN CH3CH3

⑵ 式中，y=10〜500，z=l 〜50。該（a)成份、（b)成份、及（c)成份之較佳組合爲，例如（1 )氟烯烴/含羥基之烷基乙烯基醚/聚二甲基矽氧烷單位、（2 )氟烯烴/全氟（烷基乙烯基醚）/含羥基之烷基乙烯基醚/聚二甲基矽氧烷單位、（3)氟烯烴/全氟（烷氧基烷基乙烯基醚）/含羥基之烷基乙烯基醚/聚二甲基矽氧烷單位、（4 )氟烯烴/全氟（烷基乙烯基醚）/含有羥 -26- 200538754 (23) 基之烷基乙烯基醚/聚二甲基矽氧烷單位、（5 )氟烯烴/全氟（烷氧基烷基乙烯基醚）/含有羥基之烷基乙烯基醚/聚二甲基矽氧烷單位。此含氟聚合物中，來自（a )成份之結構單位較佳爲 20〜70莫耳％，以25〜65莫耳％更佳，以30〜60莫耳％最適合〇來自（a )成份之結構單位的比例低於2 0莫耳％時，容 φ 易使所得含氟聚合物中之氟含量過少，以致所得液狀硬化性樹脂組成物之硬化物，難以成爲折射率充分低者。另一方面，來自（a )成份之結構單位的比例超過7 0，所得含氟聚合物對有機溶劑之溶解性顯著下降，同時所得液狀硬化性樹脂組成物之透明性及對基材的密著性降低。含氟聚合物中，來自（b )成份之結構單位較佳爲 1 〇〜5 0莫耳％。更佳爲下限値在1 3莫耳％以上，以2 1莫耳％以上最適合；又，更佳爲上限値在4 5莫耳％以下，以3 5莫 φ 耳％以下最適合。藉由使用依所定量含有如此之（b )成份的含氟聚合物’構成液狀硬化性樹脂組成物，其硬化物可實現良好的耐擦傷性與塵埃拭去性。另外，來自（b ) 成份之結構單位的比例低於1 0莫耳％時，含氟聚合物對有機溶劑之溶解性劣化’超過5 0莫耳％時，由液狀硬化性樹脂組成物所成之硬化物，透明性及低反射率之光學特性惡化。 (c )成份之含有偶氮基的聚矽氧烷化合物，其本身爲熱游離基產生劑’在獲得含氟聚合物之聚合反應中具有做 •27- (24) 200538754 爲聚合引發劑的作用，可與其他之游離基引發劑倂用。含氟聚合物中來自（c )成份之結構單位的比例，以一般式 (1 )表示之/段節較佳爲0.1〜20莫耳％，以0.1〜15莫耳％更佳，以0·1〜10莫耳％更適合，以0.1〜5莫耳％之比例最理想。一般式（1 )所示之聚矽氧烷段節的比例超過20莫耳％時，所得含氟聚合物之透明性劣化；又，做爲塗佈劑使用時，於塗佈之際容易排拒。該（a )〜（c )成份以外，以另使用反應性乳化劑爲 (d )成份之單體成份爲佳。藉由採用此（d )成份，使用含氟聚合物爲塗佈劑時，可獲得良好的塗佈性及平坦化性。此反應性乳化劑，尤其以使用非離子性反應性乳化劑爲佳。非離子性反應性乳化劑之具體例，有例如下述一般式 (3)或一般式（4)表示之化合物等。式 In the formula, y = 10 ~ 500 and z = l ~ 50. The preferred combination of the (a) component, (b) component, and (c) component is, for example, (1) fluoroolefin / hydroxyl-containing alkyl vinyl ether / polydimethylsiloxane unit, (2) Fluoroolefin / Perfluoro (alkyl vinyl ether) / Hydroxy-containing alkyl vinyl ether / Polydimethylsiloxane unit, (3) Fluoroolefin / Perfluoro (alkoxyalkyl vinyl ether) / Hydroxyl-containing alkyl vinyl ether / polydimethylsiloxane unit, (4) fluoroolefin / perfluoro (alkyl vinyl ether) / alkyl vinyl ether containing hydroxyl-26- 200538754 (23) group / Polydimethylsiloxane unit, (5) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / alkyl vinyl ether containing a hydroxyl group / polydimethylsiloxane unit. In this fluoropolymer, the structural unit derived from the component (a) is preferably 20 to 70 mole%, more preferably 25 to 65 mole%, and 30 to 60 mole% is most suitable. When the proportion of the structural unit is less than 20 mol%, the capacity φ tends to make the fluorine content in the obtained fluoropolymer too small, so that the hardened product of the obtained liquid curable resin composition is difficult to become a sufficiently low refractive index. On the other hand, if the proportion of the structural unit derived from the component (a) exceeds 70, the solubility of the obtained fluoropolymer in organic solvents is significantly reduced, and at the same time, the transparency of the obtained liquid hardening resin composition and the density of the substrate Reduced sex. In the fluoropolymer, the structural unit derived from the component (b) is preferably 10 to 50 mole%. More preferably, the lower limit is more than 13 mol%, and more preferably, 21 mol% or more. Furthermore, the upper limit is more preferably 45 mol% or less, and the most suitable is 35 mol% or less. By using the fluorinated polymer 'containing the (b) component in a predetermined amount to constitute a liquid curable resin composition, the cured product can achieve good scratch resistance and dust wiping property. In addition, when the proportion of the structural unit derived from the component (b) is less than 10 mol%, the solubility of the fluoropolymer to the organic solvent is deteriorated, and when it exceeds 50 mol%, it is caused by the liquid hardening resin composition. The resulting hardened material is degraded in optical properties such as transparency and low reflectance. (c) A polysiloxane compound containing an azo group, which is a thermal radical generator itself, has a role as a polymerization initiator in obtaining a fluoropolymer. 27- (24) 200538754 acts as a polymerization initiator. Can be used with other free radical initiators. The proportion of the structural unit derived from the component (c) in the fluoropolymer is preferably 0.1 to 20 mole% per segment expressed by the general formula (1), more preferably 0.1 to 15 mole%, and 0 · 1 to 10 mole% is more suitable, and a ratio of 0.1 to 5 mole% is most desirable. When the proportion of the polysiloxane segment represented by the general formula (1) exceeds 20 mol%, the transparency of the obtained fluoropolymer is deteriorated; and when it is used as a coating agent, it is easy to be discharged during coating. Reject. In addition to the components (a) to (c), a monomer component using a reactive emulsifier as the component (d) is preferred. By using this (d) component, when a fluoropolymer is used as a coating agent, good coatability and flatness can be obtained. This reactive emulsifier is particularly preferably a nonionic reactive emulsifier. Specific examples of the nonionic reactive emulsifier include a compound represented by the following general formula (3) or general formula (4).

H2n+1CnV=x 〇H2〇(CH2)mCH=CH2 ^ OCH2CH(OCH2CH2)s〇H ⑶ 式中，η爲1〜20 ; m及S爲重覆單位之數，m = 0〜4、 s = 3 〜5 0 〇 CH20(CH2)mCH=CH2 R3-〇CH2—C—CH(OCH2CH2)sOH Η ⑷ 式中，m及s爲與一般式（3)相同者；r3爲直鏈狀或支鏈狀均可之烷基，較佳爲碳數1〜40之烷基。 -28 - 200538754 參 (25) 含氟聚合物中’來自（d )成份之結構單位的比例，較佳爲〇〜1 〇莫耳％，以0 · 1〜5莫耳％更佳，以0.1〜1莫耳。/〇最適合。此比例超過1 0莫耳％時所得液狀硬化性樹脂組成物帶有黏著性之故難以處理，做爲塗佈劑使用時耐濕性下降〇 (e )成份之，可與（a )成份共聚合的（b )成份以外之單體化合物有：（1)甲基乙烯基醚、乙基乙烯基醚 φ 、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚、異丁基乙烯基醚、叔丁基乙烯基醚、正戊基乙烯基醚、正己基乙烯基醚、正辛基乙烯基醚、正（十二烷）基乙烯基醚、2-乙基己基乙烯基醚、環己基乙烯基醚等烷基乙烯基醚或環烷基乙烯基醚類；（2)乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、三甲基乙酸乙烯酯、己酸乙烯酯、巴薩吉克酸乙烯酯、硬脂酸乙烯酯等羧酸乙烯酯類；（3)(甲基 )丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丁 φ 酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸2-甲氧基乙基酯、（甲基）丙烯酸2-乙氧基乙基酯、（甲基）丙烯酸2_正丙氧基乙基酯等（甲基）丙烯酸甲酯類；（4)(甲基）丙烯酸、丁烯酸、順丁烯二酸、反丁烯二烯、衣康酸等含羧基之單體化合物等不含羥基者。較佳爲烷基乙烯基醚。含氟聚合物中，來（自）成份之結構單位的比例，較佳爲〇〜70莫耳％ ’以5〜35莫耳％更佳。此比例超過70莫耳％時’所得液狀硬化性樹脂組成物帶有黏著性之故難以處理，做爲塗佈劑使用時，耐濕性下降。 -29- 200538754 (26) 含有（D )成份時，（a )成份、（b )成份、（c )成份、（d )成份及（e )成份之較佳組合，如下述之說明。 (1)氟烯烴/含羥基之乙烯基醚/聚二甲基矽氧烷單位/ 非離子性反應性乳化劑/烷基乙烯基醚、（2 )氟烯烴/全氟 (烷基乙烯基醚）/含羥基之乙烯基醚/聚二甲基矽氧烷單位/ 非離子性反應性乳化劑/烷基乙烯基醚、（3 )氟烯烴/全氟 (烷氧基烷基乙烯基醚）/含羥基之乙烯基醚/聚二甲基矽氧 φ 烷單位/非離子性反應性乳化劑/烷基乙烯基醚、（4 )氟烯烴/全氟（烷基乙烯基醚）/含羥基之乙烯基醚/聚二甲基矽氧烷單位/非離子性反應性乳化劑/烷基乙烯基醚、（5 )氟烯烴/全氟（烷氧基烷基乙烯基醚）/含羥基之乙烯基醚/聚二甲基矽氧烷單位/非離子性反應性乳化劑/烷基乙烯基醚。可與（c )成份倂用之游離基聚合引發劑有例如：（1 )過氧化氫乙醯、過氧化二苯甲醯等二醯基過氧化物類；（ 2) 丁酮氧化物、環己酮過氧化物等酮過氧化物類；（3 )過 φ 氧化氫、叔丁基過氧化氫、異丙苯基過氧化氫等過氧化氫類 ;(4 )二叔丁基過氧化物、二異丙苯基過氧化物、二月桂醯過氧化物等二烷基過氧化物類；（5 )叔丁基過氧乙酸酯、叔丁基過氧三甲基乙酸酯等過氧酯類；（6 )偶氮雙異丁腈、偶氮雙異戊腈等偶氮系化合物類；（7 )過硫酸銨、過硫酸鈉、過硫酸鉀等過硫酸鹽類；其他，等等。該游離基聚合引發劑以外之具體例有，例如全氟乙基碘化物、全氟丙基碘化物、全氟丁基碘化物、（全氟丁基）乙基碘化物、全氟己基碘化物、2-(全氟己基）乙基碘化物、 •30- (27) 200538754 全氟庚基碘化物、全氟辛基碘化物、2-(全氟辛基）乙基碘化物、全氟癸基碘化物、2 -(全氟癸基）乙基碘化物、七氟-2-碘丙烷、全氟-3-甲基丁基碘化物、全氟-5-甲基己基碘化物、2-(全氟-5-甲基己基）乙基碘化物、全氟-7-甲基辛基碘化物、2-(全氟-7-甲基辛基）乙基碘化物、全氟-9-甲基癸基碘化物、2-(全氟-9-甲基癸基）乙基碘化物、 2,2,3,3-四氟丙基碘化物、1H，1H，5H-八氟戊基碘化物、 1H，1H，7H-(十二）氟庚基碘化物、四氟-1，2-二碘乙烷、八氟-1,4-二碘丁烷、（十二）氟-6-二碘己烷等含碘之氟化合物等等。含碘之氟化合物可單獨使用，或與該有機過氧化物、偶氮系化合物、或過硫酸鹽倂用。製造含氟聚合物之聚合方式，使用游離基聚合引發劑，可採用乳化聚合法、懸浮聚合法、塊狀聚合法或溶液聚合法之任一種；聚合操作可自分批式、半連續式或連續式之操作等適當選擇。爲獲得含氟聚合物之聚合反應，以在使用溶劑之溶劑系進行爲佳。較佳爲之有機溶劑有’例如（1 )乙酸乙酯、乙酸丁酯、乙酸異丙酯、乙酸異丁酯、乙酸溶纖劑等酯類； (2)丙酮、甲乙酮、甲異丁酮、環己酮等酮類；（3)四氫呋喃、二噁烷等環狀醚類；（4 ) N，N-二甲基甲醯胺、N，N_ 二甲基乙醯胺等醯胺類；（5)甲苯、二甲苯等芳香族烴類 ;其他，等等。進而，因應需求’亦可將醇類、脂肪族烴類等混合使用。如上所述而得之含氟聚合物’其於聚合反應所得之反應 -31 - (28) 200538754 溶液亦可直接做爲液狀硬化性樹脂組成物使用’對聚合反應溶液亦可施行適當之後處理。此後處理有例如’將聚合反應溶液滴加於由醇類所成之對該含氟聚合物不溶解的溶劑中，使該含氟聚合物凝固之一般精製方法的代表之再沉澱處理 ;接著，藉由將所得之固狀共聚物溶解於溶劑，調製成含氟聚合物之溶液。又，將自聚合反應溶液去除殘餘單體之物，直接使用爲含氟聚合物之溶液亦可。 _ 不含該（F )成份爲必要成份之第一型態的液狀硬化性樹脂組成物之固形份100重量％中，（A)含氟聚合物之配合比例通常爲7〜70重量％，藉由較佳之10〜50重量％，可使硬化膜之透明性優越。含該（F )成份爲必要成份之第二型態的液狀硬化性樹脂組成物之固形份1〇〇重量7。中，（A)含氟聚合物之配合比例通常爲5〜80重量％的範圍，較佳爲10〜80重量％，以15〜80 重量％之範圍更適合。在此範圍外時，有損防反射效果、塗 φ 膜強度下降，極不適合。 (B)熱固性化合物 (B)熱固性化合物係藉由加熱等而聚合，對液狀硬化性樹脂組成物賦予硬化性之成份。熱固性化合物有，例如各種胺基化合物、季戊四醇、聚苯酚、二醇等各種含羥基化合物，其他等等。可使用爲熱固性化合物之胺基化合物，係含有可與（A )含氟聚合物中存在之羥基反應的胺基、例如羥基烷基胺基 -32- (29) 200538754 及烷氧基烷基胺基之任一方或雙方合計2個以上的化合物；具體的有例如三聚氰胺系化合物、尿素系化合物、苯并鳥糞胺系化合物、甘脲系化合物等等。三聚氰胺化合物’一般而言係具有在三嗪環上連結氮原子之骨架的化合物；具體的有三聚氰胺、烷基化三聚氰胺、羥甲基三聚氰胺、烷氧基化甲基三聚氰胺等等，分子中以具有羥甲基及烷氧基化甲基之任一方或雙方合計2個以上者爲 φ 佳。具體而言，以三聚氰胺與甲醛在鹼性條件下反應而得之羥甲基化三聚氰胺、烷氧基化甲基三聚氰胺、或此等之衍生物爲佳；尤其從液狀硬化性樹脂組成物獲得良好的儲存穩定性之觀點、及獲得良好的反應性之觀點而言，以烷氧基化甲基三聚氰胺更爲適合。使用爲熱固性化合物之羥甲基化三聚氰胺及烷氧基化甲基三聚氰胺，沒有特別的限制，例如可使用以文獻「塑膠材料講座[8]尿素•三聚氰胺樹脂」（曰刊工業新聞公司出版）上記載之方法而得的各種樹脂狀物生醛衍糖之化素基尿甲化羥基之甲酯羥內聚酸有醛外糖以有素具尿、除素物尿合化化基系甲素化尿基 ’ 氧又烷的物酸內酯及烷氧基化甲基糖醛酸內酯等等。然後，尿素衍生物等化合物，可以使用上述文獻中記載之各種樹脂狀物。不含該（F )成份爲必要成份之第一型態的液狀硬化性樹脂組成物之固形份1〇〇重量％中，所含熱固性化合物之配合比例通常爲3〜7 0重量°/〇，較佳爲3〜5 0重量％，以5〜3 0重量0/〇更佳。熱固性化合物之使用量過少時，藉由所得液狀硬化 -33- (30) 200538754 性樹脂組成物形成之薄膜的耐久性有不充分之情況；於超出 3〜70重量％之範圍以外時，在與含氟聚合物之反應中難以避免膠化，硬化物有脆化之情況。含該（F )成份爲必要成份之第二型態的液狀硬化性樹脂組成物之固形份100重量％中，所含熱固性化合物之使用量爲5〜80重量％，較佳爲5〜70重量％，以10〜50重量％之範圍更適合。熱固性化合物之使用量過少時，藉由所得液狀硬 φ 化性樹脂組成物形成之薄膜的耐久性有不充分之情況，超過 80重量％時，在與含氟聚合物之反應中難以避免膠化，硬化物有脆化之情況。液狀硬化性樹脂組成物中，含有熱固性化合物僅與該 (A )含氟聚合物混合者亦可，含有含氟聚合物與熱固性化合物之全部反應的反應生成物、或僅將此等之一部份反應的狀態者亦可。含氟聚合物與熱固性化合物之反應，藉由例如在將含 φ 氟聚合物溶解於有機溶劑之溶液中，添加熱固性化合物，以適當之時間加熱、攪拌使反應系均勻化同時進行即可。此反應之加熱溫度較佳爲30〜150 t：之範圍，以50〜120 °C 之範圍更適合。加熱溫度低於3 0 °C時反應之進行極爲緩慢，超過1 5 0 °C時，除目標之反應外，由於熱固性化合物之羥甲基或烷氧基化甲基相互間的反應而引起交聯反應生成凝膠，極不適合·反應之進行，藉由紅外線光譜分析定量羥甲基或烷氧基化甲基之方法、或者藉由測定以再沉澱法將溶解之聚合物回收的增加量，能進行定量的確認。 -34 - (31) 200538754 又，在（A)含氟聚合物與（B )熱固性化合物之反應中，有機溶劑以使用例如與含氟聚合物之製造中所使用的有機溶劑相同者爲佳。本發明中，將如此而得之含氟聚合物與熱固性化合物的反應溶液，直接使用爲液狀硬化性樹脂組成物之溶液亦可，因應需求配合各種添加劑使用亦可 B ( C)硬化催化劑本發明所使用之硬化催化劑有例如熱酸產生劑等。熱酸產生劑係，在將該液狀硬化性樹脂組成物之薄膜等加熱硬化時，能促進硬化反應之物質，又能使其加熱條件改善爲更穩和之物質。此熱酸產生劑沒有特別的限制，可採用一般之尿素樹脂、三聚氰胺樹脂等使用爲硬化劑的各種酸類或其鹽類。具體的有例如各種脂肪族磺酸與其鹽、檸檬酸、乙酸、馬來酸等各種脂肪族羧酸與其鹽、安息香酸、 φ 苯二甲酸等各種芳香族羧酸與其鹽、烷基苯磺酸與其銨鹽、各種金屬鹽、磷酸及有機之磷酸酯等等。不含該（F )成份爲必要成份之第一型態的液狀硬化性樹脂組成物之固形份1 00重量％中，所含熱酸產生劑之使用比例通常爲0.01〜10重量％，較佳爲0.1〜5重量％。此比例過大時，液狀硬化性樹脂組成物之儲存穩定性劣化，極不適合。含該（F )成份爲必要成份之第二型態的液狀硬化性樹脂組成物之固形份1 00重量％中，所含硬化催化劑之使用量 -35 - (32) 200538754 通常爲0.1〜20重量％之範圍，較佳爲0.1〜10重量％，以3〜8重量％之範圍更適合。硬化催化劑之使用量過少時，不能獲得充分之機械強度及耐藥品性，甚爲不佳。此比例過大時，催化劑在硬化膜中做爲增塑劑而作用，有損塗膜之透明性，不能獲得充分的機械強度，非常不適合。液狀硬化性樹脂組成物中，藉由使該（B )熱固性化合物及（C )硬化催化劑之添加量控制於該特定範圍，能改善 φ 將液狀硬化性樹脂組成物硬化而得之硬化膜的特性，尤其是耐擦傷性及耐藥品性。 (D)數平均粒徑爲lOOnm以下之金屬氧化物粒子金屬氧化物粒子之數平均粒徑爲lOOnm以下。數平均粒徑超過lOOnm時，將金屬氧化物粒子均勻分散有難以進行之情況。又，金屬氧化物粒子容易沉降，有儲存穩定性不足的情況。進而所得硬化膜之透明性下降，濁度（霧値）上升。 φ 數平均粒徑以10〜80爲佳，以20〜50nm更適合。還有，「數平均粒徑」係以電子顯微鏡法測定之數平均粒徑，金屬氧化物粒子凝聚時爲一次粒徑，金屬氧化物粒子非爲球形時（例如針狀ΑΤΟ等），爲長徑（長度）與短徑（寬度）之平均。又粒子形狀爲棒狀（指縱橫比爲1 以上1 0以下之形狀而言）時，以短徑爲粒子徑。金屬氧化物粒子較佳爲使用一種或兩種以上選自氧化鈦、氧化锆、含銻氧化錫、含磷氧化錫、含錫氧化銦、二氧化矽、氧化鋁、氧化鈽、氧化鋅、含鋁氧化鋅、氧化錫 -36- 200538754 ^ (33) 、含銻氧化鋅及含銦氧化鋅所成群之金屬氧化物爲主成份的粒子。於此’亦可使用具有以該金屬氧化物以外之該一種或兩種以上的金屬氧化物被覆於金屬氧化物粒子之多層結構的金屬氧化物粒子。具有多層結構之金屬氧化物粒子的具體例有二氧化矽被覆氧化鈦粒子、氧化鋁被覆氧化鈦粒子、氧化鋁被覆氧化鈦粒子、氧化锆被覆氧化鈦粒子、氧化 0 鋁及氧化锆被覆氧化鈦粒子等等。如此之金屬氧化物粒子中，以二氧化矽爲主成份之粒子，以氧化鈦爲主成份之粒子、或氧化鋁及氧化锆被覆氧化鈦粒子更佳。藉由使用具有多層結構之金屬氧化物粒子，可抑制氧化鈦之光催化劑活性，能抑止硬化物的分解。其結果可獲得高折射率且耐光性優越之硬化膜。又，藉由使用含銻氧化錫粒子（ΑΤΟ )等，可賦予硬化膜以防靜電性，此情況如後所述，ΑΤΟ粒子偏在化之故 φ ，以較少量之添加量能使有效的防靜電性與良好的透明性兩立。以二氧化矽爲主成份之粒子，可使用眾所周知者；又，其形狀爲球狀時並不限定於通常之膠體二氧化矽、中空粒子、多孔粒子、核•殻型粒子等均可。不限定於球狀、不定形之粒子亦可。以藉由動態光散射法或電子顯微鏡觀察求得之數平均粒徑爲1〜l〇〇nm、固形份爲10〜40重量％、 pH爲2.0〜6.5之膠體二氧化矽爲佳。以二氧化矽爲主成份之粒子的市售品有，例如日產化 -37- (34) 200538754 學工業股份有限公司製之斯諾鐵庫斯〇 (以動態光散射法求得之數平均粒徑爲7nm、固形份20重量％、pH2.7 )、斯諾鐵庫斯OL (以動態光散射法求得之數平均粒徑爲1 5nm、固形份20重量％、pH2.5 )等等。又，分散劑以水或有機溶劑爲佳。有機溶劑有甲醇、異丙醇、乙二醇、丁醇、乙二醇單丙醚等醇類；甲乙酮、甲異丁酮等酮類；甲苯、二甲苯等芳香族烴類；二甲基甲醯胺、 B 二甲基乙醯胺、N-甲基吡咯烷等醯胺類；乙酸乙酯、乙酸丁酯、r-丁內酯等酯類；四氫呋喃、1，4-二噁烷等醚類等有機溶劑，其中以醇類及酮類爲佳。此等有機溶劑可單獨或兩種以上混合做爲分散劑使用。金屬氧化物粒子，藉由使用在波長5 89nm之折射率爲 1.5以上之金屬氧化物粒子，可提高構成具有兩層以上之層的硬化膜之金屬氧化物粒子爲高密度存在之層的折射率之故，適合使用爲防反射層。爲如此之目的，二氧化矽（折 φ 射率約1.45 )粒子不適合。金屬氧化物粒子爲提高以高密度存在之層的折射率時 ’金屬氧化物粒子較佳爲使用一種或兩種以上選自氧化鈦、氧化鉻、含銻氧化錫、含磷氧化錫、含錫氧化銦、氧化鋁、氧化鈽、氧化鋅、含鋁氧化鋅、氧化錫、含銻氧化鋅及含銦氧化鋅所成群之金屬氧化物爲主成份的粒子。以氧化鈦爲主成份之粒子，可使用眾所周知者；又’ 其形狀爲中空粒子、多孔粒子、核•殼型粒子等均可。又，不限定於球狀、棒狀（指縱橫爲1以上1 0以下之形狀而言） -38- 200538754 (35) 、或不定形之粒子均可，以棒狀爲佳。以電子顯微鏡法求得之數平均粒徑以1〜l〇〇nm爲佳。以氧化鈦爲主成份之粒子的市售品有，例如鐵依卡股份有限公司製，及西愛化成股份有限公司製之產品。又，氧化鈦之分散劑可使用與上述二氧化矽粒子所使用之相同者。又，本發明所使用之（D )金屬氧化物粒子，係將下述 φ 具有聚合性不飽基之有機化合物（Ab )、或含有分子中具有1以上之烷基的水解性矽化合物或其水解者等（以下稱爲「有機化合物（Ac )」）反應之方法而得。但是於此反應中，除共價鍵之外亦包含物理吸附等非共價鍵。此時，不與有機化合物（Ab )連結之金屬氧化物粒子稱爲「金屬氧化物粒子（Aa )」，與有機化合物（Ab )或（Ac )連結之粒子稱爲反應性粒子（Dab)或（Dac)。藉由金屬氧化物粒子（Ab)爲與具有聚合性不飽基之 φ 有機化合物（Ab )或（Ac )連結的反應性粒子（Dab )或 (Dac)，在（D )金屬氧化物粒子成份中具有聚合性不飽基，可與其他成份形成堅固之共價鍵，能提升所得硬化膜之耐擦傷性。 (1 )在具有聚合性不飽基之有機化合物（Ab )上的化學潤飾本發明中所使用之有機化合物（Ab )係具有聚合性不飽基的化合物；進而，以含有下述式（5)表示之基的有 -39- 200538754 (36) 機化合物爲佳。又，以含有[-〇-C( = 0)-NH-]基爲佳，進而以含有[-〇-C( = S)-NH-]基及[-S-C( = 0)-NH-]基之至少一種者爲佳。又，此有機化合物（Ab )以分子內具有矽烷醇基之化合物、或經水解生成矽烷醇基之化合物爲佳1。 Η —U—C一Ν— ⑸H2n + 1CnV = x 〇H2〇 (CH2) mCH = CH2 ^ OCH2CH (OCH2CH2) s〇H ⑶ where η is 1 ~ 20; m and S are the number of repeating units, m = 0 ~ 4, s = 3 to 5 0 〇CH20 (CH2) mCH = CH2 R3-〇CH2-C—CH (OCH2CH2) sOH Η ⑷ where m and s are the same as the general formula (3); r3 is linear or branched Any alkyl group is preferred, and an alkyl group having 1 to 40 carbon atoms is preferred. -28-200538754 (25) The proportion of the structural unit derived from (d) component in the fluoropolymer, preferably 0 to 10 mole%, more preferably 0.1 to 5 mole%, to 0.1 ~ 1 mole. / 〇 is most suitable. When the ratio exceeds 10 mol%, the obtained liquid hardening resin composition has adhesiveness and is difficult to handle. As a coating agent, the moisture resistance decreases when it is used. (E) The component can be used with the (a) component. The monomer compounds other than the copolymerized (b) component are: (1) methyl vinyl ether, ethyl vinyl ether φ, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether , Isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethyl Alkyl vinyl ethers or cycloalkyl vinyl ethers such as hexyl vinyl ether, cyclohexyl vinyl ether; (2) vinyl acetate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, Vinyl acid carboxylates such as vinyl acid esters, vinyl acetate, vinyl stearate; (3) methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl φ (meth) acrylate , Isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethyl (meth) acrylate (Meth) acrylic acid methyl esters, 2-n-propoxyethyl (meth) acrylate, etc .; (4) (meth) acrylic acid, butenoic acid, maleic acid, transbutyl Carboxyl-containing monomer compounds such as diene and itaconic acid do not contain hydroxyl groups. Alkyl vinyl ether is preferred. In the fluoropolymer, the proportion of the structural unit derived from the (self) component is more preferably 0 to 70 mol% and more preferably 5 to 35 mol%. When the ratio exceeds 70 mol%, the obtained liquid curable resin composition is difficult to handle because it has adhesiveness, and when used as a coating agent, the moisture resistance is reduced. -29- 200538754 (26) When containing (D) component, the preferred combination of (a) component, (b) component, (c) component, (d) component and (e) component is as described below. (1) fluoroolefin / hydroxyl-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (2) fluoroolefin / perfluoro (alkyl vinyl ether) ) / Hydroxy-containing vinyl ether / Polydimethylsiloxane unit / Nonionic reactive emulsifier / Alkyl vinyl ether, (3) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / Hydroxy-containing vinyl ether / Polydimethylsiloxane φ alkane unit / Nonionic reactive emulsifier / Alkyl vinyl ether, (4) fluoroolefin / Perfluoro (alkyl vinyl ether) / Hydroxy Vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier / alkyl vinyl ether, (5) fluoroolefin / perfluoro (alkoxyalkyl vinyl ether) / hydroxyl-containing Vinyl ether / polydimethylsiloxane unit / non-ionic reactive emulsifier / alkyl vinyl ether. The free radical polymerization initiators that can be used with the component (c) include, for example: (1) difluorenyl peroxides such as acetamidine hydrogen peroxide and dibenzoyl peroxide; (2) methyl ethyl ketone oxide, cyclic Ketone peroxides such as hexanone peroxide; (3) Hydrogen peroxides such as φ hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide; (4) di-tert-butyl peroxide , Dicumyl peroxide, dilauroyl peroxide, and other dialkyl peroxides; (5) tert-butyl peroxyacetate, t-butylperoxytrimethylacetate, etc. Oxyesters; (6) azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile; (7) persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; etc. Wait. Specific examples other than the radical polymerization initiator include perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, and perfluorohexyl iodide , 2- (perfluorohexyl) ethyl iodide, • 30- (27) 200538754 Perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecane Iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (Perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9- Methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5H-octafluoropentyl Iodide, 1H, 1H, 7H- (twelve) fluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane, (twelve) fluoro-6 -Iodine-containing fluorine compounds such as diiodohexane and the like. The iodine-containing fluorine compound may be used alone or in combination with the organic peroxide, azo-based compound, or persulfate. The polymerization method for manufacturing fluoropolymers uses free-radical polymerization initiators, which can adopt any of emulsification polymerization, suspension polymerization, block polymerization, or solution polymerization; the polymerization operation can be self-batch, semi-continuous or continuous The operation of the formula is appropriately selected. In order to obtain the polymerization reaction of the fluoropolymer, it is preferable to perform it in a solvent system using a solvent. Preferred organic solvents include, for example, (1) ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate and other esters; (2) acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone; (3) Cyclic ethers such as tetrahydrofuran, dioxane; (4) Amines such as N, N-dimethylformamide, N, N-dimethylacetamide; 5) Aromatic hydrocarbons such as toluene and xylene; others, and so on. Furthermore, alcohols, aliphatic hydrocarbons, and the like may be used in combination as required. The fluorinated polymer obtained as described above, and its reaction in the polymerization reaction -31-(28) 200538754 The solution can also be directly used as a liquid hardening resin composition. The polymerization reaction solution can also be subjected to appropriate post-treatment . The post-treatment is, for example, 're-precipitation treatment, which is representative of a general purification method in which the polymerization reaction solution is added dropwise to an insoluble solvent of the fluoropolymer made of alcohol to solidify the fluoropolymer; then, The obtained solid copolymer was dissolved in a solvent to prepare a fluoropolymer solution. In addition, it is also possible to use a solution containing a fluoropolymer as it is to remove residual monomers from the polymerization reaction solution. _ Of the solid content of the first type of liquid curable resin composition that does not contain the (F) component as an essential component, 100% by weight of the solid content of the (A) fluoropolymer is usually 7 to 70% by weight. By preferably 10 to 50% by weight, the transparency of the cured film can be made excellent. The solid content of the second type of liquid sclerosing resin composition containing the (F) component as an essential component is 100 wt. The compounding ratio of (A) the fluoropolymer is usually in the range of 5 to 80% by weight, preferably 10 to 80% by weight, and more preferably in the range of 15 to 80% by weight. Outside this range, the anti-reflection effect is impaired, and the strength of the coating film decreases, which is extremely unsuitable. (B) Thermosetting compound (B) A thermosetting compound is a component which is polymerized by heating or the like to impart a curability to a liquid curable resin composition. The thermosetting compounds include, for example, various amine-based compounds, pentaerythritol, polyphenol, diol, and various hydroxyl-containing compounds, among others. Amino compounds which can be used as thermosetting compounds, are those containing amine groups which can react with hydroxyl groups present in (A) fluoropolymers, such as hydroxyalkylamino groups -32- (29) 200538754 and alkoxyalkylamines Either one or both of the groups are combined with more than two compounds; specific examples include melamine-based compounds, urea-based compounds, benzoguanosine-based compounds, glycoluril-based compounds, and the like. The melamine compound is generally a compound having a skeleton connected to a nitrogen atom on a triazine ring; specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, etc. One or both of the methylol group and the alkoxylated methyl group are preferably φ in total. Specifically, a methylolated melamine, an alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine with formaldehyde under alkaline conditions is preferred; especially obtained from a liquid hardening resin composition From the viewpoint of good storage stability and from the viewpoint of obtaining good reactivity, alkoxylated methylmelamine is more suitable. There are no particular restrictions on the use of methylolated melamine and alkoxylated methylmelamine as thermosetting compounds. For example, it can be used in the document "Lectures on Plastic Materials [8] Urea · Melamine Resin" (published by Japan Industrial News) Various resins obtained by the method described in the aldehyde-derived glycoside-based urinary methylated hydroxy methyl esters of hydroxy internal polyacids have aldoses and urinary compounds, and uremic-chemical compounds based on urea The urethane's oxandanes are acid lactones and alkoxylated methyluronic acid lactones. As the compound such as a urea derivative, various resins described in the aforementioned literatures can be used. The solid content of the first type of liquid curable resin composition, which does not contain the (F) component as an essential component, is 100% by weight, and the mixing ratio of the thermosetting compound is usually 3 to 70% by weight. It is preferably 3 to 50% by weight, and more preferably 5 to 30% by weight. When the amount of the thermosetting compound is too small, the durability of the film formed from the obtained liquid-cured -33- (30) 200538754 sexual resin composition may be insufficient; when it exceeds the range of 3 to 70% by weight, It is difficult to avoid gelation in the reaction with fluoropolymer, and the hardened product may become brittle. The second-type liquid curable resin composition containing the (F) component as an essential component has a solid content of 100% by weight, and the used amount of the thermosetting compound is 5 to 80% by weight, preferably 5 to 70%. The weight% is more preferably in the range of 10 to 50 weight%. When the amount of the thermosetting compound is too small, the durability of the film formed by the obtained liquid hard phi resin composition may be insufficient. When it exceeds 80% by weight, it is difficult to avoid glue in the reaction with the fluoropolymer. The hardened material may become brittle. The liquid curable resin composition may contain a thermosetting compound only mixed with the (A) fluoropolymer, and may include a reaction product of all reactions between the fluoropolymer and the thermosetting compound, or only one of these. Partial response is also possible. The reaction between the fluoropolymer and the thermosetting compound can be performed simultaneously by, for example, adding a thermosetting compound to a solution containing a φ fluoropolymer in an organic solvent, and heating and stirring at an appropriate time to homogenize the reaction system. The heating temperature for this reaction is preferably in the range of 30 to 150 t :, more preferably in the range of 50 to 120 ° C. When the heating temperature is lower than 30 ° C, the reaction progresses very slowly. When it exceeds 150 ° C, in addition to the target reaction, the reaction is caused by the reaction of the methylol or alkoxylated methyl groups of the thermosetting compound. It is extremely unsuitable for the reaction to form a gel. The method of quantifying methylol or alkoxylated methyl by infrared spectroscopy, or measuring the increase in the amount of recovered polymer by reprecipitation, Quantitative confirmation is possible. -34-(31) 200538754 In the reaction between (A) the fluoropolymer and (B) the thermosetting compound, the organic solvent is preferably the same as the organic solvent used in the production of the fluoropolymer. In the present invention, the reaction solution of the fluoropolymer and the thermosetting compound thus obtained may be directly used as a solution of a liquid hardening resin composition, and various additives may be used in accordance with the requirements. B (C) Hardening catalyst Examples of the hardening catalyst used in the present invention include a thermal acid generator. The thermal acid generator is a substance which can accelerate the curing reaction when the liquid film of the curable resin composition is heated and cured, and can improve the heating conditions to a more stable substance. This thermal acid generator is not particularly limited, and various acids or salts thereof used as a hardener such as general urea resins and melamine resins can be used. Specific examples include various aliphatic sulfonic acids and their salts, various aliphatic carboxylic acids and their salts such as citric acid, acetic acid, and maleic acid, various aromatic carboxylic acids and their salts, and alkylbenzenesulfonic acids such as benzoic acid and φ phthalic acid. With its ammonium salts, various metal salts, phosphoric acid and organic phosphate esters, etc. The solid acid content of the first type of liquid curable resin composition not containing the (F) component as an essential component is 100% by weight, and the usage ratio of the thermal acid generator is usually 0.01 to 10% by weight, It is preferably 0.1 to 5% by weight. When the ratio is too large, the storage stability of the liquid curable resin composition is deteriorated, which is extremely unsuitable. The solid content of the second type of liquid curable resin composition containing the (F) component as an essential component is 100% by weight, and the amount of the hardening catalyst used is -35-(32) 200538754, usually 0.1 to 20 The range of weight% is preferably 0.1 to 10% by weight, and a range of 3 to 8% by weight is more suitable. When the amount of the hardening catalyst used is too small, sufficient mechanical strength and chemical resistance cannot be obtained, which is extremely poor. When the ratio is too large, the catalyst acts as a plasticizer in the hardened film, which impairs the transparency of the coating film, fails to obtain sufficient mechanical strength, and is very unsuitable. In the liquid curable resin composition, by controlling the addition amounts of the (B) thermosetting compound and (C) curing catalyst to the specific range, a cured film obtained by hardening the liquid curable resin composition can be improved. Properties, especially scratch resistance and chemical resistance. (D) Metal oxide particles having a number average particle diameter of 100 nm or less The number average particle diameter of the metal oxide particles is 100 nm or less. If the number average particle diameter exceeds 100 nm, it may be difficult to uniformly disperse the metal oxide particles. In addition, the metal oxide particles are liable to settle and the storage stability may be insufficient. Furthermore, the transparency of the obtained cured film is decreased, and the haze (haze) is increased. The φ number average particle diameter is preferably 10 to 80, and more preferably 20 to 50 nm. The "number-average particle diameter" is a number-average particle diameter measured by an electron microscope method. When the metal oxide particles are agglomerated, the particle diameter is a primary particle diameter. The average of the diameter (length) and the short diameter (width). When the particle shape is a rod shape (referring to a shape having an aspect ratio of 1 to 10), the short diameter is used as the particle diameter. The metal oxide particles are preferably one or more selected from titanium oxide, zirconia, antimony-containing tin oxide, phosphorus-containing tin oxide, tin-containing indium oxide, silicon dioxide, aluminum oxide, hafnium oxide, zinc oxide, Aluminium zinc oxide, tin oxide-36- 200538754 ^ (33), particles of metal oxides composed of antimony-containing zinc oxide and indium-containing zinc oxide. Here, it is also possible to use metal oxide particles having a multilayer structure in which metal oxide particles are coated with one or two or more metal oxides other than the metal oxide. Specific examples of the metal oxide particles having a multilayer structure include silica-coated titanium oxide particles, alumina-coated titanium oxide particles, alumina-coated titanium oxide particles, zirconia-coated titanium oxide particles, aluminum oxide, and zirconia-coated titanium oxide. Particles and more. Among such metal oxide particles, particles containing silicon dioxide as a main component, particles containing titanium oxide as a main component, or alumina and zirconia-coated titanium oxide particles are more preferable. By using metal oxide particles having a multilayer structure, the photocatalytic activity of titanium oxide can be suppressed, and the decomposition of hardened materials can be suppressed. As a result, a cured film having a high refractive index and excellent light resistance can be obtained. In addition, by using antimony-containing tin oxide particles (ATO), it is possible to impart antistatic properties to the cured film. In this case, as will be described later, the ATO particles are biased φ, and a small amount of addition can make the effective Both antistatic properties and good transparency are balanced. As the particles containing silicon dioxide as the main component, well-known ones can be used. Moreover, when the shape is spherical, it is not limited to ordinary colloidal silicon dioxide, hollow particles, porous particles, and core-shell particles. It is not limited to spherical and irregular particles. Colloidal silicon dioxide having a number average particle diameter of 1 to 100 nm, a solid content of 10 to 40% by weight, and a pH of 2.0 to 6.5 obtained by observation by a dynamic light scattering method or an electron microscope is preferred. Commercially available particles containing silicon dioxide as the main component are, for example, Nissan Kasei-37- (34) 200538754 Snow Iron Co., Ltd., manufactured by Gakuen Industry Co., Ltd. (the number average particle obtained by dynamic light scattering method) Diameter is 7nm, solid content 20% by weight, pH 2.7), snow iron OL (number average particle diameter obtained by dynamic light scattering method is 15nm, solid content 20% by weight, pH 2.5), etc. . The dispersant is preferably water or an organic solvent. Organic solvents include alcohols such as methanol, isopropanol, ethylene glycol, butanol, and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethyl methyl alcohol Ammonium amines such as fluorenamine, B dimethylacetamide, and N-methylpyrrolidine; esters such as ethyl acetate, butyl acetate, and r-butyrolactone; ethers such as tetrahydrofuran, 1,4-dioxane Organic solvents such as alcohols and alcohols and ketones are preferred. These organic solvents may be used alone or as a mixture of two or more kinds as a dispersant. By using metal oxide particles having a refractive index of 1.5 or more at a wavelength of 5 to 89 nm, the metal oxide particles can increase the refractive index of the metal oxide particles constituting a hardened film having two or more layers as a layer having a high density. Therefore, it is suitable to be used as an anti-reflection layer. For this purpose, particles of silicon dioxide (emissivity of about 1.45) are not suitable. When metal oxide particles are used to increase the refractive index of a layer having a high density, it is preferable to use one or two or more metal oxide particles selected from the group consisting of titanium oxide, chromium oxide, antimony-containing tin oxide, phosphorus-containing tin oxide, and tin. Particles composed mainly of metal oxides consisting of indium oxide, aluminum oxide, hafnium oxide, zinc oxide, aluminum-containing zinc oxide, tin oxide, antimony-containing zinc oxide, and indium-containing zinc oxide. As the particles containing titanium oxide as a main component, a well-known particle can be used. The shape of the particles can be hollow particles, porous particles, core-shell particles, or the like. In addition, the shape is not limited to a spherical shape or a rod shape (in terms of a shape having an aspect ratio of 1 to 10) -38- 200538754 (35) or irregular particles, and a rod shape is preferred. The number average particle diameter obtained by the electron microscope method is preferably 1 to 100 nm. Commercial products of titanium oxide-based particles include, for example, products manufactured by Tieka Co., Ltd. and products manufactured by Seiwa Chemical Co., Ltd. As the dispersant of titanium oxide, the same ones as those used for the silica particles can be used. The (D) metal oxide particles used in the present invention are organic compounds (Ab) having a polymerizable unsaturated group φ described below, or hydrolyzable silicon compounds containing 1 or more alkyl groups in the molecule, or the following: It is obtained by a method such as hydrolysis of a hydrolysate (hereinafter referred to as "organic compound (Ac)"). However, in this reaction, in addition to covalent bonds, non-covalent bonds such as physical adsorption are also included. At this time, the metal oxide particles not connected to the organic compound (Ab) are called "metal oxide particles (Aa)", and the particles connected to the organic compound (Ab) or (Ac) are called reactive particles (Dab) or (Dac). When the metal oxide particles (Ab) are reactive particles (Dab) or (Dac) connected to a φ organic compound (Ab) or (Ac) having a polymerizable unsaturated group, the (D) metal oxide particle component It has a polymerizable unsaturated group and can form a strong covalent bond with other components, which can improve the scratch resistance of the obtained hardened film. (1) Chemical finishing on the organic compound (Ab) having a polymerizable unsaturated group The organic compound (Ab) used in the present invention is a compound having a polymerizable unsaturated group; further, it contains the following formula (5 ) Is preferably based on -39- 200538754 (36) organic compounds. In addition, it is preferable to contain a [-〇-C (= 0) -NH-] group, and further to contain a [-〇-C (= S) -NH-] group and [-SC (= 0) -NH-] At least one of them is preferred. The organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound which is hydrolyzed to form a silanol group. U —U—C 一 Ν— ⑸

IIII

VV

[式中，U爲ΝΗ、Ο (氧原子）、或S (硫原子[Where U is ΝΗ, Ο (oxygen atom), or S (sulfur atom

V爲〇或S (i )聚合性不飽和基有機化合物（Ab )中所含之聚合性不飽和基，沒有特別的限制，適合例有例如丙烯醯基、甲基丙烯醯基、乙嫌基、丙烯基、丁烯基、苯乙烯基、乙炔基、肉桂醸基、馬來酸酯基、丙烯醯胺基等等。此聚合性不飽和基係藉由活性游離基種附加聚合2 _ 成單位。 (Π)該式（5)所示之基有機化合物中所含的該式（5)所示之基[_U-C( = V)_NH_ ]，具體的有[-0-C( = 0)-NH-]、[-0-C( = S)-NH-]、[-S-C( = 〇h NH-]、[-NH-C( = 0)-NH-]、[-NH-C( = S)-NH-]、及[-S-C( = S)- NH-]等6種。此等基可單獨一種或兩種以上組合使用。其中從熱穩定性之觀點而言，以[-〇-C( = 0)-NH-]基與、 -40- 200538754 (37) C( = S)-NH-]基及[-S-C( = 0)-NH-]基之至少一種倂用爲佳。該式（5 )所示之基[-U-C( = V)-NH-]，推測係於分子間藉氫鍵產生適度之凝聚力，形成硬化物時，賦予優越之機械強度、與基材及高折射率層之鄰接層的密著性以及耐熱性等特性。 (iii )矽烷醇基或經水解生成矽烷醇基之基 II 有機化合物（Ab )，以分子內具有矽烷醇基之化合物或經水解生成矽烷醇基之基的化合物爲佳。如此之生成砂烷醇基的化合物，有矽原子上連結烷氧基、芳氧基、乙醯氧基、胺基、鹵原子等之化合物；矽子上連結烷氧基或芳氧基之化合物，即，以含有烷氧基甲矽烷基之化合物或芳氧基甲矽烷基的化合物爲佳。矽烷醇基或生成矽烷醇基之化合物的矽烷醇基生成部位，係藉由縮合反應或接著水解進行縮合反應，與氧化物 Φ 粒子（Aa )連結之構成單位。 (iv )較佳之型態有機化合物（Ab )之較佳具體例有，例如下述式（6 ) 表示之化合物等。 (OR6)】 R73_j—丄i_R8—s—C 一U—R9—B—C—0—R10—(Z)k ⑹ Ο 〇 - 41 - (38) 200538754 式中，R6、R7爲相同或相異均可之氫原子或碳數1〜8之烷基或者芳基；例如甲基、乙基、丙基、丁基、辛基、苯基、二甲苯基等；j爲1〜3之整數。 [(R60)jR73_jSi-]所示之基有，例如三甲氧基甲矽烷基、三乙氧基甲矽烷基、三苯氧基甲矽烷基、甲基二甲氧基甲矽烷基、二甲基甲氧基矽烷基等。如此之基中，以三甲氧基甲矽烷基或三乙氧基甲矽烷基爲佳。 g R8爲具有碳數1〜1 2之脂肪族或芳香族結構的二價有機基，含直鏈狀、支鏈狀或環狀之結構亦可。具體的有伸甲基、伸乙基、伸丙基、伸丁基、伸己基、伸環己基、伸苯基、伸二甲苯基、伸（十二烷）基等。 R9爲二價之有機基；通常爲分子量14〜1萬，較佳爲選自分子量76〜5 00之二價有機基。具體例有伸己基、伸辛基、伸 (十二烷）基等直鏈狀聚伸烷基；伸環己基、伸冰片烷基等脂環式或多環式之二價有機基；伸苯基、伸萘基、伸聯苯基 φ 、聚伸苯基等二價芳香族基；以及此等之烷基取代物、芳基取代物等等。又，此等二價有機基，含有含碳原子及氫原子以外之元素的原子團亦可，含聚醚鍵、聚酯鍵、聚醯胺鍵、聚碳酸酯鍵亦可。 R1()爲（k+Ι )價之有機基，較佳爲選自直鏈狀、支鏈狀或環狀之飽和烴基、不飽和烴基。 Z爲，分子中具有在活性游離基種之存在下進行分子間交聯反應的聚合性不飽和基之一價有機基。又，k較佳爲 1〜20之整數，以1〜10之整數更佳，以1〜5之整數最理想。 -42- 200538754 (39) 式（6 )所示之化合物的具體例’有T @式i 之化合物等。V is 0 or S (i) The polymerizable unsaturated group contained in the polymerizable unsaturated organic compound (Ab) is not particularly limited. Suitable examples include acrylfluorenyl, methacrylfluorenyl, and ethylethyl. , Propenyl, butenyl, styryl, ethynyl, cinnamyl, maleate, acrylamino and the like. This polymerizable unsaturated group is additionally polymerized by living radical species into 2 units. (Π) The base [_U-C (= V) _NH_] contained in the organic compound represented by the formula (5), which is represented by [-0-C (= 0) -NH-], [-0-C (= S) -NH-], [-SC (= 〇h NH-], [-NH-C (= 0) -NH-], [-NH-C ( = S) -NH-] and [-SC (= S) -NH-], etc. These groups can be used alone or in combination of two or more. From the viewpoint of thermal stability, [- 〇-C (= 0) -NH-] group and -40-200538754 (37) C (= S) -NH-] group and [-SC (= 0) -NH-] group The base [-UC (= V) -NH-] represented by the formula (5) is presumably due to the intermolecular hydrogen bonding to generate a moderate cohesive force, and when forming a hardened material, it provides superior mechanical strength and substrate. And the high-refractive index layer adjacent to the adhesiveness and heat resistance and other characteristics. (Iii) Silanol group or a group II organic compound (Ab) which is hydrolyzed to form a silanol group, a compound having a silanol group in the molecule or A compound that generates a silanol group by hydrolysis is preferred. A compound that produces a saranol group in this way has an alkoxy group, an aryloxy group, an ethoxyl group, an amine group, a halogen atom, and the like connected to a silicon atom. A compound having an alkoxy group or an aryloxy group attached to a silicon, that is, a compound containing an alkoxysilyl group or a compound having an aryloxysilyl group is preferred. A silanol group or a compound that generates a silanol group The silanol group generating site is a constituent unit connected to the oxide Φ particles (Aa) by a condensation reaction or a condensation reaction followed by hydrolysis. (Iv) Preferred specific examples of the organic compound (Ab) in a preferred form are For example, compounds represented by the following formula (6), etc. (OR6)] R73_j— 丄 i_R8—s—C—U—R9—B—C—0—R10— (Z) k ⑹ 〇〇- 41-(38 ) 200538754 In the formula, R6 and R7 are the same or different hydrogen atom or 1 to 8 carbon or aryl group; for example, methyl, ethyl, propyl, butyl, octyl, phenyl, Xylyl, etc .; j is an integer from 1 to 3. The groups shown by [(R60) jR73_jSi-] include, for example, trimethoxysilyl, triethoxysilyl, triphenoxysilyl, Methyldimethoxysilyl, dimethylmethoxysilyl, etc. In such a base, trimethoxysilyl or triethoxy Silyl group is preferred. G R8 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and it may contain a linear, branched, or cyclic structure. Specific examples include an extended methyl group. , Ethylene, propyl, butyl, hexyl, cyclohexyl, phenyl, xylyl, dodecyl, etc. R9 is a divalent organic group; usually a molecular weight of 14 to 10,000, preferably a divalent organic group selected from a molecular weight of 76 to 5,000. Specific examples include linear polyalkylene groups such as hexyl, octyl, and dodecyl; alicyclic or polycyclic divalent organic groups such as cyclohexyl and norbornyl; and benzene Divalent aromatic groups such as phenylene, naphthyl, phenylene φ, polyphenylene; and alkyl substituents, aryl substituents, and the like. These divalent organic groups may contain atomic groups containing elements other than carbon atoms and hydrogen atoms, and may contain polyether bonds, polyester bonds, polyamide bonds, and polycarbonate bonds. R1 () is a (k + 1) -valent organic group, and is preferably selected from a linear, branched, or cyclic saturated hydrocarbon group and an unsaturated hydrocarbon group. Z is a monovalent organic group having a polymerizable unsaturated group which performs an intermolecular cross-linking reaction in the presence of an active free radical species. In addition, k is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and an integer of 1 to 5 is most preferable. -42- 200538754 (39) Specific examples of the compound represented by the formula (6) 'include compounds of the formula T @ i.

(式中「Aery 1」爲丙烯醯基，「Me」爲甲基。）本發明中所使用的有機化合物（Ab )之合成’可採用例如特開平9-1 00 1 1 1號公報上記載之方法。較佳爲藉由將疏基丙基三甲氧基矽烷與異佛爾酮二異氰酸酯’在二丁基錫二月桂酸酯之存在下混合，於60〜70 °C經數小時反應後’添加季戊四醇三丙烯酸酯，再於60〜70 °C反應數小時，製造而得 (v)反應性粒子（Dab) 使具有砂院醇基或經水解生成砂垸醇基之基的有機化合物（Ab )、與金屬氧化物粒子（Aa )混合，進行水解使兩者連結。所得反應粒子（Dab )中之有機聚合物成份，即，水解性矽烷之水解物及縮合物的比例，通常爲將乾燥粉體於空氣中完全燃燒時之質量減少％的恆量値，可藉由例如在空氣中自室溫至通常爲800 °C爲止之熱質量分析求得。對金屬氧化物粒子（Aa)之有機化合物（Ab )的連結量，以反應性粒子（Dab )[金屬氧化物粒子（Aa )及有機 -43- (40) 200538754 化合物（Ab )之合計]爲1 0 0重量％時，較佳爲〇 . 01重量％以上，以0 · 1重量％以上更佳，以1重量％以上最理想。連結於金屬氧化物粒子（Aa )之有機化合物（Ab )的連結量低於 0.01重量％時，組成物中反應性粒子（Dab )之分散性不足，所得硬化物之透明性及耐擦傷性有不充分的情況。又，製造反應性粒子（Dab )時，原料中之金屬氧化物粒子（ Aa )的配合比例，較佳爲5〜99重量％，以10〜98重量％更佳 φ 。構成反應性粒子（Dab )之金屬氧化物粒子（Aa )的含量，以反應性粒子（Dab )之65〜95重量％爲佳 (2 )分子中具有1以上之烷基的水解性矽化合物、或含有其水解物者[有機化合物（Ac )]的化學潤飾又，可將金屬氧化物粒子（Aa )中，分子中具有1以上之烷基的水解性矽化合物、或含有其水解物者[有機化合物（Ac )]反應。如此之水解性矽化合物有，三甲基甲氧基 φ 矽烷、三丁基甲氧基矽烷、二甲基二甲氧基矽烷、二丁基二甲氧基矽烷、甲基三甲氧基矽烷、丁基三甲氧基矽烷、辛基三甲氧基矽烷、（十二烷）基三甲氧基矽烷、ΐ,Μ -三甲氧基- 2,2,2-三甲基-二矽烷、六甲基-1，3_二矽氧烷、1，1，-三甲氧基-3,3,3-三甲基-1，3-二矽氧烷、α-三甲基甲矽烷基-ω-二甲基甲氧基甲矽烷基-聚二甲基矽氧烷、α-三甲基甲矽烷基-ω-三甲氧基甲矽烷基-聚二甲基矽氧烷六甲基-1,3-二矽氨烷等等。又，可使用分子中具有1以上之反應性基的水解性矽化合物。分子中具有1以上之反應性基的水解性矽化合物， -44- 200538754 (41) 例如，具有NH2基爲反應性基者有尿素丙基三甲氧基矽烷、 N-( 2-胺基乙基）-3-胺基丙基三甲氧基矽烷等，具有OH基者有雙（2_羥基乙基）-3-胺基三丙基甲氧基矽烷等，具有異氰酸酯基者有3-異氰酸酯基丙基三甲氧基矽烷等，具有硫氰酸酯基者有3-硫氰酸酯基丙基三甲氧基矽烷等，具有環氧基者有（3-環氧丙氧基丙基）三甲氧基矽烷、2- ( 3,4-環氧環己基）乙基三甲氧基矽烷等，具有硫醇基者有3-锍基丙基三 φ 甲氧基矽烷等等。較佳之化合物爲3-毓基丙基三甲氧基矽烷等。對不含該（F )成份爲必要成份之第一型態的液狀硬化性樹脂組成物之固形份1 00重量％，（ D )金屬氧化物粒子[ 包含反應性粒子（Dab ) 、（ Dac )之情況]之配合比例，通常爲10〜90重量％，較佳爲20〜80重量％。超出此範圍外時有損防反射效果、塗膜強度降低，極不適合。含該（F )成份爲必要成份之第二型態的液狀硬化性樹 φ 脂組成物之固形份1 〇〇重量7。中，所含（D )金屬氧化物粒子 [包含反應性粒子（Dab )、（ Dac )之情況]之使用比例，通常爲5〜80重量％之範圍，較佳爲1〇〜80重量％，以20〜70重量％之範圍更適合。超出此範圍外時有損防反射效果、塗膜強度下降，甚不適合。 (E )溶劑爲不使液狀硬化性樹脂組成物產生層分離，必要配合 (E-1 )快速揮發溶劑及（E-2 )緩慢揮發溶劑之兩種類的 -45- (42) 200538754 溶劑。（E-l )及（E-2 )之溶劑，分別使用一種以上。 (E-1 )快速揮發溶劑液狀硬化性樹脂組成物中所含（E -1 )快速揮發溶劑係一種或兩種以上之對該（A )含氟聚合物溶解性高的溶劑。於此所謂對含有經基之含氟聚合物溶解性高，係指將 (A)含有羥基之含氟聚合物添加於各溶劑中至可達5〇重 φ 量％，於室溫攪拌8小時後，以目視檢測調成均勻溶液而言。然後，（E _ 1 )快速揮發溶劑之相對蒸發速度，必要大於後述之（E-2 )緩慢揮發溶劑之相對蒸發速度。於此所謂「相對蒸發速度」，係指以乙酸丁酯9 0重量％蒸發之所需時間爲基準的蒸發速度之相對値而言；詳細如「化學技術」第2卷「有機溶劑」、「精製之物理性質與方法」第4 版，1 986年62頁之記載。又，（E-1 )快速揮發溶劑，以對該（D )金屬氧化物粒子之分散穩定性低爲佳.藉由（E-φ 1 )快速揮發溶劑之相對蒸發速度大於（E-2 )，對（A ) 含氟聚合物之溶解性高，且對（D )金屬氧化物粒子之分散穩定性低，在將液狀硬化性樹脂組成物塗佈於基材，使溶劑（E-1 )及（E-2 )蒸發之過程，可將（D )金屬氧化物粒子偏在化。本發明中可使用爲（E-1 )快速揮發溶劑之溶劑爲相對蒸發速度大約1.7以上的溶劑，具體的有曱乙酮（MEK相對蒸發速度3.8)、異丙醇（IPA:1.7)、甲異丁酮（MIBK : 1.6 )、甲戊酮（ΜΑΚ:0·3)、丙酮、甲丙酮等等。 -46- (43) 200538754 (E - 2 )緩慢揮發溶劑液狀硬化性樹脂組成物中所含（Ed )緩慢揮發溶劑，係一種或兩種以上之對該（D )金屬氧化物粒子分散穩定性高的溶劑。於此所謂對（D )金屬氧化物粒子之分散穩定性高，係指將玻璃板浸漬於金屬氧化物粒子分散液，使（D ) 金屬氧化物粒子附黏於玻璃壁，將（D )金屬氧化物粒子黏 φ 之玻璃板浸漬於各溶劑時，（D )金屬氧化物粒子，以目視檢測、均勻分散於該溶劑中之意。又（E-2 )緩慢揮發溶劑 ’對該（A )含氟聚合物之溶解性以較低爲佳。本發明中可使用爲（E-2 )緩慢揮發溶劑之溶劑爲相對蒸發速度大約1 · 7以下的溶劑。具體的有甲醇（相對蒸發速度 2.1 )、異丙醇（IPA :1.7)、正丁醇（n-BuOH:0.5)、叔丁醇、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、乙基溶纖劑、丙基溶纖劑、丁基溶纖劑等等。 φ 本發明所使用之（E-1 )快速揮發溶劑及/或（E-2 )緩慢揮發溶劑，可直接使用該（A)含氟聚合物之製造中所使用的溶劑。本發明中所使用之（E-1 )快速揮發溶劑與（E-2 )緩慢揮發溶劑，必要具有相溶性。相溶性爲，在組成物之具體的構成中，不致使（E-1 )快速揮發溶劑與（E-2 )緩慢揮發溶劑分離之程度的相溶性即可。於此，選擇之溶劑，屬於本發明中所使用之（E-1 ) 快速揮發溶劑、或（E-2 )緩慢揮發溶劑的那一種，係由 -47- 200538754 (44) 選擇之複數的溶劑種類相對而決定；因此相對蒸發速度爲 1 · 7之異丙醇，使用爲（E -1 )快速揮發溶劑亦可，使用爲 (E-2 )緩慢揮發溶劑亦可。對液狀硬化性樹脂組成物中之溶劑[包含（E -1 )成份及（E-2 )成份]以外的成份之總量1 〇〇重量份，溶劑（E-1 )及溶劑（E-2)之合計量通常爲300〜5000重量份，較佳爲 3 00〜4 0 00重量份，以使用300〜3 000重量份更適合。溶劑（ φ Ε·1 )與溶劑（E-2 )之配合比，可於i : 99〜99 ; i之範圍任意選擇。 (F )活性能量線硬化性化合物活性能量線硬化性化合物，係本發明中第二型態之液狀硬化性樹脂組成物所使用的必要成份。本發明中所使用之活性能量線硬化性化合物，係分子內含有2以上之聚合性不飽和基的化合物。此化合物適合使 φ 用於提高組成物之成膜性，只要爲分子內含有2以上之聚合性不飽和基者，沒有特別的限制，例如有三聚氰胺丙烯酸酯類、（甲基）丙烯酸酯類、乙烯基化合物類等。其中以（甲基）丙烯酸酯類爲佳。本發明中所使用之（F )成份的具體例列舉如下。 (甲基）丙烯酸酯類有，三羥甲基丙烷三（甲基）丙烯酸酯、二（三羥甲基丙烷）四（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸 -48- 200538754 (45) 酯、丙三醇三（甲基）丙烯酸酯、三（2-羥基乙基）三聚異氰酸酯三（甲基）丙烯酸酯、、乙二醇二（甲基）丙烯酸酯、1,3-丁二醇二（甲基）丙烯酸酯、ι，4-丁二醇二（甲基）丙烯酸酯、1，6-己二醇二（甲基）丙烯酸酯、季戊二醇二（甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲基）丙烯酸酯、二丙二醇二（甲基）丙烯酸酯、雙（ 2-羥基乙基）三聚異氰酸酯二（甲基）丙烯酸酯、以及此等 φ 之始發醇類的環氧乙烷或環氧丙烷之附加物的聚（甲基）丙烯酸酯類、分子內具有2以上之（甲基）丙烯醯基的低聚酯 (甲基）丙烯酸酯類、低聚醚（甲基）丙烯酸酯類、低聚胺基甲酸酯（甲基）丙烯酸酯類、及低聚環氧（甲基）丙烯酸酯類之外，尙有下述述式（8)表示之化合物等等。其中以二季戊四醇六（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二（三羥甲基丙烷）四（甲基）丙烯酸酯、下述式（8)表示之化合物爲佳(In the formula, "Aery 1" is acrylfluorenyl, and "Me" is methyl.) The synthesis of the organic compound (Ab) used in the present invention can be described in, for example, Japanese Patent Application Laid-Open No. 9-1 00 1 11 Method. Preferably, pentaerythritol triacrylic acid is added by mixing thiopropyltrimethoxysilane and isophorone diisocyanate 'in the presence of dibutyltin dilaurate and reacting at 60 to 70 ° C for several hours' Ester, and then reacted at 60 ~ 70 ° C for several hours to produce (v) reactive particles (Dab). The organic compound (Ab) having a sand alcohol group or a base that is hydrolyzed to form a sand alcohol group, and a metal. The oxide particles (Aa) are mixed and hydrolyzed to connect the two. The proportion of the organic polymer component in the obtained reaction particles (Dab), that is, the hydrolysate and condensate of the hydrolyzable silane, is usually a constant amount that reduces the mass of the dry powder when it is completely burned in the air. For example, it can be obtained by thermal mass analysis in the air from room temperature to usually 800 ° C. The amount of the organic compound (Ab) connected to the metal oxide particles (Aa) is represented by the reactive particles (Dab) [total of the metal oxide particles (Aa) and organic -43- (40) 200538754 compound (Ab)]. In the case of 100% by weight, it is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and most preferably 1% by weight or more. When the amount of the organic compound (Ab) connected to the metal oxide particles (Aa) is less than 0.01% by weight, the dispersibility of the reactive particles (Dab) in the composition is insufficient, and the transparency and abrasion resistance of the obtained hardened material are inferior. Inadequate situation. In the production of reactive particles (Dab), the mixing ratio of the metal oxide particles (Aa) in the raw material is preferably 5 to 99% by weight, and more preferably 10 to 98% by weight φ. The content of the metal oxide particles (Aa) constituting the reactive particles (Dab) is preferably 65 to 95% by weight of the reactive particles (Dab) (2) a hydrolyzable silicon compound having 1 or more alkyl groups in a molecule, Or chemical retouching of the hydrolysate [organic compound (Ac)], and hydrolyzable silicon compounds having 1 or more alkyl groups in the molecule of the metal oxide particles (Aa), or those containing the hydrolysate [ Organic compound (Ac)]. Examples of such hydrolyzable silicon compounds include trimethylmethoxy φ silane, tributyl methoxy silane, dimethyl di methoxy silane, di butyl di methoxy silane, methyl tri methoxy silane, and butyl Trimethoxysilane, octyltrimethoxysilane, (dodecyl) trimethoxysilane, fluorene, M -trimethoxy-2,2,2-trimethyl-disilanes, hexamethyl-1, 3_disilaxane, 1,1, -trimethoxy-3,3,3-trimethyl-1,3-disilaxane, α-trimethylsilyl-ω-dimethylmethyl Oxysilyl-polydimethylsilane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsilane hexamethyl-1,3-disilamin And so on. Further, a hydrolyzable silicon compound having one or more reactive groups in the molecule can be used. Hydrolyzable silicon compounds with a reactive group of 1 or more in the molecule, -44- 200538754 (41) For example, those with a NH2 group as a reactive group include urea-propyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropyltrimethoxysilane, etc., those having OH group include bis (2-hydroxyethyl) -3-aminotripropylmethoxysilane, etc., and those having isocyanate group have 3-isocyanate group Propyltrimethoxysilane, etc., those with thiocyanate groups are 3-thiocyanatopropyltrimethoxysilane, etc., and those with epoxy groups are (3-glycidoxypropyl) trimethoxy Silyl, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc., and those having a thiol group include 3-amidinopropyltriφmethoxymethoxysilane, and the like. Preferred compounds are 3-cyanopropyltrimethoxysilane and the like. 100% by weight of the solid content of the first type of liquid hardening resin composition containing the (F) component as an essential component, (D) metal oxide particles [including reactive particles (Dab), (Dac In the case of)], the mixing ratio is usually 10 to 90% by weight, preferably 20 to 80% by weight. Outside this range, the antireflection effect is impaired, and the strength of the coating film is reduced, which is extremely unsuitable. The solid content of the second type of liquid sclerosing tree φ-lipid composition containing the (F) component as an essential component is 1000 weights7. In the use ratio of (D) metal oxide particles [in the case where reactive particles (Dab) and (Dac) are included]), the range is usually 5 to 80% by weight, preferably 10 to 80% by weight. A range of 20 to 70% by weight is more suitable. Beyond this range, the antireflection effect is impaired, and the strength of the coating film is reduced, making it unsuitable. (E) Solvent In order to prevent layer separation of the liquid curable resin composition, two types of -45- (42) 200538754 (E-1) fast-volatile solvents and (E-2) slow-volatile solvents must be added. The solvents of (E-1) and (E-2) may be used alone or in combination. (E-1) Fast volatilizing solvent The (E-1) fast volatilizing solvent contained in the liquid curable resin composition is one or two or more solvents having high solubility in the (A) fluoropolymer. The so-called high solubility of the fluorinated polymer containing a warp group means that (A) a fluorinated polymer containing a hydroxyl group is added to each solvent to a weight of 50% by weight and stirred at room temperature for 8 hours. After that, it was adjusted to a uniform solution by visual inspection. Then, the relative evaporation rate of (E _ 1) fast volatilizing solvent must be greater than the relative evaporation rate of (E-2) slowly volatilizing solvent described later. The so-called “relative evaporation rate” here refers to the relative rate of evaporation rate based on the time required for 90% by weight of butyl acetate to evaporate. For details, refer to “Chemical Technology” Volume 2 “Organic Solvents”, “ Refined Physical Properties and Methods ", 4th edition, 62 pages 1986. In addition, (E-1) is a fast volatilizing solvent, preferably with low dispersion stability of the (D) metal oxide particles. With (E-φ 1), the relative evaporation rate of the fast volatilizing solvent is greater than (E-2) It has high solubility to (A) fluoropolymer and low dispersion stability to (D) metal oxide particles. When a liquid hardening resin composition is applied to a substrate, the solvent (E-1 ) And (E-2) evaporation process, (D) metal oxide particles can be biased. The solvent that can be used as the (E-1) fast-evaporating solvent in the present invention is a solvent having a relative evaporation rate of about 1.7 or more. Specific examples include acetophenone (MEK relative evaporation rate 3.8), isopropanol (IPA: 1.7), and Isobutanone (MIBK: 1.6), methylpentanone (MAK: 0 · 3), acetone, methylacetone, and the like. -46- (43) 200538754 (E-2) Slow volatilization solvent (Ed) The slow volatilization solvent contained in the liquid hardening resin composition is one or two or more kinds of the (D) metal oxide particles which are dispersed and stabilized. Highly solvent. The high dispersion stability of (D) metal oxide particles here means that a glass plate is immersed in a metal oxide particle dispersion to make (D) metal oxide particles adhere to the glass wall, and (D) metal When a glass plate with oxide particles attached to φ is immersed in each solvent, the (D) metal oxide particles are visually detected and uniformly dispersed in the solvent. (E-2) Slowly volatilizing the solvent 'is preferred for its low solubility to the (A) fluoropolymer. The solvent that can be used in the present invention (E-2) as a slowly volatile solvent is a solvent having a relative evaporation rate of about 1 · 7 or less. Specific examples are methanol (relative evaporation rate 2.1), isopropanol (IPA: 1.7), n-butanol (n-BuOH: 0.5), tert-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl Base cellosolve, propyl cellosolve, butyl cellosolve, etc. φ The (E-1) fast-volatile solvent and / or (E-2) slow-volatile solvent used in the present invention can be used directly as the solvent used in the production of the (A) fluoropolymer. The (E-1) fast-volatile solvent and (E-2) slow-volatile solvent used in the present invention must be compatible. The compatibility is such that the specific composition of the composition is such that the compatibility between the (E-1) rapid volatilization solvent and the (E-2) slow volatilization solvent is not separated. Here, the selected solvent belongs to the (E-1) fast volatilizing solvent or (E-2) slow volatilizing solvent used in the present invention, which is a plurality of solvents selected from -47-200538754 (44). The type is relatively determined; therefore, isopropanol with a relative evaporation rate of 1 · 7 can also be used as a fast-evaporating solvent (E -1), or it can be used as a slow-evaporating solvent (E-2). 100 parts by weight of the total amount of the components other than the solvent [including the (E -1) component and the (E-2) component] in the liquid curable resin composition, the solvent (E-1) and the solvent (E- 2) The total amount is usually 300 to 5000 parts by weight, preferably 300 to 4,000 parts by weight, and more preferably 300 to 3,000 parts by weight. The mixing ratio of the solvent (φE · 1) and the solvent (E-2) can be arbitrarily selected in the range of i: 99 to 99; i. (F) Active-energy-ray-curable compound The active-energy-ray-curable compound is an essential component used in the second type of liquid curable resin composition in the present invention. The active energy ray-curable compound used in the present invention is a compound containing two or more polymerizable unsaturated groups in the molecule. This compound is suitable for using φ to improve the film-forming property of the composition, and is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule. Examples include melamine acrylates, (meth) acrylates, Vinyl compounds and so on. Of these, (meth) acrylates are preferred. Specific examples of the (F) component used in the present invention are listed below. (Meth) acrylates include trimethylolpropane tri (meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Methacrylic acid ester, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylic acid -48- 200538754 (45) ester, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) Based) trimeric isocyanate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, ι, 4-butanediol di (meth) Based) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( Meth) acrylates, dipropylene glycol di (meth) acrylates, bis (2-hydroxyethyl) trimeric isocyanate di (meth) acrylates, and ethylene oxide of these origin alcohols or Poly (meth) acrylates of propylene oxide additives, having 2 or more in the molecule (Meth) acrylic acid-based oligoester (meth) acrylates, oligoether (meth) acrylates, oligourethane (meth) acrylates, and oligoepoxy In addition to (meth) acrylic acid esters, there are compounds such as the following formula (8). Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, and the following formula (8) The compound represented is preferred

OAcryl V〇\^\^OAcryl T L 〇 OAcryl ⑻ (式中，「Acryl」爲丙烯醯基。）乙烯基化合物類有，二乙烯基苯、乙二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚等。 -49- (46) 200538754OAcryl V〇 \ ^ \ ^ OAcryl TL 〇OAcryl ⑻ (where "Acryl" is acrylfluorenyl.) Vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, and diethylene glycol diethylene. Ether, triethylene glycol divinyl ether, and the like. -49- (46) 200538754

如此之（F )成份的市售品有，例如三和化學股份有限公司製之商品名：尼卡拉庫MX-302、東亞合成股份有限公司製之商品名：阿洛尼庫斯^4-400、1^-408、？^-450、^4-3 05、M-3 09、M-310、M-315、M-3 20、M-3 5 0、M-3 60、 M-208、M-210、M-215、M-220、M-225、M-23 3、M-240 、M-245、M-260、M_270、M-1100、M- 1 200、M-1210、 M-1310、M- 1 600、M-221、M-203、TO-924、TO- 1 270、 TO-1231、TO-595、TO-756、TO-1343、TO-902、TO-904 、TO-90 5、TO- 1 3 3 0、日本化藥股份有限公司製之商品名 :卡亞拉多 D-3 10、D-3 3 0、DPHA、DPCA-20、DPCA-30、 DPCA-60、DPCCA-120、DN-0075、DN-2475、SR-295、 SR-355 、 SR-399E 、 SR-494 、 SR-9041 、 SR-368 、 SR-415 、 SR-444 、 SR-454 、 SR-492 、 SR-499 、 SR-502 、 SR-9020 、 SR-9035 、 SR-111 、 SR-212 、 SR-213 、 SR-230 、 SR-259 、 SR-268 、 SR-272 、 SR-344 、 SR-349 、 SR-601 、 SR-602 、 SR-610 、 SR-9003 、 PET-30 、 T-1420 、 GPO-303 、 TC-120S 、HDDA、NPGDA、TPGDA、PEG400DA、MANDA、HX-220、HX-620、R-551、R-712、R-167、R-526、R-604、R-684 ' TMPTA、THE-3 3 0、TPA-3 20、TPA-3 3 0、KS-HDDA 、KS_TPGDA、KS_TMPTA、共榮社化學股份有限公司製之商品名；來多丙烯酸酯PE-4A、DPE-6A、DTMP-4A等等。含有（F )成份爲必要成份之第二型態的液狀硬化性樹脂組成物之固形份i 00重量％中，（F )活性能量線硬化性化合物之配合比例，通常爲5〜80重量％之範圍，較佳爲 -50- (47) 200538754 5〜70重量％，以5〜5 0重量％更適合·活性能量線硬化性化合物之配合量過少時，不能獲得充分之塗膜強度；相反的，超過8 0重量％時防反射效果下降，極不適合。藉由在液狀硬化性樹脂組成物中添加活性能量線硬化性化合物，能獲得更佳之使液狀硬化性樹脂組成物硬化而得的硬化膜之特性，尤其是耐擦傷性及耐藥品性更爲優異〇 B 含有（F )成份爲必要成份之第二型態的液狀硬化性樹脂組成物中，除該（A )〜（F )成份以外，可添加改善液狀硬化性樹脂組成物之塗佈性及硬化後之薄膜物性的任意成份、以及對塗膜賦予感光性之（G )光聚合引發劑。 (G)光聚合引發劑光聚合引發劑之例有，例如苯乙酮、苯乙酮苄基縮酮、蒽醌、1- ( 4-異丙基苯基）-2-羥基-2-甲基-丙烷-1-酮、 φ 咔唑、咕噸酮、4-氯二苯甲酮、4,4’-二胺基二苯甲酮、 1,1-二甲氧基脫氧苯偶因、3,3’-二甲基-4-甲氧基二苯甲酮 ’噻噸酮、2,2-二甲氧基-2-苯基苯乙酮、1- (4-月桂基苯基 )-2-羥基-2-甲基丙烷-1-酮、2-甲基-1-[4-(甲硫基）苯基 ]-2-嗎啉（代）丙烷-1-酮、三苯基胺、2,4,6_三甲基苯甲醯基二苯基膦氧化物、1-羥基環己基苯基酮、2-羥基-2-甲基_1_苯基丙烷-1-酮、芴酮、芴、苯甲醛、苯偶因乙基醚、苯偶因丙基醚、二苯甲酮、米希勒酮、3-甲基苯乙酮、 3,3’，4,4’-四（叔丁基過氧碳醯基）二苯甲酮（BTTB ) 、2- -51 - 200538754 (48) (二甲基胺基）-l-[4-(嗎啉基）苯基;]-2-苯基甲基-1-丁酮、4-苯甲醯基-4’-甲基二苯基硫化物、苯甲基或BTTB與咕噸、噻噸、香豆素、酮香豆素、其他之色素敏化劑的組合等等此等光聚合引發劑中，較佳爲2,2-二甲氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1·酮、丨·羥基環己基苯基酮、2,4,6 -二甲基苯甲醯基二苯基膦氧化物、2 -甲基- l- [4-(甲硫基）苯基]-2-嗎啉（代）丙烷-1-酮、2-(二甲基胺基）-φ 1-[4-(嗎啉基）苯基]-2-苯基甲基-1-丁酮等等。以1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基）苯基]_2_嗎啉（代）丙烷-1-酮、2-(二甲基胺基）-1-[4-(嗎啉基）苯基]-2-苯基甲基-1-丁酮等更適合。含有（F )成份爲必要成份之第二型態的液狀硬化性樹脂組成物之固形份100重量份中，（G )光聚合引發劑之配合比例，通常爲〇·1〜1〇重量％之範圍，較佳爲0.1〜5重量％，以0.5〜3重量％之範圍更適合。光聚合引發劑之配合比例過少 φ 時，不能引發光聚合；相反的，超過1 〇重量％時，催化劑在硬化膜中成爲增塑劑之作用，有損透明性，不能獲得充分的機械強度，甚不適合。 (Η)添加劑液狀硬化性樹脂組成物中，爲改善該液狀硬化性樹脂組成物之塗佈性及硬化後之薄膜的物性、對塗膜賦予感光性，可添加各種添加劑。液狀硬化性樹脂組成物中可添加之添加劑有，例如具 -52- 200538754 (49) 有羥基之各種聚合物或單體、顏料或染料等著色劑、防老劑及吸收紫外線劑等穩定化劑、感光性酸產生劑、界面活性劑、聚合抑制劑等等。尤其爲改善形成之硬化膜的硬度及耐久性，以添加光酸產生劑爲佳。特別是選擇不使液狀硬化性樹脂組成物硬化後之透明性下降，且在其溶液中均勻溶解者爲佳。 φ ( i )含羥基之聚合物可配合於液狀硬化性樹脂組成物之含羥基的聚合物有，例如將羥基乙基（甲基）丙烯酸酯等含羥基之共聚合性單體聚合而得的聚合物、酚醛樹脂或甲酚樹脂等眾所周知的具有苯酚骨架之樹脂等。 (ii)顏料或染料等著色劑可配合於液狀硬化性樹脂組成物之著色劑有，例如（1 φ )鋁白、黏土、碳酸鋇、硫酸鋇等底質顏料，（2 )鋅白、鉛白、黃鉛、鉛丹、群青、普魯士藍、氧化鈦、鉻酸鋅、氧化鐵紅、碳黑等無機顏料，（3 )艷洋紅6B、永久紅6B、永久紅R、聯苯胺黃、酞菁藍、酞菁綠等有機顏料，（4 )洋紅、蕊香紅等鹼性染料，（5 )直接猩紅、直接橘等直接染料，（6 )羅色靈、米塔尼爾黃等酸性染料、其他等等 (iii )防老劑、吸收紫外線劑等穩定化劑 -53- (50) 200538754 t 線劑，可使用眾所周知者。防老劑之具體例有’例如二叔丁基苯酚、焦苯醌、對苯二酚、亞甲藍、叔丁基鄰苯二酚、單甲基對苯二酚、戊基醌、戊氧基對苯二酚、正丁苯酚、對苯二酚單丙醚、4,4’-{1-〔4-[1-( 4-羥基甲基乙基]苯基〕亞乙基）一*本酣、1，1，3 -二（2,5_ 羥基苯基）-3-苯基丙烷、二苯基胺類、對苯二胺 φ 嗪、锍基苯并咪唑等等。又，吸收紫外線劑之具體例有，例如苯基水代表之水楊酸酯吸收紫外線劑、二羥基二苯甲酮 4-甲氧基二苯甲酮等二苯甲酮系吸收紫外線劑、系吸收紫外線劑、氰基丙烯酸酯系吸收紫外線劑料之添加劑，可使用爲吸收紫外線劑。 (iv )感光性酸產生劑 φ 可配合於液狀硬化性樹脂組成物之感光性酸係能賦予該液狀硬化性樹脂組成物之塗膜感光性由照射如光等放射線使該塗膜光硬化之物質。此產生劑有’例如（1 )碑鐵鹽、鹽、銹鹽、重氮鹽、吡啶鐵鹽等各種鑰鹽；（2 ) /3 -酮酯、/3 -碘等之^ ·重氮化合物等硕化合物；（3 )烷基磺酸院基磺酸酯、芳基磺酸酯、亞胺磺酸酯等磺酸酿下述一般式（9 )表示之硫醯亞胺化合物類；（5 般式（1 )表示之重氮甲烷化合物類；其他等等。培酚、對苄基醚、基苯酚、苯基）-1-二甲基-4· 類、吩噻楊酸酯爲、2-羥基- 苯并三唑等各種塑產生劑，，例如藉感光性酸鑰鹽、銨醯硕與此酯、鹵化 i ; ( 4 ) )下述一 -54- (51) 200538754Such commercially available (F) ingredients are, for example, the product name made by Sanwa Chemical Co., Ltd .: Nikaraku MX-302, and the product name made by Toa Kosei Co., Ltd .: Alonikos ^ 4-400 , 1 ^ -408,? ^ -450, ^ 4-3 05, M-3 09, M-310, M-315, M-3 20, M-3 5 0, M-3 60, M-208, M-210, M-215 , M-220, M-225, M-23 3, M-240, M-245, M-260, M_270, M-1100, M- 1 200, M-1210, M-1310, M- 1 600, M-221, M-203, TO-924, TO- 1 270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-90 5, TO- 1 3 3 0, trade name of Nippon Kayaku Co., Ltd .: Cayalado D-3 10, D-3 3 0, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCCA-120, DN-0075 , DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR -502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601 , SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551 , R-712, R-167, R-526, R-604, R-684 'TMPTA, THE-3 3 0, TPA-3 20, TPA-3 3 0, KS-HDDA, KS_TPGDA, KS_TMPTA Trade name of Kyoeisha Chemical Co., Ltd.; to multi-acrylate PE-4A, DPE-6A, DTMP-4A and the like. In the solid content i 00% by weight of the second type of liquid curable resin composition containing the (F) component as an essential component, the proportion of the (F) active energy ray-curable compound is usually 5 to 80% by weight. The range is preferably -50 to (47) 200538754 5 to 70% by weight, and 5 to 50% by weight is more suitable. When the blending amount of the active energy ray-curable compound is too small, sufficient coating film strength cannot be obtained; If it exceeds 80% by weight, the antireflection effect decreases, which is extremely unsuitable. By adding an active energy ray-curable compound to the liquid curable resin composition, it is possible to obtain better characteristics of a cured film obtained by hardening the liquid curable resin composition, and in particular, abrasion resistance and chemical resistance are improved. The second type of liquid curable resin composition containing (F) component as an essential component is excellent. In addition to the components (A) to (F), a liquid curable resin composition can be added to improve the liquid curable resin composition. Any component of coating properties and physical properties of the thin film after curing, and a (G) photopolymerization initiator that imparts sensitivity to the coating film. (G) Photopolymerization initiator Examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl -Propane-1-one, φ carbazole, glutanone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone 'thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-laurylphenyl) 2-Hydroxy-2-methylpropane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholine (substituted) propane-1-one, triphenyl Amine, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl_1-phenylpropane-1-one, Fluorenone, hydrazone, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, michelone, 3-methylacetophenone, 3,3 ', 4,4'- Tetrakis (tert-butylperoxycarbamyl) benzophenone (BTTB), 2-51-200538754 (48) (dimethylamino) -l- [4- (morpholinyl) phenyl;] 2-phenylmethyl-1-butanone, 4-benzylidene-4'-methyldiphenyl sulfide, benzyl or BTTB, Among these photopolymerization initiators, coumarin, ketocoumarin, and other combinations of pigment sensitizers, 2,2-dimethoxy-2-phenylacetophenone, 2 -Hydroxy-2-methyl-1-phenylpropane-1 · ketone, 丨 Hydroxycyclohexylphenyl ketone, 2,4,6-Dimethylbenzylidene diphenylphosphine oxide, 2-methyl -L- [4- (methylthio) phenyl] -2-morpholino (propanyl) propan-1-one, 2- (dimethylamino) -φ 1- [4- (morpholinyl) Phenyl] -2-phenylmethyl-1-butanone and the like. 1-Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] _2_morpholine (substituted) propane-1-one, 2- (dimethylamino) 1- [4- (morpholinyl) phenyl] -2-phenylmethyl-1-butanone and the like are more suitable. The compounding ratio of the (G) photopolymerization initiator in 100 parts by weight of the solid content of the second type of liquid curable resin composition containing the (F) component as an essential component is usually 0.1 to 10% by weight. The range is preferably 0.1 to 5% by weight, and more preferably 0.5 to 3% by weight. When the proportion of the photopolymerization initiator is too small φ, photopolymerization cannot be initiated; on the contrary, when it exceeds 10% by weight, the catalyst acts as a plasticizer in the cured film, which impairs transparency and fails to obtain sufficient mechanical strength. Not very suitable. (I) Additives Various additives can be added to the liquid curable resin composition in order to improve the coating properties of the liquid curable resin composition, the physical properties of the cured film, and to impart sensitivity to the coating film. Additives that can be added to the liquid curable resin composition are, for example, -52- 200538754 (49) various polymers or monomers with hydroxyl groups, colorants such as pigments and dyes, antioxidants, and stabilizers such as ultraviolet absorbers , Photosensitive acid generator, surfactant, polymerization inhibitor and so on. In particular, in order to improve the hardness and durability of the formed cured film, it is preferable to add a photoacid generator. In particular, it is preferable to select one that does not lower the transparency of the liquid curable resin composition after hardening and that it evenly dissolves in the solution. φ (i) a hydroxyl-containing polymer can be blended with the liquid-curable resin composition and the hydroxyl-containing polymer is, for example, obtained by polymerizing a hydroxyl-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate Polymers, phenolic resins, cresol resins, and other well-known resins with a phenol skeleton. (ii) Pigments such as pigments or dyes can be added to the liquid hardening resin composition. For example, (1 φ) aluminum white, clay, barium carbonate, barium sulfate and other ground pigments, (2) zinc white, Lead white, yellow lead, lead red, ultramarine, Prussian blue, titanium oxide, zinc chromate, iron oxide red, carbon black and other inorganic pigments, (3) brilliant magenta 6B, permanent red 6B, permanent red R, benzidine yellow, Organic pigments such as phthalocyanine blue and phthalocyanine green, (4) basic dyes such as magenta and vermiculite red, (5) direct dyes such as scarlet and direct orange, and (6) acidity such as rosin and mitanil yellow Dyes, others, etc. (iii) Stabilizers such as antioxidants, UV absorbers, etc. -53- (50) 200538754 t String agents, well-known ones can be used. Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyroquinone, hydroquinone, methylene blue, tert-butylcatechol, monomethylhydroquinone, pentylquinone, and pentoxy Hydroquinone, n-butylphenol, hydroquinone monopropyl ether, 4,4 '-{1- [4- [1- (4-hydroxymethylethyl] phenyl] ethylene) Hydrazone, 1,1,3-bis (2,5-hydroxyphenyl) -3-phenylpropane, diphenylamines, p-phenylenediamine φ azine, fluorenyl benzimidazole and the like. Specific examples of the ultraviolet absorbing agent include, for example, salicylates represented by phenyl water, ultraviolet absorbing agents, and benzophenone-based ultraviolet absorbing agents such as dihydroxybenzophenone 4-methoxybenzophenone. Ultraviolet absorbing agents and cyanoacrylate-based additives for ultraviolet absorbing materials can be used as ultraviolet absorbing agents. (iv) Photosensitive acid generator φ A photosensitive acid that can be blended with the liquid curable resin composition can impart a coating film sensitivity to the liquid curable resin composition. The coating film is irradiated with radiation such as light. Hardened substance. This generating agent includes, for example, (1) various key salts such as iron salts, salts, rust salts, diazonium salts, and pyridinium iron salts; (2) diazonium compounds such as / 3-ketoesters and / 3-iodine. And other master compounds; (3) sulfonic acid such as alkylsulfonic acid, sulfonic acid ester, arylsulfonic acid ester, imine sulfonic acid ester, etc., and thioimine compounds represented by the following general formula (9); Diazomethane compounds represented by the general formula (1); others and the like. Phenol, p-benzyl ether, phenylphenol, phenyl) -1-dimethyl-4 ·, phenothionate is 2 -Hydroxy-benzotriazole and other plastic generators, for example, by the use of photosensitive acid salt, ammonium sulfonate and this ester, halogenated i; (4)) the following one -54- (51) 200538754

式中，X爲伸烷基、伸芳基、伸烷氧基等二價之基；R4爲院基、芳基、鹵素取代院基、鹵素取代芳基等一價之基。 n2 r5o2s-c-so2r6 ⑽ 式中’ R5及R6互爲相同或相異均可之院基、芳基、鹵素取代烷基、鹵素取代芳基等一價之基。感光性酸產生劑可單獨使用或兩種以上倂用。對液狀硬化性樹脂組成物之固形份1 0 0重量份，感光性酸產生劑之使用比例較佳爲〇〜20重量份，以〇·ι〜1〇重量份更適合。此比例過大時，硬化膜之強度劣化、透明性降低，極不適合 (v )界面活性劑液狀硬化性樹脂組成物中，爲改善該液狀硬化性樹脂組成物之塗佈性可配合界面活性劑。此界面活性劑可使用眾所周知者，具體的可使用例如各種陰離子系界面活性劑、陽離子系界面活性劑、非離子系界面活性劑，尤其爲使 -55- 200538754 ♦ (52) 硬化膜具有優異之強度，且具有良好的光學特性，以使用陽離子系界面活性劑爲佳。進而以使用季銨鹽更佳。其中尤其使用季聚醚銨鹽時，能更改善拭去性特別適合。季聚醚銨鹽之陽離子系界面活性劑有，旭電化工業公司製之阿得卡可魯CC-15、CC-36、CC-42等。界面活性劑之使用比例，對液狀硬化性樹脂組成物之固形份1 〇〇重量份，較佳爲爲5重量份以下。 (vi )聚合抑制劑可配合於液狀硬化性樹脂組成物之熱聚合抑制劑有，例如焦培酚、對苯醌、對苯二酚、亞甲藍、叔丁基鄰苯二酚、單苄基醚、甲基對苯二酚、戊基醌、戊氧基對苯二酚、正丁基苯酚、苯酚、對苯二酚單丙醚、4,4’·{1-〔4·[1-(4-羥基苯基）-1-甲基乙基]苯基〕亞乙基}二苯酚、 1，1，3-三（2,5-二甲基-4-羥基苯基）-3-苯基丙烷等等。此 φ 熱聚合抑制劑，對液狀硬化性樹脂組成物之固形份1 00重量份，以使用5重量份以下爲佳。 (vii) ( E)成份以外之溶劑液狀硬化性樹脂組成物中，可添加（E )成份以外之溶劑。如此之溶劑的種類與配合量，本不損及本發明之效果的範圍，可自由選擇。硬化膜之特徵爲，將該液狀硬化性樹脂組成物硬化而得，且具有2層以上之多層結構。尤其以具有由該（D)金 -56- (53) 200538754 屬氧化物粒子高密度存在的1以上之層，與該（D)金屬氧化物粒子實質上不存在的1以下之層所成二層以上的層結構爲佳。由該液狀硬化性樹脂組成物形成硬化膜時，以對基材 (使用構件）進行塗佈爲佳。塗佈方法可使用浸漬法、噴霧法、棒桿塗佈法、滾筒塗佈法、旋轉塗佈法、幕簾塗佈法、照相凹版印刷法、絲網印製法、或噴墨法等方法。又，使液狀硬化性樹脂組成物硬化之方法，沒有特別的限制，例如以加熱硬化爲。此情況，以於30〜200 °C加熱1〜180分鐘爲佳。藉由如此之加熱，可不損傷基材及形成之硬化膜，能更有效獲得防反射性優異之硬化膜。較佳爲於50〜180 °C加熱1〜120分鐘，以於80〜150 °C加熱1〜60 分鐘適合。又，液狀硬化性樹脂組成物藉由添加該（F )成份及/ 或該任意添加成份之光酸產生劑，以活性能量線照射而硬 φ 化亦可。於此所謂活性能量線定義爲，將產生活性種之化合物分解可產生活性種的能量線。如此之活性能量線有，可見光、紫外線、紅外線、X射線、α射線、Θ射線、r射線等光能量線等。但從具有一定之能量水平、硬化速度快、且照射裝置比較便宜又小型的觀點而言，以紫外線爲佳。此情況，例如使用紫外線照射裝置（鹵化金屬燈、高壓水銀燈等），能以0.001〜10J/cm2之光照射條件施行硬化 ;照射條件並不限定於此，以0 · 0 1〜5 J / c m2更佳，以 0.1〜3 J/cm2最適合。又’藉由紫外線硬化時，以添加可提升 -57- 20G538754 (54) 0.1〜3J/cm2最適合。又，藉由紫外線硬化時，以添加可提升硬化速度之放射線（光）聚合引發劑爲佳。還有，硬化膜之硬化程度，例如使用三聚氰胺化合物做爲硬化性化合物時，藉由紅外線分光分析三聚氰胺化合物之羥甲基或烷氧基化甲基之量，或使用索克斯累特萃取器測定膠化率，可定量的確認。液狀硬化性樹脂組成物係含有（B )熱固性化合物、與 B ( F)活性能量線硬化性化合物的雙方之故，爲更有效的硬化，以倂用該加熱與活性能量射之照射爲佳。藉由倂用加熱與活性能量線之照射，能改善硬化膜之耐擦傷性及耐藥品性〇在塗佈液狀硬化性樹脂組成物後之使組成物中的溶劑 (E-1)及溶劑（E-2)蒸發乾燥之過程中，（D)金屬氧化物粒子偏在化於塗佈基底側（與鄰接層之境界附近），或其相反側。因此，在硬化膜之一方的界面附近，（D )金屬氧 φ 化物粒子以高密度存在，在硬化膜之另一方的界面附近， (D)金屬氧化物粒子實質上不存在之故，形成低折射率之樹脂層。因而，藉由使由液狀硬化性樹脂組成物所成之塗膜硬化，可獲得實質上具有二層以上之多層結構的硬化膜。此等形成分離之各層，可藉由例如以電子顯微鏡觀察所得膜之剖面而確認。所謂（D )金屬氧化物粒子高密度存在之層，係指金屬氧化物粒子聚集的部份之意，係實質上以金屬氧化物粒子爲主成份所構成之層，於層內部有與（A )成份等共存的情況。另一方面，所金屬氧化物粒子實質上不存在 -58- (55) 200538754 發明之效果的範圍，少量含有亦可。此層實質上係由（A ) 及（B )成份、或（A ) 、（ B )及（F )成份之硬化物等金屬氧化物粒子以外的成份所構成之層。本發明之硬化膜，大多數的情況係具有形成金屬氧化物粒子高密度存在之層、與金屬氧化物粒子實質上不存在之層，分別連續之層的二層結構。基材使用PET樹脂（包含具有易黏著層之PET樹脂 )等時，通常依順序使基材之層、金屬氧化物粒子高密度 φ 存在之層、金屬氧化物粒子實質上不存在之層，鄰接而形成〇所得硬化膜在其膜厚方向之折射率爲〇·〇5〜0.8改變爲佳，以0.1〜0.8改變更適合。進而，該折射率改變在該實質上二層結構之境界附近具有主要的改變爲佳。折射率之改變的程度，可藉由（D )金屬氧化物粒子之含量、種類，（A)含氟聚合物之含量、組成’及（B)熱固性化合物之含量、種類，加以調整。 φ 又，硬化膜中低折射率部份之折射率爲例如1.3〜1.5 ’ 高折射率部份之折射率爲I·6〜2.2。【實施方式】 [實施例] 下述說明中之「部」或「％」’除特別說明外爲「重量份」、或「重量％」。 [製造例1] -59 - 200538754 (56) (具有聚合性不飽和基之有機化合物的合成）在附置攪拌器的容器內之锍基丙基三甲氧基矽烷22 1重量份及二丁基錫二月桂酸酯1重量份的混合溶液中，將異佛爾酮二異氰酸酯222重量份於乾燥空氣中50 °C下以1小時滴加後，更於70 °C下攪拌3小時。接著，在此反應溶液中，於3 0 °C下以1小時滴加新中村化學公司製之NK酯A-TMM-3LM-N (由季戊四醇三丙烯酸酯 φ 60重量％與季戊四醇四丙烯酸酯40重量％所成。其中與反應有關者，僅具有羥基之季戊四醇三丙烯酸酯。）549重量份後，更於60 °C下攪拌1 〇小時，即得反應液。此反應液中之生成物，即殘餘於具有聚合性不飽基之有機化合物中的異氰酸量，以FT-IR測定之結果爲0.1重量％以下，確認各反應大略定量的進行。生成物之紅外線吸收光譜爲，原料中之锍基的特徵之25 50卡鎖的吸收尖峰、及原料異氰酸酯化合物的特徵之2260卡鎖的吸收光峰消失，可觀察 φ 到新的胺基甲酸酯鍵、及-S(C = 0)NH-基之特徵的1 660卡鎖之尖峰、及丙烯氧基之特徵的1 720卡鎖之尖峰，表示生成同時具有聚合性不飽基之丙烯氧基、與-S(C = 0)NH-基、胺基甲酸酯鍵之丙烯氧基潤飾烷氧基矽烷。藉由上述，即得具有硫代胺基甲酸酯鍵、胺基甲酸酯鍵、烷氧基甲矽烷基、聚合性不飽和基之化合物[該式（4 )所示之化合物（Ab )] 773重量份與和反應無關之季戊四醇四丙烯酸酯220重量份的組成物（A-1)(以下此組成物亦稱爲「烷氧基矽烷1」）。 -60- (57) 200538754 [製造例2] [胺基甲酸酯丙烯酸酯（式（8 )所示之化合物）的合成] 在附置攪拌器的容器內之由異佛爾酮二異氰酸酯18·8重量份與二丁基錫二月桂酸酯0 · 2重量份所成的溶液中，於1 0 °C以1小時滴加新中村化學公司製之NK_ A-TMM-3LM-N ( 與反應有關者，僅具有羥基之季戊四醇三丙烯酸酯。）93重量份後，於6 0 °C攪拌6小時，即得反應液。 φ 此反應液中之生成物，即與製造例1同樣的進行，殘餘異氰酸酯量以下FT-IR測定之結果爲〇.1重量％以下，確認反應大略定量的進行。又，確認分子內含有胺基甲酸酯鍵、及丙烯醯基（聚合性不飽和基）。藉由上述，即得胺基甲酸酯六丙烯酸酯（該式（9)所示之化合物]75重量份、及與反應無關之季戊四醇四丙烯酸酯3 7重量份混合的組成物（A-2)。 φ [製造例3] (含有二氧化矽粒子之硬塗層用組成物的調製）將在製造例1製得之含聚合性不飽基的組成物（A-1 ) 2.3 2重量份、二氧化矽粒子溶膠（甲乙酮二氧化矽溶膠，曰產化學工業股份有限公司製之MEK-ST，數平均粒徑0.022 μιη，二氧化矽濃度30% ) 9 1.3重量份（二氧化矽粒子爲27重量份）、離子交換水0.12重量份、及對-羥基苯基單甲醚 0.01重量份之混合液，於60 t攪拌4小時後，添加原甲酸甲酯1·36重量份，再於同溫度攪拌1小時，即得反應性粒子 -61 - 200538754 (58) [分散液（A - 3 )]。在鋁皿中秤取此分散液（A - 3 ) 2 g後’ 於1 75 °C之加熱板上乾燥1小時’求得秤量之固形份含量爲3 0.7 °/。。又，秤取2 g之分散液於磁性坩堝後，在8 0 t：之加熱板上預熱3 0分鐘，藉由於7 5 0 °C之馬弗爐中燒成1小時後的無機殘渣，求得固形份中之無機含量爲90%。將此分散液（A-3 ) 98.6g、組成物（A-2 ) 3.4g、1-羥基環己基苯基酮2. lg、依爾加丘爾907 {吉巴特殊化學品公司 φ 製，2-甲基-1-[4-(甲硫基）苯基]-2-嗎啉代）丙烷-卜酮 }1.2g、二季戊四醇六丙烯酸酯（DPHA) 33.2g、環己酮7g 混合攪拌，即得含有二氧化砂粒子之硬塗層用組成物（固形份濃度50% ) 145g。 [製造例4] (含有氧化锆粒子之組成物的調製）將第一稀元素化學工業股份有限公司製之UEP-100 ( φ 一次粒徑10〜30 μιη) 300重量份，添加於700重量份之甲乙酮（ΜΕΚ )中，以玻璃小珠施行168小時之分散，去除玻璃小珠即得氧化鉻分散溶膠950重量份。秤取氧化锆分散溶膠2g於鋁皿後，於120 °C之加熱板上乾燥1小時，求得秤量之固形份含量爲30%。將此氧化鉻分散溶膠100g、製造例1合成之組成物（A-1 ) 0.86g、二季戊四醇六丙烯酸酯 (DPHA ) 13.4g、對-甲氧基苯酚0.016g、離子交換水〇.〇3 3 g之混合液，於60 °C攪拌3小時後，添加原甲酸甲酯 0.3 3 2g，再於同溫度下加熱攪拌1小時，即得表面改變氧化 -62- 200538754 (59) 鍩粒子之分散液1 1 6 g。將此分散液1 1 6 g，製造例2合成之組成物（A-2 ) 1.34g、1-羥基環己基苯基酮l.26g、依爾加丘爾907 {吉巴特殊化學品公司製，2-甲基(甲硫基 )苯基]-2-嗎啉（代）丙烷- l-酮 }0.76g，MEK2846g攪拌混合，即得含有氧化锆粒子之組成物（固形份濃度4% ) 2 9 6 4 g ° φ [製造例5] [含有含錫氧化銦（ITO)粒子之組成物的調製] 將富士化學股份有限公司製之ITO溶膠（1〇重量％之 IPA溶膠）700g、DPHA29.5g、{2 -甲基-1-[4-(甲硫基）苯基]-2 -嗎啉（代）丙烷-1 -酮} 1 g、異丙醇1 7 6 9 · 5 g混合，即得固形份濃度4%之含IT0粒子的組成物。 [製造例6] φ [含有含銻氧化錫（ΑΤΟ)粒子之組成物的調製] 將ΑΤΟ粒子（石原鐵庫諾股份有限公司製之SN-100P ，—次粒徑10〜3 〇nm )、分散劑（旭電化工業股份有限公司製之阿得卡普魯洛尼庫TR_701 )、及甲醇、以 9 0 / 2.7 8 / 2 1 1 (重量比）之配合量混合（全固形份含量爲3 1 % ，全無機含量29_6%)。在塗料搖勻器之50ml塑料瓶中’加入玻璃小珠4〇g (多興利可公司製，BZ_01、小珠徑0.lmm、體積約1 6ml )，與上述混合液3〇g ’分散3小時’即得中値粒徑80nm之分散溶膠。將此分散溶膠304g ’組成物（A-1 -63- (60) 200538754 )5.6g、對-甲氧基苯酚O.Olg、離子交換水〇.i2g之混合液，於6 0 °C攪拌3小時後，添加原甲酸甲酯1 .3 g，再於同一溫度加熱攪拌1小時，即得表面改性ΑΤΟ粒子之分散液3 1 1 g 。將此分散液2 7 8 · 3 g、組成物（A - 2 ) 1 · 7 g、季戊四醇三丙烯酸酯8.59g、{2-甲基- l-[4-(甲硫基）苯基]-2-嗎啉（代 )丙烷-l-酮 }〇.88g、甲醇33g、丙二醇單甲醚1 675g混合攪拌，即得含有ΑΤΟ粒子之組成物（固形份濃度5% ) 2000 g [製造例7] [含有含鋁氧化鋅（含A1之ΖηΟ)粒子之組成物的調製] 將氧化鋅粒子（堺化學公司製之含Α1的ΖηΟ，一次粒徑1 0〜2 Onm )、分散劑（楠本化成股份有公司製之哈依普拉多ED151)及丙二醇單甲醚，以27.6/4.8/6 7.6 (重量比）之配合量混合（全固形份含量爲30%、全無機含量27.6% ) 。在塗料搖勻器之50ml塑料瓶中，加入氧化銷小珠40g (小珠徑0.1mm )與上述混合液30g。分散8小時，即得中値粒徑 4 Onm之分散溶膠。於此溶膠290g中，加入季戊四醇三丙烯酸酯10g、{2-甲基-1-[4-(甲硫基）苯基]_2_嗎啉（代）丙烷-1 _酮} 0.5 g、丙二醇單甲醚2 1 3 8 g，混合攪拌，即得含有含鋁氧化鋅粒子之組成物（固形份濃度4%) 243 8§ ° [製造例8] [二氧化矽被覆Ti02粒子分散液（S-1)之調製] -64- 200538754 (61) 加入二氧化矽被覆之氧化鈦微粉末3 5 0重量份、環氧乙烷-環氧丙烷共聚物（平均聚合度約20 ) 80重量份、異丙醇 1 000重量份、丁基溶纖劑1 000重量份，以玻璃小珠施行1〇小時之分散，去除玻璃小珠，即得二氧化矽被覆Ti〇2粒子分散液（S- 1 ) 2430重量份。將所得二氧化矽被覆Ti02粒子分散液秤量於鋁皿上，於1 20 °C之加熱板上乾燥1小時，求得全固形濃度（分散液中之溶劑以外的成份總量之比例）爲1 7 ϋ 重量％。又，將此二氧化矽被覆Ti02粒子分散液秤量於磁性坩堝中，在80 °C之加熱板上預備乾燥30分鐘後，於750 °C 之馬弗爐中燒成1小時，由所得無機殘渣量，及全固形份濃度求得全固形份中之無機含量爲82重量％。以電子顯微鏡觀察此固形物之結果，短軸平均粒徑1 5nm、長軸平均粒徑 4 6nm、縱橫比爲3 . 1。 [製造例9] φ [球狀氧化鉻粒子分散液（S-2)之製造] 將球狀氧化锆微粉末（住友大阪榭面多股份有限公司製，數平均一次粒徑0.01 μιη) 300重量份添加於甲乙酮700重量份中，以珠璃小珠施行1 68小時之分散，去除珠璃小珠，即得甲乙酮氧化鉻溶膠9 5 0重量份。秤量分散溶膠2g於鋁皿中後，於1 20 t之加熱板上乾燥1小時，求得秤量之固形份含量爲3 0%。此固形物之電子顯微鏡觀察的結果，短軸平均粒徑15nm、長軸平均粒徑20nm、縱橫比1.3。 -65· (62) 200538754 [製造例l 〇 ](含氟聚合物1之製造）以氮氣光分取代內容積1 . 5 L之附置電磁攪拌器的不銹鋼製壓熱器後，加入乙酸乙酯5 00 g、全氟（丙基乙烯基醚 )43.2g、乙基乙烯基醚41.2g、羥基乙基乙烯基醚21.5g、非離子性反應性乳化劑之「阿得卡利阿受普NE-30」（旭電化工業股份有限公司製）40· 5g、含偶氮基之聚二甲基矽氧烷的「VPS-1001」（和光純藥工業股份有限公司製）6.0g、 B 及過氧化月桂醯基1.25g，以乾冰-甲醇冷卻至-50 °C後’再度以氮氣將系內之氧氣去除。接著加入六氟丙烯97.4g，開始升溫。壓熱器內之溫度達60 °C時的壓力5.3 xl05pa。其後，於70 t：攪拌20小時繼續反應，將壓熱器水冷至壓力降爲1.7 xl〇5pa時停止反應。達室溫後，放出未反應單體’打開壓熱器’即得固形份濃度2 6.4%之聚合物溶液。將所得聚合物溶液注入甲醇中析出聚合物後，以甲醇洗淨，於50 °C進行真空乾燥，即得220g φ 之含氟聚合物1。所得聚合物，藉由凝膠滲透色譜法確認聚苯乙烯換算數平均分子量（Μη)爲48000，藉由DSC確認玻璃轉移溫度（ Tg)爲26.8 °C，及藉由茜素配位劑法確認氟含量爲50.3%。 [製造例Π](含氟聚合物2之製造）以氮氣充分取代內容積1 ·5之附置電磁攪拌器的不銹鋼製壓熱器後，加入乙酸乙酯5 0〇g ’全氟（丙基乙烯基醚） 75.4g、乙基乙烯基醚3 4g、羥基乙基乙烯基醚41.6g、非離 -66- (63) 200538754 嚤子性反應性乳化劑之「阿得卡利阿受普NE-30」（旭電化工業股份有限公司製）50g、含偶氮基之聚二甲基矽氧烷的「 VPS-1001」（和光純藥工業股份有限公司製）7.5g、及過氧化月桂醯基1.25g，以乾冰-甲醇冷卻至-50它後，再度以氮氣將系內之氧氣去除。接著加入六氟丙烯99· lg，開始升溫。壓熱器內之溫度達6 0 °C時的壓力5 · 3 X 1 05 p a。其後，於7 0 °C攪拌2 0小時 φ 繼續反應，將壓熱器水冷至壓力降爲1 ·7 X 1 〇5pa時停止反應。達室溫後，放出未反應單體，打開壓熱器，即得固形份濃度3 1 %之聚合物溶液。將所得聚合物溶液注入甲醇與水之混合溶劑中析出聚合物後，以甲醇洗淨，於50 t進行真空乾燥，即得22 0g之含氟聚合物2。所得聚合物，藉由凝膠滲透色譜法確認聚苯乙烯換算數平均分子量（Μη )爲37000，藉由DSC確認玻璃轉移溫度（Tg)爲29.4 °C。 φ [製造例1 2 ][連結具有聚合性不飽基之有機化合物的反應性二氧化矽被覆Ti〇2粒子溶膠（化合物Z-1))之製造] 將製造例8製得之二氧化矽被覆Ti〇2粒子分散液（S-1) (全固形份濃度1 7%，粒子濃度1 5 % ) 5 5 6重量份、製造例1 製得之烷氧基矽烷1的溶液2.2重量份、蒸餾水0.23重量份、對苯二酚單甲醚0.04重量份混合，於65 t加熱攪拌。4小時後，添加原甲酸甲酯2.5g，再加熱1小時，即得固形份18%之反應性二氧化矽被覆Ti02粒子溶膠[化合物（Z-1 )]。與製造8同樣的測定粒徑之結果，數平均粒徑（短軸平均粒徑） 67- 200538754 (64) 爲 1 5nm 〇 [製造例13][連結具有聚合性不飽和基之有機化合物的反應性氧化鋁、氧化锆被覆Ti02粒子溶膠（化合物（Z-2 ))之製造] 將氧化鋁、氧化锆被覆Ti02粒子分散液（鐵依卡股份有限公司製，全固形份濃度28%，粒子濃度24% ) 3 94重量份 φ 、製造例1製得之烷氧基矽烷1的溶液2.2重量份、蒸餾水0.23 重量份、對苯二酚單醚〇.〇4重量份混合，於65 °C加熱攪拌。4小時後，添加原甲酸甲酯2.5重量份，再加熱1小時，即得固形份25%之反應性氧化鋁、氧化锆被覆Ti02粒子溶膠[ 化合物（Z-2 )]。與製造例8同樣的測定粒徑之結果，數平均粒徑（短軸平均粒徑）爲20 μιη。 [製造例14][連結具有聚合性不飽和基之有機化合物的反應 φ 性氧化鉻粒子溶膠（化合物（Ζ-3 ))之製造] 將製造例9製得之球狀氧化鉻粒子分散液（S-2 )(粒子濃度3 0% ) 3 1 5重量份、製造例1製得之烷氧基矽烷1的溶液2.2重量份、蒸觀水〇·23重量份、對苯二酷單醚〇.〇4重量份混合，於65 °C加熱攪拌。4小時後，添加原甲酸甲酯2.5重量份，再加熱1小時，即得固形份3 1 %之反應性氧化鉻粒子溶膠[化合物（Z-3 )]。與製造例8同樣的測定粒徑之結果，數平均粒徑（短軸平均粒徑）爲1 5 μιη。 -68- 200538754 (65) [製造例1 5 Π連結具有聚合性不飽和基之有機化合物的反應性氧化鋁、氧化锆被覆Ti02粒子溶膠（化合物（Ζ-4 ))之製造] 將氧化鋁、氧化銷被覆Ti02粒子分散液（鐵依卡股份有限公司製，全固形份濃度28%，粒子濃度24% ) 3 3 3.7重量份，製造例1製得之烷氧基矽烷1的溶液5.4重量份、蒸餾水0.20重量份、對苯二酚單醚0.03重量份混合，於65 °C加 φ 熱攪拌。4小時後，添加原甲酸甲酯2.2重量份，再加熱1小時，即得固形份32%之反應性氧化鋁、氧化鉻被覆Ti02粒子溶膠[化合物（Z-4 )]。與製造例8同樣的測定粒徑之結果，數平均粒徑（短軸平均粒徑）爲20nm。製造例1 6，係不含（F )成份爲必要成份之第一型態的液狀硬化性樹脂組成物之製造例。 [製造例16] φ ( 1 )液狀硬化性樹脂組成物1-1〜1-5之製造藉由將製造例8所得二氧化砂被覆氧化欽分散液（S -1 )24g (固形份4.08g )、製造例1〇所得之含氟聚合物l.2g 、交聯性化合物之甲氧基化甲基三聚氰胺「薩依美魯3 03」 (三井薩依鐵庫股份有限公司製）1.2g與硬化催化劑之催化劑405 0 (三井薩依鐵庫股份有限公司製，芳香族磺酸化合物）〇.68g，溶解於溶劑之甲乙酮32g、甲異丁酮24g、叔丁醇1 6g中，即得組成物I_ 1。與製造例9同樣的測定此液狀硬化性樹脂組成物中之全固形份濃度爲7.5重量％。 -69 - 200538754 (66) 將各成份依下述表1之配合比例配合，得組成物1-2〜1-5。還有，組成2〜5中，使用丁醇，溶劑之組成爲甲乙酮/異丙醇/甲異 = 40/20/3 0/ 1 0 ° (2 )液狀硬化性樹脂組成物1-6之製造除使用卡依納-ADS (耶魯夫·阿多凱 φ 有限公司製，六氟丙烯、四氟乙烯及二氟乙不含羥基及聚合性不飽和基）以外，與液狀成物（組成1 )之製造同樣的進行，即得液組成物（組成1-6 )。樣的進行即丁醇替代叔酮/正丁醇 •曰本股份之共聚物，化性樹脂組硬化性樹脂In the formula, X is a divalent group such as an alkylene group, an arylene group, or an alkoxy group; R4 is a monovalent group such as a group, an aryl group, a halogen-substituted group, or a halogen-substituted aryl group. n2 r5o2s-c-so2r6 中 In the formula, 'R5 and R6 are the same or different from each other, such as a radical, aryl, halogen-substituted alkyl, and halogen-substituted aryl. The photosensitive acid generator can be used alone or in combination of two or more. The solid acid content of the liquid curable resin composition is 100 parts by weight, and the use ratio of the photosensitive acid generator is preferably 0 to 20 parts by weight, and more preferably 0 to 10 parts by weight. When the ratio is too large, the strength of the cured film is deteriorated and the transparency is reduced, and it is extremely unsuitable for the (v) surface active agent liquid hardening resin composition. To improve the coating property of the liquid hardening resin composition, interfacial activity may be matched. Agent. As the surfactant, a well-known one can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In particular, -55- 200538754 ♦ (52) The cured film has excellent properties. Strength and good optical characteristics, it is better to use cationic surfactant. It is more preferable to use a quaternary ammonium salt. Among them, especially when a quaternary polyether ammonium salt is used, it is particularly suitable for improving the wipeability. The cationic surfactants of the quaternary polyether ammonium salts include Adkacolu CC-15, CC-36, CC-42 and the like manufactured by Asahi Denka Chemical Industry Co., Ltd. The proportion of the surfactant used is preferably 1,000 parts by weight to the solid content of the liquid curable resin composition, and preferably 5 parts by weight or less. (vi) Thermal polymerization inhibitors that can be compounded with the liquid hardening resin composition include, for example, pyrogallol, hydroquinone, hydroquinone, methylene blue, tert-butylcatechol, mono Benzyl ether, methyl hydroquinone, pentylquinone, pentyl hydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 '· {1- [4 · [ 1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylene} diphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- 3-phenylpropane and more. The φ thermal polymerization inhibitor is preferably 100 parts by weight based on the solid content of the liquid curable resin composition, and preferably 5 parts by weight or less. (vii) Solvents other than (E) Components A solvent other than (E) components may be added to the liquid curable resin composition. The type and blending amount of such solvents can be freely selected without impairing the scope of the effect of the present invention. The cured film is obtained by curing the liquid curable resin composition and has a multilayer structure of two or more layers. In particular, a layer having a layer of 1 or more existing in the (D) gold-56- (53) 200538754 metal oxide particles with a high density and a layer of 1 or less having a substantially non-existent metal oxide particle in (D) A layer structure above the layer is preferred. When forming a cured film from this liquid curable resin composition, it is preferable to coat the substrate (using member). The coating method may be a dipping method, a spray method, a rod coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a screen printing method, or an inkjet method. There is no particular limitation on the method for curing the liquid curable resin composition, and for example, heat curing is used. In this case, it is preferable to heat at 30 to 200 ° C for 1 to 180 minutes. By such heating, the substrate and the formed hardened film are not damaged, and a hardened film having excellent antireflection properties can be obtained more effectively. The heating is preferably performed at 50 to 180 ° C for 1 to 120 minutes, and the heating is preferably performed at 80 to 150 ° C for 1 to 60 minutes. In addition, the liquid-curable resin composition may be hardened by irradiation with an active energy ray by adding the (F) component and / or the photo-acid generator of the optional added component. Here, the so-called active energy ray is defined as an energy ray that can generate active species by decomposing a compound that generates active species. Examples of such active energy rays include light energy rays, ultraviolet rays, infrared rays, X-rays, α rays, θ rays, and r rays. However, from the viewpoint of having a certain energy level, fast curing speed, and relatively inexpensive and compact irradiation equipment, ultraviolet rays are preferred. In this case, for example, an ultraviolet irradiation device (metal halide lamp, high-pressure mercury lamp, etc.) can be used for curing under a light irradiation condition of 0.001 to 10 J / cm2; the irradiation condition is not limited to this, and 0. 0 1 to 5 J / c m2 is more preferable, and 0.1 ~ 3 J / cm2 is most suitable. And when it is hardened by ultraviolet rays, it can be improved by adding -57-20G538754 (54) 0.1 ~ 3J / cm2. When curing by ultraviolet rays, it is preferable to add a radiation (photo) polymerization initiator which can increase the curing speed. In addition, the degree of hardening of the cured film, for example, when a melamine compound is used as the hardening compound, the amount of hydroxymethyl or alkoxylated methyl groups of the melamine compound is analyzed by infrared spectroscopy, or a Soxhlet extractor is used The gelation rate can be measured and quantitatively confirmed. The liquid curable resin composition contains both (B) a thermosetting compound and B (F) an active energy ray-curable compound. For more effective curing, it is better to use this heating and irradiation with active energy. . By applying heating and irradiation with active energy rays, the scratch resistance and chemical resistance of the cured film can be improved. The solvent (E-1) and the solvent in the composition are applied after the liquid curable resin composition is applied. (E-2) In the process of evaporation and drying, (D) the metal oxide particles are biased on the side of the coating substrate (near the boundary with the adjacent layer), or on the opposite side. Therefore, (D) metal oxide particles are present at a high density near the interface on one side of the cured film, and (D) metal oxide particles are substantially absent near the interface on the other side of the cured film, forming a low level. Refractive index resin layer. Therefore, by curing a coating film made of a liquid curable resin composition, a cured film having a multilayer structure of substantially two or more layers can be obtained. The formation of these separate layers can be confirmed by observing the cross section of the obtained film with an electron microscope, for example. The so-called (D) layer with high density of metal oxide particles refers to the part where the metal oxide particles are aggregated. It is a layer consisting essentially of metal oxide particles as the main component. ) Coexistence of ingredients. On the other hand, the metal oxide particles do not substantially exist. The range of the effect of the invention is -58- (55) 200538754, and it may be contained in a small amount. This layer is essentially a layer composed of components other than metal oxide particles such as (A) and (B) components, or hardened products of (A), (B), and (F) components. In most cases, the cured film of the present invention has a two-layer structure in which a layer that forms a high density of metal oxide particles and a layer that does not substantially exist with the metal oxide particles are separate layers. When a PET resin (including a PET resin having an easily-adhesive layer) is used as a base material, a layer of the base material, a layer in which metal oxide particles are present at a high density φ, and a layer in which metal oxide particles are substantially absent are adjacent to each other in order. The refractive index in the thickness direction of the cured film obtained by forming 0 is preferably changed from 0.05 to 0.8, and more preferably changed from 0.1 to 0.8. Furthermore, it is preferable that the refractive index change has a major change near the boundary of the substantially two-layer structure. The degree of change in refractive index can be adjusted by the content and type of (D) metal oxide particles, (A) content and composition of fluoropolymer, and (B) content and type of thermosetting compound. φ The refractive index of the low refractive index portion in the cured film is, for example, 1.3 to 1.5 ', and the refractive index of the high refractive index portion is I · 6 to 2.2. [Embodiment] [Example] "Part" or "%" in the following description is "part by weight" or "% by weight" unless otherwise specified. [Production Example 1] -59-200538754 (56) (Synthesis of an organic compound having a polymerizable unsaturated group) 1 part by weight of fluorenylpropyltrimethoxysilane in a vessel equipped with a stirrer and dibutyltin dilaurate In a mixed solution of 1 part by weight of an acid ester, 222 parts by weight of isophorone diisocyanate was added dropwise at 50 ° C in dry air for 1 hour, and then stirred at 70 ° C for 3 hours. Next, in this reaction solution, NK ester A-TMM-3LM-N (made from pentaerythritol triacrylate φ60% by weight and pentaerythritol tetraacrylate 40) was added dropwise at 30 ° C over 1 hour at 30 ° C. It is made by weight%. Among them, pentaerythritol triacrylate having only a hydroxyl group is involved in the reaction.) After 549 parts by weight, it was stirred at 60 ° C for 10 hours to obtain a reaction solution. The product in this reaction solution, that is, the amount of isocyanate remaining in the organic compound having a polymerizable unsaturated group, was measured by FT-IR and was 0.1% by weight or less. It was confirmed that each reaction proceeded in a substantially quantitative manner. The infrared absorption spectrum of the product is that the absorption peak of 25-50 locks of the characteristics of the fluorene group in the raw material and the absorption light peak of 2260 locks of the characteristics of the isocyanate compound of the raw material disappear, and φ can be observed to the new amino formic acid The ester bond, and the peak of 1 660 latching characteristic of the -S (C = 0) NH- group, and the peak of 1 720 latching characteristic of the propyleneoxy group, indicating the generation of propylene oxide with polymerizable unsaturated groups at the same time. Group, acryloxy-modified alkoxysilane with -S (C = 0) NH- group, urethane bond. According to the above, a compound having a thiocarbamate bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group can be obtained [a compound (Ab) represented by the formula (4) 773 parts by weight of a composition (A-1) of 220 parts by weight of pentaerythritol tetraacrylate unrelated to the reaction (hereinafter this composition is also referred to as "alkoxysilane 1"). -60- (57) 200538754 [Production Example 2] [Synthesis of urethane acrylate (compound represented by formula (8))] Isophorone diisocyanate 18 · in a container equipped with a stirrer To a solution of 8 parts by weight and 0.2 parts by weight of dibutyltin dilaurate, NK_ A-TMM-3LM-N (related to the reaction) manufactured by Shin Nakamura Chemical Co., Ltd. was added dropwise at 10 ° C for 1 hour. , Pentaerythritol triacrylate having only hydroxyl groups.) After 93 parts by weight, it was stirred at 60 ° C for 6 hours to obtain a reaction solution. φ The product in this reaction solution was carried out in the same manner as in Production Example 1. The result of the FT-IR measurement below the amount of residual isocyanate was 0.1% by weight or less, and it was confirmed that the reaction proceeded approximately quantitatively. In addition, it was confirmed that a urethane bond and an acryl group (polymerizable unsaturated group) were contained in the molecule. Based on the above, a composition (A-2) in which 75 parts by weight of urethane hexaacrylate (the compound represented by the formula (9)) and 37 parts by weight of pentaerythritol tetraacrylate unrelated to the reaction is obtained is obtained. ) Φ [Production Example 3] (Preparation of composition for hard coat layer containing silicon dioxide particles) The polymerizable unsaturated group-containing composition (A-1) obtained in Production Example 1 was 2.3 2 parts by weight 、 Silica dioxide particle sol (Methyl ethyl ketone silica sol, MEK-ST manufactured by Yusan Chemical Industry Co., Ltd., number average particle size 0.022 μm, silicon dioxide concentration 30%) 9 1.3 parts by weight (silica dioxide particles are 27 parts by weight), 0.12 parts by weight of ion-exchanged water, and 0.01 parts by weight of p-hydroxyphenyl monomethyl ether, and after stirring at 60 t for 4 hours, 1.36 parts by weight of methyl orthoformate was added, and the same Stir at temperature for 1 hour to obtain reactive particles -61-200538754 (58) [dispersion (A-3)]. After weighing 2 g of this dispersion (A-3) in an aluminum dish, at 1 75 ° C Dry on a hot plate for 1 hour 'to obtain a solid content of 3 0.7 ° /. Weigh 2 g of the dispersion into a magnetic After the pot was preheated for 30 minutes on a hot plate at 80 t: The inorganic content of the solid content was 90% based on the inorganic residue after firing for 1 hour in a muffle furnace at 750 ° C. 98.6 g of this dispersion (A-3), 3.4 g of composition (A-2), 2. lg of 1-hydroxycyclohexylphenyl ketone, lglacur 907 {made by Jiba Specialty Chemicals Corporation φ 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino) propane-butanone} 1.2g, dipentaerythritol hexaacrylate (DPHA) 33.2g, cyclohexanone 7g By stirring, 145 g of a hard coating composition (solid content concentration 50%) containing sand dioxide particles was obtained. [Manufacturing Example 4] (Preparation of composition containing zirconia particles) 300 parts by weight of UEP-100 (φ primary particle size 10 to 30 μιη) manufactured by Daiichi Element Chemical Co., Ltd. was added to 700 parts by weight In methyl ethyl ketone (MEK), the glass beads were dispersed for 168 hours, and the glass beads were removed to obtain 950 parts by weight of a chromium oxide dispersion sol. After weighing 2 g of the zirconia-dispersed sol in an aluminum dish, it was dried on a hot plate at 120 ° C for 1 hour to obtain a solid content of 30%. 100 g of this chromium oxide dispersed sol, 0.86 g of the composition (A-1) synthesized in Production Example 1, 13.4 g of dipentaerythritol hexaacrylate (DPHA), 0.016 g of p-methoxyphenol, and ion-exchanged water 0.03 3 g of the mixture was stirred at 60 ° C for 3 hours, then 0.3 3 2 g of methyl orthoformate was added, and then heated and stirred at the same temperature for 1 hour to obtain the surface-modified oxide-62- 200538754 (59) Liquid 1 1 6 g. 1 16 g of this dispersion was prepared, 1.34 g of the composition (A-2) synthesized in Production Example 2, 1.26 g of 1-hydroxycyclohexylphenyl ketone, and Ilgachur 907 {manufactured by Jiba Specialty Chemicals Co., Ltd. , 2-methyl (methylthio) phenyl] -2-morpholine (substituted) propane-l-one} 0.76g, MEK2846g, and mixed by stirring to obtain a composition containing zirconia particles (solid content concentration 4%) 2 9 6 4 g ° φ [Production Example 5] [Preparation of composition containing tin-containing indium oxide (ITO) particles] 700 g of ITO sol (10% by weight IPA sol) manufactured by Fuji Chemical Co., Ltd. and DPHA29 .5g, {2-methyl-1- [4- (methylthio) phenyl] -2-morpholino (propane) -1-one} 1 g, isopropanol 1 7 6 9 · 5 g mixed That is, a composition containing ITO particles with a solid concentration of 4% is obtained. [Manufacturing Example 6] φ [Preparation of composition containing antimony-containing tin oxide (ATO) particles] ATO particles (SN-100P manufactured by Ishihara Tiekuno Co., Ltd., with a secondary particle size of 10 to 300 nm), Dispersant (Adekproluniku TR_701 manufactured by Asahi Chemical Industry Co., Ltd.), and methanol, mixed with a mixing amount of 9 0 / 2.7 8/2 1 1 (weight ratio) (the total solid content is 3) 1%, total inorganic content 29_6%). Into a 50 ml plastic bottle of a paint shaker, 40 g of glass beads (manufactured by Dorsett Rico, BZ_01, bead diameter of 0.1 mm, and volume of about 16 ml) were added, and 30 g of the above mixed solution was dispersed. In 3 hours, a dispersion sol with a particle size of 80 nm was obtained. 304 g of this dispersed sol (A-1 -63- (60) 200538754) 5.6 g, p-methoxyphenol O.Olg, ion-exchanged water 0.12 g of a mixed solution were stirred at 60 ° C for 3 After 1 hour, 1.3 g of methyl orthoformate was added, and then heated and stirred at the same temperature for 1 hour to obtain a surface-modified ATO particle dispersion 3 1 1 g. This dispersion 2 7 8 · 3 g, composition (A-2) 1 · 7 g, pentaerythritol triacrylate 8.59 g, {2-methyl-l- [4- (methylthio) phenyl]- 2-morpholine (substituted) propane-l-one} .88 g, 33 g of methanol, and 1 675 g of propylene glycol monomethyl ether were mixed and stirred to obtain a composition containing ATO particles (solid content concentration 5%) 2000 g [Production Example 7 ] [Preparation of composition containing aluminum oxide-containing zinc oxide (containing ZηΟ of A1) particles] Zinc oxide particles (Zeta containing A1 of Zynol Corporation, primary particle size of 10 to 2 Onm), a dispersant (Nanmoto Chemical Co., Ltd.) Shares include the company's Haiprado ED151) and propylene glycol monomethyl ether, which are mixed in a compounding amount of 27.6 / 4.8 / 6 7.6 (weight ratio) (the total solid content is 30% and the total inorganic content is 27.6%). In a 50 ml plastic bottle of a paint shaker, 40 g of oxidized pin beads (bead diameter 0.1 mm) and 30 g of the above-mentioned mixed liquid were added. Disperse for 8 hours to obtain a dispersed sol with a median particle size of 4 Onm. To 290 g of this sol, 10 g of pentaerythritol triacrylate, {2-methyl-1- [4- (methylthio) phenyl] _2_morpholine (substituted) propane-1_one} 0.5 g, and propylene glycol mono Methyl ether 2 1 3 8 g, mixed and stirred to obtain a composition containing aluminum oxide-containing zinc oxide particles (solid content concentration 4%) 243 8§ ° [Manufacturing Example 8] [Silica dioxide-coated Ti02 particle dispersion (S- 1) Modulation] -64- 200538754 (61) Add silicon dioxide-coated titanium oxide fine powder 3 50 parts by weight, ethylene oxide-propylene oxide copolymer (average degree of polymerization about 20) 80 parts by weight, 1,000 parts by weight of propanol and 1,000 parts by weight of butyl cellosolve were dispersed with glass beads for 10 hours, and the glass beads were removed to obtain a silica-coated Ti02 particle dispersion (S-1) 2430 weight Serving. The obtained silica-coated Ti02 particle dispersion was weighed on an aluminum dish, and dried on a hot plate at 120 ° C for 1 hour. The total solid concentration (the ratio of the total amount of components other than the solvent in the dispersion) was determined to be 1 7 ％% by weight. In addition, this silicon dioxide-coated Ti02 particle dispersion was weighed in a magnetic crucible, preliminarily dried on a heating plate at 80 ° C for 30 minutes, and then fired in a muffle furnace at 750 ° C for 1 hour. The obtained inorganic residue was The amount and the total solid content concentration obtained the inorganic content in the total solid content of 82% by weight. As a result of observing the solid with an electron microscope, the average particle diameter of the short axis was 15 nm, the average particle diameter of the long axis was 46 nm, and the aspect ratio was 3.1. [Production Example 9] φ [Production of spherical chromium oxide particle dispersion liquid (S-2)] Spherical zirconia fine powder (manufactured by Sumitomo Osaka Kementa Co., Ltd., number average primary particle size 0.01 μιη) 300 weight Added to 700 parts by weight of methyl ethyl ketone, dispersed for 68 hours with beads and beads, and removed beads and beads to obtain 950 parts by weight of methyl ethyl ketone chromium oxide sol. After weighing 2g of the dispersed sol in an aluminum dish, it was dried on a hot plate at 120 t for 1 hour, and the solid content of the weighing was determined to be 30%. As a result of observation with an electron microscope of this solid, the average particle diameter of the short axis was 15 nm, the average particle diameter of the long axis was 20 nm, and the aspect ratio was 1.3. -65 · (62) 200538754 [Manufacturing example 10] (manufactured by fluoropolymer 1) Replace the inner volume 1.5 L stainless steel autoclave with electromagnetic stirrer with nitrogen light, and add ethyl acetate 5 00 g, 43.2 g of perfluoro (propyl vinyl ether), 41.2 g of ethyl vinyl ether, 21.5 g of hydroxyethyl vinyl ether, non-reactive emulsifiers -30 "(manufactured by Asahi Chemical Industry Co., Ltd.) 40 · 5g, azo group-containing polydimethylsiloxane" VPS-1001 "(manufactured by Wako Pure Chemical Industries, Ltd.) 6.0g, B and Oxidize 1.25g of lauryl hydrazone, cool to -50 ° C with dry ice-methanol, and remove the oxygen in the system with nitrogen again. Next, 97.4 g of hexafluoropropylene was added, and the temperature was started to rise. The temperature in the autoclave reaches a pressure of 5.3 x l05pa at 60 ° C. Thereafter, the reaction was continued at 70 t: stirring for 20 hours, and the reaction was stopped when the autoclave was water-cooled to a pressure drop of 1.7 x 105 Pa. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid concentration of 2 6.4%. The obtained polymer solution was poured into methanol to precipitate a polymer, and the polymer was washed with methanol and vacuum-dried at 50 ° C to obtain 220 g of fluoropolymer 1 of φ. The obtained polymer was confirmed by gel permeation chromatography to have a polystyrene-equivalent number-average molecular weight (Mη) of 48,000, DSC to confirm that the glass transition temperature (Tg) was 26.8 ° C, and that to be confirmed by the alizarin complexing agent method. The fluorine content was 50.3%. [Manufacturing example Π] (Production of fluoropolymer 2) After fully replacing the stainless steel autoclave with an electromagnetic stirrer with an internal volume of 1 · 5 with nitrogen, 500 g of ethyl perfluoro (propyl) was added. (Vinyl ether) 75.4g, ethyl vinyl ether 3 4g, hydroxyethyl vinyl ether 41.6g, non-ion-66- (63) 200538754 Gardenia reactive emulsifier "Adekalea AP" -30 "(manufactured by Asahi Denka Kogyo Co., Ltd.) 50 g, 7.5 g of" VPS-1001 "(manufactured by Wako Pure Chemical Industries, Ltd.) containing polydimethylsiloxane containing azo groups, and laurel peroxide Based on 1.25 g, it was cooled to -50 with dry ice-methanol, and then the oxygen in the system was removed again with nitrogen. Next, hexafluoropropylene 99 · lg was added, and the temperature was started to rise. The temperature in the autoclave is 5 · 3 X 1 05 p a at 60 ° C. After that, it was stirred at 70 ° C for 20 hours. Φ continued the reaction, and the autoclave was cooled with water until the pressure dropped to 1 · 7 X 105 Pa, and the reaction was stopped. After reaching room temperature, the unreacted monomer was discharged and the autoclave was opened to obtain a polymer solution having a solid concentration of 31%. The obtained polymer solution was poured into a mixed solvent of methanol and water to precipitate a polymer, and the polymer was washed with methanol and vacuum-dried at 50 t to obtain 220 g of a fluoropolymer 2. The obtained polymer was confirmed to have a polystyrene-equivalent number average molecular weight (Mη) of 37,000 by gel permeation chromatography, and a glass transition temperature (Tg) of 29.4 ° C was confirmed by DSC. φ [Manufacturing Example 1 2] [Production of reactive silica-coated Ti02 particle sol (compound Z-1)) that connects organic compounds having polymerizable unsaturated groups] Silicon dioxide obtained in Manufacturing Example 8 Covered Ti〇2 particle dispersion (S-1) (full solid content concentration 17%, particle concentration 15%) 5 5 6 parts by weight, 2.2 parts by weight of the solution of the alkoxysilane 1 obtained in Production Example 1, 0.23 parts by weight of distilled water and 0.04 parts by weight of hydroquinone monomethyl ether were mixed, and heated and stirred at 65 t. After 4 hours, 2.5 g of methyl orthoformate was added and heated for 1 hour to obtain a reactive silica dioxide-coated Ti02 particle sol [compound (Z-1)] having a solid content of 18%. As a result of measuring the particle diameter in the same manner as in Production 8, the number average particle diameter (short-axis average particle diameter) 67-200538754 (64) was 15 nm. [Production Example 13] [Reaction of connecting organic compound having polymerizable unsaturated group Of alumina and zirconia-coated Ti02 particle sol (compound (Z-2))] Alumina and zirconia-coated Ti02 particle dispersion (manufactured by Tieka Co., Ltd., full solids concentration 28%, particle concentration 24%) 3 94 parts by weight φ, 2.2 parts by weight of a solution of the alkoxysilane 1 obtained in Production Example 1, 0.23 parts by weight of distilled water, 0.44 parts by weight of hydroquinone monoether, and heated at 65 ° C Stir. After 4 hours, 2.5 parts by weight of methyl orthoformate was added and heated for 1 hour to obtain a reactive alumina and zirconia-coated Ti02 particle sol [compound (Z-2)] with a solid content of 25%. As a result of measuring the particle diameter in the same manner as in Production Example 8, the number average particle diameter (minor axis average particle diameter) was 20 μm. [Production Example 14] [Production of reaction φ-type chromium oxide particle sol (compound (Z-3)) that links organic compounds having polymerizable unsaturated groups] A spherical chromium oxide particle dispersion liquid prepared in Production Example 9 ( S-2) (particle concentration 30%) 3 1 5 parts by weight, 2.2 parts by weight of a solution of the alkoxysilane 1 prepared in Production Example 1, distilled water 0.23 parts by weight, terephthalic acid monoether. .04 parts by weight are mixed, and heated and stirred at 65 ° C. After 4 hours, 2.5 parts by weight of methyl orthoformate was added and heated for 1 hour to obtain a reactive chromium oxide particle sol [compound (Z-3)] with a solid content of 31%. As a result of measuring the particle diameter in the same manner as in Production Example 8, the number average particle diameter (minor axis average particle diameter) was 15 μm. -68- 200538754 (65) [Production Example 1 5 Manufacture of reactive alumina and zirconia-coated Ti02 particle sol (compound (Z-4)) connected with organic compound having polymerizable unsaturated group] Alumina, Oxide pin-coated Ti02 particle dispersion (manufactured by Tieka Co., Ltd., full solids concentration 28%, particle concentration 24%) 3 3 3.7 parts by weight, 5.4 parts by weight of the solution of the alkoxysilane 1 produced in Production Example 1 Mix 0.20 parts by weight of distilled water and 0.03 parts by weight of hydroquinone monoether, and stir at 65 ° C with φ. After 4 hours, 2.2 parts by weight of methyl orthoformate was added and heated for 1 hour to obtain a reactive alumina and chromium oxide-coated Ti02 particle sol [compound (Z-4)] with a solid content of 32%. As a result of measuring the particle diameter in the same manner as in Production Example 8, the number average particle diameter (minor axis average particle diameter) was 20 nm. Manufacturing Example 16 is a manufacturing example of the liquid hardening resin composition of the first type that does not contain (F) component as an essential component. [Production Example 16] Production of φ (1) liquid curable resin composition 1-1 to 1-5. 24 g (solid content 4.08) of the oxide dispersion (S -1) coated with the dioxide dioxide obtained in Production Example 8 was prepared. g) 1.2 g of fluoropolymer obtained in Production Example 10, methoxylated methyl melamine "Saimiru 3 03" (made by Mitsui Sayi Iron Depot Co., Ltd.) of a crosslinkable compound 4068 of catalyst with a hardening catalyst (made by Mitsui Sakai Iron Co., Ltd., aromatic sulfonic acid compound) 0.68 g, dissolved in 32 g of methyl ethyl ketone, 24 g of methyl isobutyl ketone, and 16 g of tert-butyl alcohol Composition I_ 1. The concentration of the total solid content in this liquid curable resin composition was measured in the same manner as in Production Example 9 and was 7.5% by weight. -69-200538754 (66) Each component is blended according to the mixing ratio in Table 1 below to obtain a composition 1-2 to 1-5. In addition, in the compositions 2 to 5, butanol is used, and the composition of the solvent is methyl ethyl ketone / isopropanol / methyliso = 40/20/3 0/1 0 ° (2) Liquid hardening resin composition 1-6 Except for using Kayna-ADS (manufactured by Yalef Adoka φ Co., Ltd., hexafluoropropylene, tetrafluoroethylene, and difluoroethyl do not contain hydroxyl groups and polymerizable unsaturated groups), and liquid products (composition 1) The production is carried out in the same manner to obtain a liquid composition (composition 1-6). This process is the replacement of tertiary ketone / n-butanol with butanol. • Copolymer of this stock, chemical resin group, hardening resin.

-70- 200538754 (67)-70- 200538754 (67)

組成1-6 1 ^Τ) (Ν 1 51.3 r-H in 00 100 組成1-5 Ό (N 1 On 1 (N ο 100 組成1-4 〇 1 兰 1 VO (N VO (Ν 101 組成1-3 (N 1 On 1 100 組成1-2 1 1 〇 100 組成1-1 25.1 1 1 (Τ) Τ-Η F-H 00 100 組成物之固形份的組成(重量％) 製造例10 卡依納-ADS 耧燦嫲屮，M 鵾〇安 Η 祕鹏二氧化矽被覆Ti〇2 薩依美魯303 催化劑4050 合計含氟聚合物1 含氟聚合物(無羥基）金屬氧化物粒子熱固性化合物硬化催化劑(熱酸產生劑）成分 Q g U -71 - (68) 200538754 表1中之略號爲如下者。 (A) 含氟聚合物：上述製造例1製得之含氟聚合物。卡依納AD S :耶魯夫•阿多凱姆•日本股份有限公司製；六氟丙烯、四氟乙烯、二氟乙烯之共聚物’不含羥基及聚合性不飽和基。 (B) 金屬氧化物粒子氧化鋁、氧化鍩被覆Ti02粒子分散液：鐵依卡股份有限 φ 公司製，全固形份濃度28%、粒子濃度24%、數平均粒徑 20nm 〇二氧化矽被覆Ti02粒子分散液：製造例2製得者。 (E)薩依美魯3 03:甲氧基化甲基三聚氰胺，三并薩依鐵庫股份有限公司製。 (F )催化劑4050 :三井薩依鐵庫股份有限公司製，芳香族磺酸化合物。製造例17〜24，係含有（F )成份爲必要成份之第二型 φ 態的液狀硬化性樹脂組成物之製造例。 [製造例17] (液狀硬化性樹脂組成物II-1之調製）藉由將製造例12所得之反應性二氧化矽被覆Ti02粒子溶膠[化合物（Z-1 )、反應性粒子50.6g ) 280.9g、製造例1 1 所得之（含氟聚合物2 ) 23 · 1 g、熱固性化合物之甲氧基化甲基三聚氰胺「薩依美魯3 03」（三井薩依鐵庫股份有限公司製）14.3g、與硬化催化劑之「催化劑4050」（三井薩依鐵 -72- (69) 200538754 % 庫股份有限公司製，芳香族磺酸化合物’有效成份濃度32% )1 1.9g，活性能量線硬化性化合物之該式（8 )所示的製造例2製得之組成物（A - 2 ) 2 · 0 g、二季戊四醇六丙烯酸酯（曰本化藥股份有限公司製，商品名：卡亞拉多DPHA-2C) 5.3g 、光聚合引發劑之{2 -甲基- l- [4-(甲硫基）苯基]-2 -嗎啉 (代）丙烷- l-酮}(依爾加丘爾907 ’吉巴特殊化學品公司製）l.Og、溶解於溶劑之甲乙酮300g、甲異丁醇320g、叔 φ 丁醇2 1 3 g中，即得液狀硬化性樹脂組成物Π-1。與製造例8 同樣的測定此液狀硬化性樹脂組成物之全固形份濃度（液狀硬化性樹脂組成物之固形份的比例）爲8 · 5重量％。 [製造例18〜24] (液狀硬化性樹脂組成物II-2〜II-8之調製）除將組成物之各成份的配合比例依表2所示改變以外，與製造例1 7同樣的進行，即調製成液狀硬化性樹脂組成 • 物 II-2〜II-8。液狀硬化性樹脂組成物II-2〜II-8之固形份組成，如表2 所示。 -73- 200538754 (70) 製造例 24 00 1 HH HH 寸 r-Η 寸 ?—Η Η 〇 ο ο ο (Ν 00 (Ν (N 卜 ο ο r*H 製造例 23 卜 1 HH ο (Ν (Ν τ-Η 〇 ο ο ο Ο 〇 (N O Ο Ο f-H 製造例 22 1 HH HH ο (Ν (Ν τ-Η 〇 ο ο ο Ο νο 〇 (N o ο ο 1—Η 製造例 21 I ΗΗ ΗΗ ο 00 CN (Ν Os 00 m d ο Ο ο ο 〇 (N o ▼-H Ο Ο 製造例 20 寸 1 ΗΗ ►—Η r-H 00 r-H ο cn ο ο ο ο ο 寸 in 〇 (N 〇 r-H Ο ο ^-Η 製造例 19 1 Η-Η ΗΗ τ—Η m (Ν 00 m ο ο ο ο ο m 〇 (N o Ο Ο r-H 製造例 18 (Ν I ΗΗ ΗΗ (Ν 00 m ο ο Ο ο ο m 〇 (N 〇 Ο ο r-H 製造例 17 r-H 1 ΗΗ ΗΗ ^-Η m (Ν m ▼—Η 00 ο ο Ο ο ο m 〇 (N o ο ο r-H 組成物之固形份的成份組成 (質量％) 液狀硬化性樹脂組成物製造例11 薩依美魯303 催化劑4050 製造例12 (ζ-1) m m ^ 製造例14 (Ζ-3) 製造例9 (Ζ-2) 製造例15 (Ζ-4) 卡亞拉多 DPHA-2C 製造例2 依爾加丘爾 907 合計含氟聚合物2 熱固性化合物硬化催化劑金屬氧化物微粒子溶膠 i_^_ DD ^ is 光聚合引發劑 /—·Ν PQ y^-N Q ϋ -74- 200538754 (71) 實施例I-1〜1-5及評估例1-1，係使用上述製造例16製得之液狀硬化性樹脂組成物1-1〜1-6之層合物的實施例及評估例。 [實施例1-1、比較例1] (層合物之製作） (1 )硬塗層之製作使用金屬絲棒桿塗佈器（基1 2 )，將製造例3調製成之含二氧化矽粒子的硬塗層用組成物（固形份濃度45% ) 塗佈於三乙醯基纖維素薄膜（洛弗公司製，膜厚80 μιη) 後，於烘箱中8 〇 °C乾燥1分鐘。接著，藉由在空氣下，使用高壓水銀燈以0.6J/cm2之光照射條件照射紫外線’形成硬化膜層。以觸針式膜厚計測定硬化膜層之膜厚爲5 μιη ° (2)聚噻吩層（導電層、防靜電層）之製作將氧化劑之FeCl2，在甲醇、2-丁醇及乙基溶纖劑分別以6 : 3 : 1之比例混合而成的溶劑中溶解成3重量％，即調製成催化劑溶液。在設置硬塗層之三乙醯基纖維素薄膜表面上，將該調製之催化劑溶液以旋轉塗佈後，使所得催化劑塗膜於60 °C乾燥3分鐘。接著，將此形成硬塗層及催化劑塗膜之聚酯薄膜，裝置於設計生成飽和狀態之3,4-伸乙二氧基噻吩單體的CVD 小室，使3，4 _伸乙二氧基噻吩進行聚合反應3 0秒鐘後，以 -75- (72) 200538754 4 甲醇溶劑洗淨並去除未反應物，形成導電層。 (3 )中折射率層之製作使用金屬絲棒桿塗佈器（#3 )，將製造例4調製之含有氧化鍩粒子的組成物（固形份濃度4% )，塗佈於（2 ) 製成之聚噻吩層上後，於烘箱中80 °C乾燥1分鐘。接著，藉由在氮氣氣體環境下，使用高壓水銀燈，以〇·6 J/cm2之 φ 光照射條件照射紫外線，形成硬化膜層。以反射分光計算出硬化膜層之膜厚爲65 μιη。 (4 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（#3 )，分別將製造例16所得之組成I-1〜1-6的液狀硬化性樹脂組成物，塗佈於（3 )製成之中折射率層上後，藉由於烘箱中120 °C加熱10分鐘，形成膜厚爲0.2 μιη之硬化膜層。 [實施例1-2、比較例2] (層合物之製作） (1)聚噻吩層（導電層、防靜電層）之製作在三乙醯基纖維素薄膜表面上，將實施例1-1 ( 2 )調製之催化劑溶液以旋轉塗佈後，使所得催化劑塗膜於6 0 °C乾燥3分鐘。接著，將此形成催化劑塗膜之聚酯薄膜裝置於，設計生成飽和狀態之3,4-伸乙二氧基噻吩單體的CVD小室，使 -76- 200538754 (73) 3，4-伸乙二氧基噻吩進行聚合反應30秒鐘後，以甲醇溶劑洗淨並去除未反應物，形成導電層。 (2 )硬塗層之製作使用金屬絲棒桿塗佈器（基1 2 )，將製造例3調製成之含有二氧化矽粒子的硬塗層用組成物（固形份濃度45 % )塗佈於（1 )形成之導電層上後，在烘箱中80 °C乾燥1 φ 分鐘。接著，藉由在空氣下，使用高壓水銀燈’以 0.6J/cm2之光照射條件照射紫外線，形成硬化膜層。 (3 )中折射率層之製作使用金屬絲棒桿塗佈器（基3 )，將製造例5調製成之含有ITO粒子的組成物（固形份濃度4% )，塗佈於（2)製成之硬塗層上後，於烘箱中80 °C乾燥1分鐘。接著，藉由在氮氣氣體環境下，使用高壓水銀燈，以〇.6J/cm2之光照 φ 射條件照射紫外線，形成硬化膜層。以反射分光計算出硬化膜層之膜厚爲65 nm。 (4 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（#3 )，分別將製造例1 6所得之組成1-1〜1-6的液狀硬化性樹脂組成物，塗佈於（3)製成之中折射率層上後，藉由在烘箱中1 2 0 °C加熱1 〇分鐘，形成膜厚爲0.2 μιη之硬化膜層。 -77- (74) 200538754 [實施例1-3、1-4及比較例3、4] (層合物之製作） (1)聚噻吩層（導電層、防靜電層）之製作與實施例1-2 ( 1 )同樣的製作。 (2 )硬塗層之製作與實施例1-2 ( 1 )同樣的製作。 (3 )中折射率層之製作使用金屬絲棒桿塗佈器（基3 )，將替代製造例5調製之ITO粒子的製造例6或7調製之含有ΑΤΟ粒子的組成物（固形份濃度5% )或含有Α1之ΖηΟ粒子組成物（固形份濃度4% )，塗佈於（2 )製成之硬塗層上後，於烘箱中80 °C乾燥 1分鐘。接著，藉由在氮氣氣體環境下，使用高壓水銀燈，以0.6J/cm2之光照射條件照射紫外線，形成硬化膜層。 φ 以反射分光計算出硬化膜層之膜厚爲65 nm。 (4 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（#3 )，分別將製造例1 6所得之組成1-1〜1-6的液狀硬化性樹脂組成物，塗佈於（3 )製成之中折射率層上後，藉由在烘箱中1 2 0 °C加熱1 〇分鐘’形成膜厚爲0.2 μηι之硬化膜層。 [實施例1-5、比較例5] -78- 200538754 (75) (層合物之製作） (1)聚噻吩層（導電層、防靜電層）之製作與實施例1-2 ( 1)同樣的製作。 (2 )硬塗層之製作與實施例1-2 ( 1 )同樣的製作。 (3 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（基3 )，分別將製造例16所得之組成1-1〜1-6的液狀硬化性樹脂組成物，塗佈於（2)製成之硬塗層上後，藉由在120 °C烘箱中加熱10分鐘，形成膜厚爲0.2 μιη之硬化膜層。 [評估例1-1] (層合物之評估）以穿透型電子顯微鏡觀察實施例1-1〜1-5及比較例1〜5所得之層合物的剖面，確認使用組成1-1、1-2、1-3、1-5之層合物中，低折射率層與高折射率層分離爲兩層。此時，低折射率爲金屬氧化物粒子實質上不存在之層游離基聚合引發劑金屬氧化物粒子高密度存在之層，高折射率層爲金屬氧化物粒子高密度存在之層。使用組成1-4之層合物中，高折射率層與低折射率層爲均勻結構，並無層分離。使用組成1-6之層合物中，高折射率層與低折射率層一部份凝聚，並無層分離。 -79- (76) 200538754 圖8爲兩層分離、不分離（一部份凝聚）、及均勻結構之各狀態的示意圖。藉由分光反射率測定裝置（將大型試料室積分球附屬裝置1 50-09090組入之自動記錄分光光度計U-3410，日立製作所股份有限公司製），測定波長550nm之反射率，評估使用組成1-1、1-2、Ι·3、Ι·5之防反射用層合物的防反射性。具體而言，以鋁之蒸鍍膜中的反射率爲基準（1 〇〇% )，測定 φ 防反射用層合物（防反射膜）之反射率。其結果，於波長 5 5 Onm，任一種層合物之反射率均爲1 %以下。實施例II-1〜II-5及評估例II-1，係使用上述製造例 17〜24製得之層合物Π-1〜Π-8的層合物之實施例及評估例。 [實施例Π-1] (層合物之製作） (1 )硬塗層之製作 φ 使用金屬絲棒桿塗佈器（基1 2 )，將製造例3調製成之含有二氧化矽粒子的硬塗層用組成物（固形份濃度45% )塗佈於三乙醯基纖維素薄膜（洛弗公司製，膜厚80 μιη )後，於烘箱中80 。(：乾燥1分鐘。接著，藉由在空氣下使用高壓水銀燈，以〇.6J/cm2之光照射條件照射紫外線，形成硬化膜層。以觸針式膜厚計測定硬化膜層之膜厚爲5 μιη (2)聚噻吩層（導電層、防靜電層）之製作 -80- 200538754 (77) 將氧化劑之FeCl2，在甲醇、2-丁醇及乙基溶纖劑分別以6 : 3 : 1之比例混合而成的溶劑中溶解成3重量％，即調製成催化劑溶液。在設置硬塗層之三乙醯基纖維素薄膜表面上，將該調製之催化劑溶液以旋轉塗佈後，使所得催化劑塗膜於60 °C乾燥3分鐘。接著，將此形成硬塗層及催化劑塗膜之聚酯薄膜，裝 φ 置於設計生成飽和狀態之3,4-伸乙二氧基噻吩單位的CVD 小室，使3,4-伸乙二氧基噻吩進行聚合反應30秒鐘後，以甲醇溶劑洗淨並去除未反應物，形成導電層。 (3 )中折射率層使用金屬絲棒桿塗佈器（#3 )，將製造例4調製之含有氧化銷粒子的組成物（固形份濃度4% )，塗佈於（2 ) 製成之聚噻吩層上後，於烘箱中80 °C乾燥1分鐘。接著， φ 藉由在氮氣氣體環境下使用高壓水銀燈，以〇.6J/cm2之光照射條件照射紫外線，形成硬化膜層。以反射分光計算出硬化膜層之膜厚爲65 nm。 (4 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（#3 )，分別將製造例17〜24所得之液狀硬化性樹脂組成物II-1〜II-8，塗佈於（3 )製成之中折射率層上後，於烘箱中1 4 0 °C乾燥2分鐘。藉由在大氣下使用歐庫公司製之輸送帶式水銀燈，照射〇.6J/cm2之 -81 - (78) 200538754 紫外線，形成膜厚O·2 Km之硬化膜層。又，使用金屬絲棒桿塗佈器（#3 ) ’分別將製造例 17〜24所得之液狀硬化性樹脂組成物II-1〜Π-8，塗佈於（3 ) 製成之中折射率層上後，藉由在烘箱中120 °c加熱10分鐘，形成膜厚0.2 μιη之硬化膜層。 [實施例ΙΙ-2] (層合物之製作） (1)聚噻吩層（導電層、防靜電層）之製作在三乙醯基纖維素薄膜表面上，將實施例ΙΙ-1 ( 2 )調製之催化劑溶液以旋轉塗佈後’使所得催化劑薄膜於60 °C乾燥3分鐘。接著，將此形成催化劑塗膜之聚酯薄膜裝置於’設計生成飽和狀態之3,4·伸乙二氧基噻吩單體的CVD小室’使 3，4-伸乙二氧基噻吩進行聚合反應30秒鐘後，以甲醇洗淨 φ 並去除未反應物形成導電層。 (2 )硬塗層之製作使用金屬絲棒桿塗佈器（# 1 2 )，將製造例3調製成之含有二氧化矽粒子的硬塗層用組成物（固形份濃度45% ) 塗佈於（1 )形成之導電層上後，於烘箱中8 0 °C乾燥1分鐘。接著，藉由在空氣下使用高壓水銀燈，以〇·6 J/cm2之光照射條件照射紫外線，形成硬化膜層。 -82- (79) 200538754 (3 )中折射率層之製作使用金屬絲棒桿塗佈器（# 3 ) ’將製造例5調製之含有I Τ Ο粒子的組成物（固形份濃度4 % )’塗佈於（2 )製成之硬塗層上後’於烘箱中8 〇 °C乾燥1分鐘。接著’藉由在氮氣氣體環境下使用高壓水銀燈，以〇.6J/cm2之光照射條件照射紫外線，形成硬化膜層。以反射分光計算出硬化膜層之膜厚爲65 nm。 (4 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（#3)，分別將製造例17〜24所得之液狀硬化性樹脂組成物Π-1〜Π-8，塗佈於（3 )製成之中折射率層上後，於烘箱中140 °C乾燥2分鐘。藉由在大氣下使用歐庫公司製之輸送帶式水銀燈，照射〇.6J/cm2之紫外線，形成膜厚0.2 μηι之硬化膜層。又，使用金屬絲棒桿塗佈器（#3 )，分別將製造例 φ 17〜24所得之液狀硬化性樹脂組成物ΙΙ·1〜ΙΙ-8，塗佈於（3) 製成之中折射率層上後，藉由在烘箱中120 °c加熱10分鐘，形成膜厚〇·2 μιη之硬化膜層。 [實施例 ΙΙ-3、ΙΙ-4] (層合物之製作） (1)聚噻吩層（導電層、防靜電層）之製作與實施例Π-2 ( 1)同樣的製作。 -83· 200538754 (80) (2 )硬塗層之製作與實施例Π-2 ( 2 )同樣的製作。 (3 )中折射率層之製作使用金屬絲棒桿塗佈器（#3 )，將替代製造例5調製之ITO粒子的製造例6或7調製之含有ΑΤΟ粒子的組成物（固形份濃度5%)或含有Α1之ΖηΟ粒子組成物（固形份濃度4% φ )，塗佈於（2 )製成之硬塗層上後，於烘箱中80 °C乾燥 1分鐘。接著，藉由在氮氣氣體環境下使用高壓水銀燈’ 以0.6J/cm2之光照射條件照射紫外線，形成硬化膜層。以反射分光計算出硬化膜層之膜厚爲65 nm。 (4 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（#3)，分別將製造例17〜24所得之液狀硬化性樹脂組成物Π-1〜II-8，塗佈於（3 )製成之 φ 中折射率層上後，於烘箱中140 °C乾燥2分鐘。藉由在大氣下使用歐庫公司製之輸送帶式水銀燈，照射〇·6J/cm2之紫外線，形成膜厚〇·2 μιη之硬化膜層。又，使用金屬絲棒桿塗佈器（#3 )，分別將製造例 17〜24所得之液狀硬化性樹脂組成物11_1〜Π-8，塗佈於（3) 製成之中折射率層上後’藉由在烘箱中12 〇 C加熱1〇为鐘。形成膜厚0·2 μιη之硬化膜層。 [實施例ΙΙ-5] -84- 200538754 (81) (層合物之製作） (1)聚噻吩層（導電層、防靜電層）之製作與實施例II-2 ( 1)同樣的製作。 (2 )硬塗層之製作與實施例II-2 ( 1 )同樣的製作。 B ( 3 )高折射率層與低折射率層之製作使用金屬絲棒桿塗佈器（#3)，分別將製造例17〜24所得之液狀硬化性樹脂組成物Π-1〜II-8，塗佈於（2 )製成之硬塗層上後，於烘箱中140 °C乾燥2分鐘。藉由在大氣下使用歐庫公司製之輸送帶式水銀燈，照射〇.6J/cm2之紫外線，形成膜厚0.2 μιη之硬化膜層。又，使用金屬絲棒桿塗佈器（#3 )，分別將製造例 17〜24所得之液狀硬化性樹脂組成物ΙΙ-1〜ΙΙ-8，塗佈於（2) φ 製成之硬塗層上後，藉由在烘箱中120 °C加熱1〇分鐘，形成膜厚爲0.2 μιη之硬化膜層。 [評估例ΙΙ-1] (層合物之評估）以穿透型電子顯微鏡觀察實施例II-1〜ΙΙ-5所得之層合物的剖面，確認低折射率層與高折射率層層分離爲兩層。此時，低折射率層爲金屬氧化物粒子實質上不存在之層，高折射率層爲金屬氧化物粒子高密度存在之層。 -85- 200538754 (82) 圖9爲兩層分離、不分離（一部份凝聚）、及均勻結構之各狀態的示意圖之電子顯微鏡照相。藉由分光反射率測定裝置（將大型試料室積分球附屬裝置1 50-09090組入之自動記錄分光光度計u-3410，日立製作所股份有限公司製），測定波長5 5 Onm之反射率，評估所得防反射用層合物之防反射性。具體而言，以鋁之蒸鍍膜中的反射率爲基準（1 0 0 % )，測定防反射用層合物（防反射膜）之反射率。其結果，於波長550nm，任一種層合物之反射率均爲1%以下。 [產業上利用性] 本發明之層合物的製造方法，能以氣相聚合形成導電層之故，可製造均勻的導電層。又，可由1之塗膜形成2以上之層，能簡化具有兩層以上之多層結構的層合物之製造步驟。因此，本發明之層合物的製造方法，特別適合使用 φ 於防反射膜、透鏡、選擇穿透膜濾光片等光學材料之形成。又，所得層合物，可利用於含有氟含量高之層，適合使用於對基材要求耐候性之塗料、耐候薄膜、塗覆及其他用途。並且，該層合物對基材之密著性優異、耐擦傷性高、能賦予良好的防反射效果之故，極適合做爲防反射膜；藉由使用於各種顯示裝置，能提升其辨識性。【圖式簡單說明】圖1 A爲「由1之塗膜形成2以上之層」的說明圖。 -86-Composition 1-6 1 ^ Τ) (N 1 51.3 rH in 00 100 Composition 1-5 Ό (N 1 On 1 (N ο 100 Composition 1-4 〇1 Blue 1 VO (N VO (Ν 101 Composition 1-3 ( N 1 On 1 100 Composition 1-2 1 1 〇100 Composition 1-1 25.1 1 1 (Τ) Τ-Η FH 00 100 Composition of the solid content of the composition (% by weight) Manufacturing Example 10 Cayenne-ADS 耧灿嫲屮, M 鵾〇安 Η Mipeng silica-coated Ti0 2 Saimiru 303 Catalyst 4050 Total fluoropolymer 1 fluoropolymer (non-hydroxyl) metal oxide particle thermosetting compound hardening catalyst (thermoacid generation) Agent) Ingredient Q g U -71-(68) 200538754 The abbreviations in Table 1 are as follows. (A) Fluoropolymer: The fluoropolymer obtained in the above Production Example 1. Kayna AD S: Yale Made by Cardiff Adokim Japan Co., Ltd .; Copolymer of hexafluoropropylene, tetrafluoroethylene, and difluoroethylene 'does not contain hydroxyl groups and polymerizable unsaturated groups. (B) Metal oxide particles alumina, hafnium oxide Coated Ti02 particle dispersion: manufactured by Tieka Co., Ltd., with a total solids concentration of 28%, particle concentration of 24%, and number average particle size of 20 nm. Silicon-coated Ti02 particle dispersion: Produced in Production Example 2. (E) Saimiru 3 03: Methoxylated methyl melamine, manufactured by Sanno Saekiku Co., Ltd. (F) Catalyst 4050: Mitsui Aromatic sulfonic acid compound manufactured by Satie Iron Depot Co., Ltd. Manufacturing Examples 17 to 24 are manufacturing examples of the second type φ-state liquid hardening resin composition containing (F) component as an essential component. [Manufacture Example 17 (Preparation of liquid curable resin composition II-1) The reactive silica dioxide obtained in Production Example 12 was coated with a Ti02 particle sol [compound (Z-1), 50.6 g of reactive particles) 280.9 g 1. 23 g (of fluoropolymer 2) obtained in Production Example 1 1. 14.3 g of methoxylated methyl melamine "Saimiru 3 03" (manufactured by Mitsui Sayi Iron Depot Co., Ltd.), a thermosetting compound "Catalyst 4050" with hardening catalyst (Mitsui Saite Iron-72- (69) 200538754% Co., Ltd., aromatic sulfonic acid compound 'active ingredient concentration 32%) 1 1.9g, active energy ray hardening compound The composition (A-2) obtained in Production Example 2 shown by the formula (8) 2 · 0 g, dipentaerythritol hexaacrylate (produced by Benben Pharmaceutical Co., Ltd., trade name: Cayalado DPHA-2C) 5.3 g, {2-methyl-l- [4- (Methylthio) phenyl] -2 -morpholine (substituted) propane-l-one} (Ilgachur 907 'manufactured by Giba Specialty Chemicals Co., Ltd.) 1.0 g, methyl ethyl ketone dissolved in a solvent 300 g, Among 320 g of isobutanol and 2 1 g of tert-φ butanol, a liquid curable resin composition Π-1 was obtained. The total solids concentration of the liquid curable resin composition (the ratio of the solid content of the liquid curable resin composition) was measured in the same manner as in Production Example 8 to be 8.5% by weight. [Production Examples 18 to 24] (Preparation of liquid curable resin composition II-2 to II-8) The same as Production Example 17 except that the mixing ratio of each component of the composition was changed as shown in Table 2. It is prepared to form a liquid hardening resin composition II-2 to II-8. The solid content composition of the liquid curable resin composition II-2 to II-8 is shown in Table 2. -73- 200538754 (70) Manufacturing example 24 00 1 HH HH inch r-Η inch? —Η Η 〇ο ο ο (Ν 00 (Ν (N ο ο ο r * H) Manufacturing Example 23 Π 1 HH ο (Ν ( Ν τ-Η 〇ο ο ο Ο 〇 (NO Ο Ο fH Manufacturing Example 22 1 HH HH ο (Ν (Ν τ-Η 〇ο ο ο Ο νο 〇 (N o ο ο 1—Η Manufacturing Example 21 I ΗΗ ΗΗ ΗΗ ο 00 CN (Ν Os 00 md ο Ο ο ο ο 〇 (N o ▼ -H Ο Ο Manufacture Example 20 inch 1 ΗΗ ►—Η rH 00 rH ο cn ο ο ο ο ο ο inch 〇 (N 〇rH Ο ο ^ ^ -Η Manufacturing Example 19 1 Η-Η ΗΗ τ—Η m (Ν 00 m ο ο ο ο ο m 〇 (N o Ο Ο rH Manufacturing Example 18 (Ν I ΗΗ ΗΗ (Ν 00 m ο ο ο ο ο ο m 〇 (N 〇〇 ο rH Manufacturing Example 17 rH 1 ΗΗ ΗΗ ^ -Η m (Ν m ▼ —Η 00 ο ο ο ο ο m 〇 (N o ο ο rH) Manufacturing Example 11 of Spheroid Curable Resin Composition Saimimer 303 Catalyst 4050 Manufacturing Example 12 (ζ-1) mm ^ Manufacturing Example 14 (Z-3) Manufacturing Example 9 (Z-2) Manufacturing Example 15 (Z-4) Cayalado DPHA-2C Production Example 2 Ilgachur 907 Total Fluoropolymer 2 Thermosetting Compound Hardening catalyst metal oxide fine particle sol i _ ^ _ DD ^ is a photopolymerization initiator /-· N PQ y ^ -NQ ϋ -74- 200538754 (71) Examples I-1 ~ 1-5 and Evaluation Example 1-1, Examples and evaluation examples of the laminates using the liquid curable resin composition 1-1 to 1-6 obtained in the above Production Example 16. [Example 1-1, Comparative Example 1] Production) (1) Production of hard coat layer A composition for a hard coat layer containing silicon dioxide particles prepared in Production Example 3 using a wire rod applicator (base 1 2) (solid content concentration 45%) After coating on a triethyl cellulose cellulose film (manufactured by Lofer, film thickness 80 μm), it was dried in an oven at 80 ° C. for 1 minute. Then, a high-pressure mercury lamp was used at 0.6 J / cm 2 in the air. The light irradiation conditions irradiate ultraviolet rays to form a hardened film layer. The thickness of the hardened film layer is 5 μm as measured by a stylus film thickness. (2) Production of a polythiophene layer (conductive layer, antistatic layer) , Dissolved in a solvent of methanol, 2-butanol, and ethyl cellosolve in a ratio of 6: 3: 1, dissolved into 3% by weight, that is, prepared into a catalyst Solution. On the surface of the triethyl cellulose cellulose film provided with a hard coat layer, the prepared catalyst solution was spin-coated, and the obtained catalyst coating film was dried at 60 ° C for 3 minutes. Next, this polyester film forming a hard coat layer and a catalyst coating film is installed in a CVD chamber designed to generate a saturated 3,4-ethylenedioxythiophene monomer, so that 3,4_ethylenedioxy After the thiophene was polymerized for 30 seconds, it was washed with -75- (72) 200538754 4 methanol solvent to remove unreacted materials to form a conductive layer. (3) Production of the middle refractive index layer Using a wire rod applicator (# 3), a composition containing ytterbium oxide particles (solid content concentration 4%) prepared in Production Example 4 was applied to (2). The resulting polythiophene layer was dried in an oven at 80 ° C for 1 minute. Next, under a nitrogen gas environment, a high-pressure mercury lamp was used to irradiate ultraviolet rays under a φ light irradiation condition of 0.6 J / cm2 to form a cured film layer. The film thickness of the hardened film layer was calculated by reflection spectroscopy to be 65 μm. (4) Preparation of high-refractive index layer and low-refractive index layer Using a wire rod applicator (# 3), the liquid hardening resin composition having the composition I-1 to 1-6 obtained in Production Example 16 was respectively used. After being coated on the intermediate refractive index layer made in (3), a hardened film layer having a film thickness of 0.2 μm was formed by heating at 120 ° C for 10 minutes in an oven. [Example 1-2, Comparative Example 2] (Production of laminate) (1) Production of polythiophene layer (conductive layer, antistatic layer) On the surface of triethylfluorene-based cellulose film, Example 1- 1 (2) After the prepared catalyst solution is spin-coated, the obtained catalyst coating film is dried at 60 ° C for 3 minutes. Next, this catalyst film-forming polyester film was installed in a CVD cell designed to generate a saturated 3,4-ethylenedioxythiophene monomer, so that -76- 200538754 (73) 3,4-ethylene After the dioxythiophene was polymerized for 30 seconds, it was washed with a methanol solvent to remove unreacted materials, thereby forming a conductive layer. (2) Production of hard coat layer A wire rod applicator (base 1 2) was used, and the composition for a hard coat layer (solid content concentration: 45%) containing silicon dioxide particles prepared in Production Example 3 was applied. After the conductive layer formed in (1) was dried in an oven at 80 ° C for 1 φ minutes. Next, a hardened film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.6 J / cm2 using a high-pressure mercury lamp 'in the air. (3) Production of the middle refractive index layer Using a wire rod applicator (base 3), the composition containing solid ITO particles (solid content concentration 4%) prepared in Production Example 5 was applied to (2) After the hard coating is completed, it is dried in an oven at 80 ° C for 1 minute. Next, under a nitrogen gas environment, a high-pressure mercury lamp was used to irradiate ultraviolet rays under a light irradiation condition of 0.6 J / cm2 to form a cured film layer. The thickness of the hardened layer was calculated by reflection spectroscopy to be 65 nm. (4) Production of high-refractive index layer and low-refractive index layer Using a wire rod applicator (# 3), the liquid hardenable resins having a composition of 1-1 to 1-6 obtained in Production Example 16 were respectively used. After being coated on the middle refractive index layer made in (3), the hardened film layer was formed by heating at 120 ° C for 10 minutes in an oven to a thickness of 0.2 μm. -77- (74) 200538754 [Examples 1-3, 1-4 and Comparative Examples 3, 4] (Production of laminates) (1) Production and examples of polythiophene layer (conductive layer, antistatic layer) 1-2 (1) Same production. (2) Production of hard coat layer The same production as in Example 1-2 (1) was performed. (3) Production of the medium refractive index layer Using a wire rod applicator (base 3), the composition containing ΑΟΟ particles prepared in place of Manufacturing Example 6 or 7 prepared by Manufacturing Example 5 (solid content concentration 5) %) Or a composition containing Zn particles of A1 (solid content concentration: 4%), coated on the hard coat layer made in (2), and dried in an oven at 80 ° C for 1 minute. Next, under a nitrogen gas environment, a high-pressure mercury lamp was used to irradiate ultraviolet rays under a light irradiation condition of 0.6 J / cm2 to form a cured film layer. φ Calculated by reflection spectrometry, the film thickness of the hardened layer is 65 nm. (4) Production of high-refractive index layer and low-refractive index layer Using a wire rod applicator (# 3), the liquid hardenable resins having a composition of 1-1 to 1-6 obtained in Production Example 16 were respectively used. After being coated on the intermediate refractive index layer made in (3), a hardened film layer having a film thickness of 0.2 μm was formed by heating in an oven at 120 ° C for 10 minutes. [Example 1-5, Comparative Example 5] -78- 200538754 (75) (Production of laminate) (1) Production of polythiophene layer (conductive layer, antistatic layer) and Example 1-2 (1) The same made. (2) Production of hard coat layer The same production as in Example 1-2 (1) was performed. (3) Preparation of high-refractive index layer and low-refractive index layer Using a wire rod applicator (base 3), the liquid hardening resin composition having a composition of 1-1 to 1-6 obtained in Production Example 16 was respectively used. After being coated on the hard coat layer made in (2), a hardened film layer having a film thickness of 0.2 μm was formed by heating in an oven at 120 ° C for 10 minutes. [Evaluation Example 1-1] (Evaluation of Laminate) The cross sections of the laminates obtained in Examples 1-1 to 1-5 and Comparative Examples 1 to 5 were observed with a transmission electron microscope, and the composition 1-1 was confirmed to be used. In the laminates of 1-2, 1-3, and 1-5, the low-refractive index layer and the high-refractive index layer are separated into two layers. At this time, the low-refractive index layer is a layer in which radical polymerization initiator metal oxide particles are present at a high density, and the high-refractive index layer is a layer in which metal oxide particles are present at a high density. In the laminates of composition 1-4, the high-refractive index layer and the low-refractive index layer have a uniform structure without layer separation. In the laminates composed of 1-6, the high-refractive index layer and the low-refractive index layer partly aggregated without layer separation. -79- (76) 200538754 Figure 8 is a schematic diagram of the states of two layers of separation, non-separation (partial condensation), and uniform structure. Using a spectroscopic reflectance measuring device (automatic recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere accessory device 1 50-09090, manufactured by Hitachi, Ltd.), the reflectance at a wavelength of 550 nm was measured and the composition used was evaluated Anti-reflection properties of the anti-reflection laminates of 1-1, 1-2, I · 3, and I · 5. Specifically, the reflectance of the φ anti-reflection laminate (anti-reflection film) was measured based on the reflectance (100%) in the aluminum vapor-deposited film. As a result, at a wavelength of 5 5 Onm, the reflectance of any of the laminates was 1% or less. Examples II-1 to II-5 and evaluation example II-1 are examples and evaluation examples of the laminates Π-1 to Π-8 prepared using the above-mentioned manufacturing examples 17-24. [Example Π-1] (Production of laminate) (1) Production of hard coat layer φ Using a wire rod applicator (base 1 2), the product containing silicon dioxide particles prepared in Production Example 3 was prepared. The composition for a hard coat layer (solid content concentration: 45%) was applied to a triethylfluorene-based cellulose film (manufactured by Love Company, film thickness: 80 μm), and then dried in an oven at 80 ° C. (: Dry for 1 minute. Then, by using a high-pressure mercury lamp under air, irradiate ultraviolet rays under the light irradiation condition of 0.6 J / cm2 to form a cured film layer. The film thickness of the cured film layer was measured with a stylus film thickness meter as 5 μιη (2) Production of polythiophene layer (conducting layer, antistatic layer) -80- 200538754 (77) FeCl2 as oxidant, methanol, 2-butanol and ethyl cellosolve respectively 6: 3: 1 The solvent prepared by mixing at a ratio of 3% by weight is dissolved to prepare a catalyst solution. On the surface of the triethylfluorene cellulose film provided with a hard coat layer, the prepared catalyst solution is spin-coated, and the obtained The catalyst coating film was dried at 60 ° C for 3 minutes. Then, the polyester film forming the hard coating layer and the catalyst coating film was placed in a CVD unit designed to generate saturated CVD units of 3,4-ethylenedioxythiophene. In a small chamber, 3,4-ethylenedioxythiophene is polymerized for 30 seconds, and then washed with methanol solvent to remove unreacted materials to form a conductive layer. (3) The middle refractive index layer is coated with a metal wire rod (# 3), the composition containing the oxidation pin particles prepared in Production Example 4 (Concentration of solid content 4%), coated on the polythiophene layer made in (2), and dried in an oven at 80 ° C for 1 minute. Then, φ was used in a nitrogen gas environment by using a high-pressure mercury lamp, and 6J / cm2 light irradiation conditions irradiate ultraviolet rays to form a hardened film layer. The thickness of the hardened film layer is calculated by reflection spectrometry to be 65 nm. (4) Production of high refractive index layer and low refractive index layer Use wire rod coating The cloth device (# 3) was coated with the liquid hardening resin compositions II-1 to II-8 obtained in Manufacturing Examples 17 to 24 on the middle refractive index layer prepared in (3), and then placed in an oven. 1 40 ° C for 2 minutes. By using a belt-type mercury lamp made by Oku Corporation in the atmosphere, it is irradiated with -81-(78) 200538754 of 0.6J / cm2 to form a hardened film with a thickness of O · 2 Km. The film layer was prepared by applying the liquid hardening resin composition II-1 to Π-8 obtained in Production Examples 17 to 24 using a wire rod applicator (# 3) to (3). After the intermediate refractive index layer was formed, a hardened film layer having a film thickness of 0.2 μm was formed by heating in an oven at 120 ° C for 10 minutes. [Example I1-2] (Laminate Production) (1) Production of polythiophene layer (conductive layer, antistatic layer) On the surface of triethylfluorene cellulose film, the catalyst solution prepared in Example 11-1 (2) was spin-coated to obtain The catalyst film was dried at 60 ° C for 3 minutes. Next, the polyester film device forming the catalyst coating film was placed in a CVD chamber designed to generate a saturated 3,4 ethylenedioxythiophene monomer in the 3,4 -After carrying out the polymerization reaction of ethylenedioxythiophene for 30 seconds, φ was washed with methanol, and unreacted materials were removed to form a conductive layer. (2) Production of hard coat layer Using a wire rod applicator (# 1 2), a composition for a hard coat layer containing solid silicon dioxide particles prepared in Production Example 3 (solid content concentration: 45%) was applied. After the conductive layer (1) was formed, it was dried in an oven at 80 ° C for 1 minute. Next, a high-pressure mercury lamp was used in the air to irradiate ultraviolet rays under a light irradiation condition of 0.6 J / cm2 to form a cured film layer. -82- (79) 200538754 (3) Production of the refractive index layer Using a wire rod applicator (# 3) 'I Example 5 composition containing solid ITO particles prepared in Preparation Example 5 (solid content concentration 4%) 'After coating on the hard coat made of (2)', dry in an oven at 80 ° C for 1 minute. Next, by using a high-pressure mercury lamp under a nitrogen gas environment and irradiating ultraviolet rays under a light irradiation condition of 0.6 J / cm2, a cured film layer is formed. The thickness of the hardened film was calculated by reflection spectroscopy to be 65 nm. (4) Preparation of high-refractive index layer and low-refractive index layer Using a wire rod applicator (# 3), the liquid hardening resin composition obtained in Manufacturing Examples 17 to 24 was Π-1 to Π-8, respectively. After coating on the intermediate refractive index layer made in (3), it is dried in an oven at 140 ° C for 2 minutes. By using a conveyor-type mercury lamp manufactured by Oku Corporation under the atmosphere, it was irradiated with ultraviolet light of 0.6 J / cm2 to form a hardened film layer having a thickness of 0.2 μm. In addition, using a wire rod applicator (# 3), the liquid hardening resin composition 1-1 · 1 ~ ΙΙ-8 obtained in Production Examples φ 17 to 24 was applied to (3). After being coated on the refractive index layer, a hardened film layer having a film thickness of 0.2 μm was formed by heating in an oven at 120 ° C for 10 minutes. [Examples III-3, III-4] (Production of laminate) (1) Production of polythiophene layer (conductive layer, antistatic layer) The same production as in Example Π-2 (1) was performed. -83 · 200538754 (80) (2) Production of hard coat layer The same production as in Example Π-2 (2). (3) Production of the medium refractive index layer Using a wire rod applicator (# 3), a composition containing ΑΟΟ particles prepared in place of Manufacturing Example 6 or 7 prepared by Manufacturing Example 5 (solid content concentration 5) %) Or a composition containing Zn particles of A1 (solid content concentration: 4% φ), coated on a hard coat layer made in (2), and dried in an oven at 80 ° C for 1 minute. Next, a high-pressure mercury lamp was used under a nitrogen gas environment to irradiate ultraviolet rays under a light irradiation condition of 0.6 J / cm2 to form a cured film layer. The thickness of the hardened film was calculated by reflection spectroscopy to be 65 nm. (4) Preparation of high-refractive index layer and low-refractive index layer Using a wire rod applicator (# 3), the liquid hardening resin composition obtained in Manufacturing Examples 17 to 24 was Π-1 to II-8, respectively. After coating on the φ medium refractive index layer made in (3), it is dried in an oven at 140 ° C for 2 minutes. By using a conveyor-type mercury lamp manufactured by Oku Co. under the atmosphere, ultraviolet light of 0.6 J / cm2 was irradiated to form a hardened film layer having a film thickness of 0.2 μm. In addition, using a wire rod applicator (# 3), the liquid curable resin compositions 11_1 to Π-8 obtained in Production Examples 17 to 24 were applied to (3) to form a middle refractive index layer. Go up and down 'by heating in an oven at 120 ° C for 10 minutes. A hardened film layer with a film thickness of 0.2 μm was formed. [Example 11-5] -84- 200538754 (81) (Production of laminate) (1) Production of polythiophene layer (conductive layer, antistatic layer) The same production as in Example II-2 (1) was performed. (2) Production of hard coat layer The same production as in Example II-2 (1) was performed. B (3) Preparation of high-refractive index layer and low-refractive index layer Using a wire rod applicator (# 3), the liquid curable resin composition obtained in Production Examples 17 to 24 was Π-1 to II- 8. After coating on the hard coat layer made in (2), dry in an oven at 140 ° C for 2 minutes. By using a conveyor-type mercury lamp manufactured by Oku Corporation in the atmosphere, ultraviolet light of 0.6 J / cm2 was irradiated to form a hardened film layer having a thickness of 0.2 μm. In addition, using a wire rod applicator (# 3), the liquid curable resin compositions 1-1-1 to Ι-8 obtained in Production Examples 17 to 24 were applied to (2) φ made of hardened resin. After coating, a hardened film layer having a film thickness of 0.2 μm was formed by heating in an oven at 120 ° C for 10 minutes. [Evaluation Example II-1] (Evaluation of Laminate) The cross section of the laminate obtained in Examples II-1 to Ι-5 was observed with a transmission electron microscope, and it was confirmed that the low refractive index layer and the high refractive index layer were separated. For two floors. At this time, the low refractive index layer is a layer in which metal oxide particles are not substantially present, and the high refractive index layer is a layer in which metal oxide particles are present at a high density. -85- 200538754 (82) Fig. 9 is an electron microscope photograph of each state of two-layer separation, non-separation (partial condensation), and uniform structure. Using a spectroscopic reflectance measuring device (automatic recording spectrophotometer u-3410 incorporating a large sample chamber integrating sphere accessory device 1 50-09090, manufactured by Hitachi, Ltd.), the reflectance at a wavelength of 5 5 Onm was measured and evaluated Antireflection property of the obtained antireflection laminate. Specifically, the reflectance of the anti-reflection laminate (anti-reflection film) was measured on the basis of the reflectance (100%) in the aluminum vapor-deposited film. As a result, at a wavelength of 550 nm, the reflectance of any of the laminates was 1% or less. [Industrial Applicability] Since the method for producing a laminate of the present invention can form a conductive layer by gas phase polymerization, a uniform conductive layer can be manufactured. In addition, two or more layers can be formed from the coating film of 1, which can simplify the manufacturing steps of a laminate having a multilayer structure of two or more layers. Therefore, the method for producing a laminate of the present invention is particularly suitable for forming an optical material such as an antireflection film, a lens, and a selective transmission film filter. In addition, the obtained laminate can be used for a layer containing a high fluorine content, and is suitable for use in coatings, weather-resistant films, coatings, and other applications that require weather resistance to a substrate. In addition, the laminate is excellent in adhesion to the substrate, has high abrasion resistance, and can provide a good anti-reflection effect, which is extremely suitable as an anti-reflection film; by using it in various display devices, its identification can be improved. Sex. [Brief description of the drawings] FIG. 1A is an explanatory diagram of “forming a layer of 2 or more from a coating film of 1”. -86-

200538754 (83) 圖1B爲「由1之塗膜形成2以上之層」的說圖1C爲「由1之塗膜形成2以上之層」的說圖1D爲「由1之塗膜形成2以上之層」的說圖1E爲「由1之塗膜形成2以上之層」的說圖2爲本發明之一實施形態的防反射膜之g 圖3爲本發明之其他實施形態的防反射膜二圖4爲本發明之其他實施形態的防反射膜；^ 圖5爲本發明之其他實施形態的防反射膜；^ 圖6爲本發明之其他實施形態的防反射膜二圖7爲本發明之其他實施形態的防反射膜；^ 圖8爲使用不含（F )成份爲必要成份之第狀硬化性樹脂組成物製作之硬化膜的兩層分離一部份凝聚）及均勻結構之各狀態的示意照相圖9爲使用含有（F )成份爲必要成份之第狀硬化性樹脂組成物製作之硬化膜的兩層分離一部份凝聚）及均勻結構之各狀態的示意電子【主要元件符號說明】200538754 (83) Fig. 1B is "the formation of 2 or more layers from the 1 coating film" Fig. 1C is "the formation of 2 or more layers from the 1 coating film" Fig. 1D is "the formation of 2 or more layers from the 1 coating film" 1E is an illustration of "a layer of 2 or more is formed by a coating film of 1" Fig. 2 is an anti-reflection film of one embodiment of the present invention g Fig. 3 is an anti-reflection film of another embodiment of the present invention Fig. 4 is an anti-reflection film according to another embodiment of the present invention; ^ Fig. 5 is an anti-reflection film according to another embodiment of the present invention; ^ Fig. 6 is an anti-reflection film according to another embodiment of the present invention; Anti-reflection film according to another embodiment; ^ FIG. 8 shows the states of the two layers separated and partially agglomerated) and a uniform structure of a cured film made of a first curable resin composition containing no (F) component as an essential component; and a uniform structure. Fig. 9 is a schematic diagram of each state of the two layers of the cured film made of the first curable resin composition containing the (F) component as an essential component, separated and partially agglomerated) and the uniform structure of each state [Description of the main component symbols 】

1 :金屬氧化物粒子高密度存在之層 1 a :金屬氧化物粒子高密度存在之層 lb :金屬氧化物粒子高密度存在之層 3:金屬氧化物粒子實質上不存在之層 X :粒子X 明圖。明圖。明圖。明圖。面圖。 L剖面圖。 L剖面圖。 L剖面圖。 :剖面圖。 :剖面圖。一型態的液、不分離（〇二型態的液、不分離（顯微鏡照相 -87- (84)1: Layer with high density of metal oxide particles 1 a: Layer with high density of metal oxide particles lb: Layer with high density of metal oxide particles 3: Layer with substantially no metal oxide particles X: Particle X Mingtu. Mingtu. Mingtu. Mingtu. Face view. L sectional view. L sectional view. L sectional view. : Sectional view. : Sectional view. Type I liquid, without separation (〇 Type II liquid, without separation (Micrograph -87- (84)

Y :粒子Y 1 0 :基材 2 0 :防靜電層 3 0 :硬塗層 4 0 :高折射率層 5 0 :低折射率層 6 0 :中折射率層Y: particle Y 1 0: substrate 2 0: antistatic layer 3 0: hard coat layer 4 0: high refractive index layer 50 0: low refractive index layer 60 0: medium refractive index layer

200538754200538754

Claims

200538754 (1) X. Application for Patent Scope 1. A method for manufacturing a laminate, which is a method for manufacturing a laminate having a substrate, a conductive layer thereon, and a multilayer structure; A monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene, Kethylenedioxythiophene, and derivatives thereof is subjected to gas phase polymerization to form a conductive layer; containing the following components (A), ( B), (c), (D), (φ E-1) and (E-2) liquid hardening resin composition are applied to form a coating film; the solvent is evaporated from the coating film of this 1 , Forming a layer of 2 or more; [liquid curable resin composition] (A) fluorinated polymer (B) thermosetting compound (C) curing catalyst φ (D)-one or two or more of the average particle diameter is 100 nm The following metal oxide particles (hereinafter referred to as "(D) metal oxide particles") (E -1)-one or two or more types of solvents having high solubility in (A) fluoropolymer (hereinafter referred to as "(E-1) Quickly volatile solvent") (E-2)-one or two or more pairs of (D) metal oxide particles Solvent with high dispersion stability and compatibility with (E-1) fast volatilizing solvent (hereinafter referred to as "(E-2) slow volatilizing solvent"); Moreover, the relative evaporation rate of (E-1) fast volatilizing solvent Greater than (E_2) the relative evaporation rate of slowly volatile solvents. -89- 200538754 (2) 2. A method for manufacturing a laminate, which is a method for manufacturing a laminate having a substrate, a conductive layer thereon, and a multilayer structure; characterized in that at least one Monomers selected from the group consisting of pyrrole, thiophene, furan, selenophene, 3'4-ethylenedioxythiophene, and derivatives thereof are subjected to gas phase polymerization to form a conductive layer; containing the following component (A) , (Β), (C), (D), (Ε-1), (Ed), and (F) liquid sclerosing resin compositions are subjected to φ cloth to form a coating film; The coating film is evaporated to form a layer of 2 or more; [Liquid hardening resin composition] (A) Fluoropolymer (B) Thermosetting compound (C) Hardening catalyst (D) — one or two or more average particles Φ metal oxide particles with a diameter of 100 nm or less (hereinafter referred to as "(D) metal oxide particles") (E-1)-one or two or more solvents having high solubility in (A) fluoropolymer (Hereinafter referred to as "(E-1) fast volatilizing solvent") (E-2) — dispersion of one or two or more pairs of (D) metal oxide particles Highly qualitative solvents that are compatible with (E-1) fast-evaporating solvents (hereinafter referred to as "(E-2) slow-evaporating solvents"); (F) active energy ray hardening compounds; and (E-1 ) The relative evaporation rate of fast volatile solvents is greater than (E-2) The relative evaporation rate of slow volatile solvents. -90-200538754 (3) 3 · The method for producing a laminate according to item 1 or 2 of the scope of patent application, wherein the (A) fluoropolymer is a fluoropolymer having a hydroxyl group in the molecule. 4. The method for producing a laminate according to item 2 of the patent application scope, wherein the solid content of the liquid curable resin composition is 100% by mass, and the component (B) contains 5 to 80% by mass. 5. The method for producing a laminate according to item 1 of the application, wherein the (C) curing catalyst is a thermal acid generator. • 6. The method for producing a laminate according to item 2 of the patent application scope, wherein the solid content of the liquid curable resin composition is 100% by mass, and the component (c) contains 0.1 to 20% by mass. 7 · The method for manufacturing a laminate according to item 1 of the scope of patent application, wherein (D) the refractive index of the metal oxide particles is 1.50 or more. 8. The method for manufacturing a laminate according to item 1 of the scope of patent application, wherein the (D) metal oxide particles are selected from one or two or more kinds selected from titanium oxide, zirconia, antimony-containing tin oxide, and phosphorus-containing Particles mainly composed of metal oxides of tin oxide, tin-containing indium oxide, φ alumina, cerium oxide, zinc oxide, aluminum-containing zinc oxide, tin oxide, antimony-containing zinc oxide, and indium-containing zinc oxide. 9. The method for manufacturing a laminate according to item 1 of the scope of patent application, wherein the (D) metal oxide particles are particles containing titanium oxide as a main component. 10. The method for producing a laminate according to item 2 of the scope of the patent application, wherein the (D) metal oxide particles are selected from one or two or more kinds selected from titanium oxide, zirconia, antimony-containing tin oxide, and tin-containing Indium oxide, silicon dioxide, aluminum oxide, hafnium oxide, zinc oxide, aluminum oxide-containing zinc oxide, tin oxide, antimony-containing zinc oxide, and indium-containing zinc oxide are metal-based particles. -91-200538754 (4) 1 1 · The method for manufacturing a laminate according to item 1 or 2 of the scope of patent application, wherein the (D) metal oxide particles are metal oxide particles having a multilayer structure. 1 2. The method for producing a laminate according to item 2 of the patent application range, wherein the (D) metal oxide particles are connected to an organic compound having a polymerizable unsaturated group. 1 3 · The method for manufacturing a laminate according to item 1 or 2 of the scope of patent application, wherein the (E-1) rapidly volatile solvent is one or two or more kinds of (D) metal oxide particles having low dispersion stability (E-2) The slowly evaporating solvent is one or two or more solvents having low solubility in (A) fluoropolymer. 14. The method for manufacturing a laminate according to item 1 or 2 of the scope of the patent application, wherein each of the layers of the 2 or more layers is a layer in which metal oxide particles exist at a high density, or a layer in which metal oxide particles are not substantially present, At least one layer is a layer in which metal oxide particles are present at a high density. 1 5 · The method for producing a laminate according to item 1 or 2 of the scope of patent application, wherein the two or more layers are two layers. 16. The method for producing a laminate according to item 1 of the scope of patent application, wherein the layer 2 or more is further hardened by heating. 17. The method for producing a laminate according to item 2 of the scope of patent application, wherein the layer is hardened by heating the 2 or more layers and / or by irradiating radiation. 1 8 · The method for manufacturing a laminate according to item 1 or 2 of the scope of patent application, wherein the laminate is an optical part. 19. The method for manufacturing a laminate according to item 1 or 2 of the scope of patent application, wherein the laminate in -92-200538754 (5) is an anti-reflection film. 20. The method for manufacturing a laminate according to item 15 of the scope of patent application, wherein the laminate is on a substrate, and at least an antistatic layer, a high refractive index layer, and a low The anti-reflection film of the refractive index layer; the conductive layer is an antistatic layer; the two layers in item 15 of the patent application range are made of a high refractive index layer and a low refractive index layer. 2 1 · The method for manufacturing a laminate according to item 20 of the patent application scope, wherein the refractive index of the low refractive index layer at 5.89nm is 1.20 ~ 1.55; the refractive index of the high refractive index layer at 5.89nm is 1.50 ~ 2.20, higher than the refractive index of the low refractive index layer. 22. The method for manufacturing a laminate according to item 15 of the patent application scope, wherein the laminate is on a substrate, and at least an antistatic layer, a medium refractive index layer, and a high refractive index are laminated in order from the side near the substrate. The anti-reflection film of the refractive index layer and the low refractive index layer; the conductive layer is an antistatic layer; the two layers in item 15 of the patent scope of the application are made of a high refractive index layer and a low refractive index layer. 23. The method for manufacturing a laminate according to item 22 of the patent application scope, wherein the refractive index of the low refractive index layer at 5.89nm is 1.20 ~ 1.55; the refractive index of the intermediate refractive index layer at 5.89nm is 1.50 ~ 1.90, The refractive index of the low-refractive index layer is high; the refractive index of the high-refractive index layer at 1.589 nm is 1.5 to 1.20, which is higher than the refractive index of the middle-refractive index layer. 24. The method for producing a laminate according to claim 20, wherein a hard coat layer is formed on the substrate. -93 · 200538754 (6) 2 5. A kind of laminate, which is characterized by being produced by a method for producing a laminate such as the item 1 or 2 of the scope of patent application.

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