201033659 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用於液晶顯示裝置等之偏光板與 其製造方法。 【先前技術】 偏光板係使用作爲液晶顯示裝置中偏光的供給元件， 以及偏光的檢測元件。以往，偏光板係使用於摻雜碘等， 並經延伸之由聚乙烯醇（PVA)膜所構成之偏光鏡的至少單 面，黏接由三乙酸纖維素（TAC)所構成之保護膜者等。此 時，若保護膜本身存在雙折射，則作爲偏光板的機能會大 幅降低，故爲了防止其發生，目前已使用以溶劑鑄模法所 製作之無光學異向性之TAC膜。 上述以往之偏光板中，爲使PV A膜高倍率延伸因而於 緩和方向會產生較大的應力。保護膜需要具備耐受該應力 之剛性，而將TAC用作保護膜時，於液晶電視等之大畫面 用途中，於膜周邊部之偏光鏡的收縮應力有時會超出TAC 的剛性而引起變形，使得起因於此所生成之TAC保護膜的 雙折射導致褪色產生。 於特開2005-92 1 12號公報中，作爲取代TAC保護膜 者，已提案有活性能量線硬化型樹脂組成物之硬化物。根 據該技術，可獲得雙折射較小、耐濕熱性優異之偏光板。 然而，僅雙折射較小，於上述之偏光鏡的收縮應力較大處 之雙折射仍會變化，使得作爲偏光板的機能受損。 先前技術文獻 -4 - 201033659 〔專利文獻1〕日本專利特開2005 -92 1 1 2號公報 【發明內容】 發明所欲解決之課題 本發明之目的在於提供一種保護膜爲透明，即使施加 應力其雙折射亦不易變化之偏光板與其製造方法。 用以解決課題之手段 本發明者爲了達成上述目的而努力硏究的結果發現： 偏光鏡之至少一面藉由含有特定樹脂之活性能量線硬化型 樹脂組成物之硬化物所構成之保護膜所保護之偏光板，其 保護膜爲透明，即使施加應力其雙折射亦不易變化、而完 成本發明》 亦即，本發明提供一種偏光板，其具有偏光鏡之至少一 面係由樹脂所構成之保護膜所保護之構造，其特徵在於： 上述樹脂，係含有纖維素衍生物之活性能量線硬化性樹脂 組成物之硬化物；該纖維素衍生物，其葡萄糖骨架之羥基 之部分，係被含有不飽和羧酸醯基之基所取代。上述含有 不飽和羧酸醯基之基，係含有下述式（1)所表示之基： 〇 〇 〇 -CNH-fA^NHC-xHA^X^C-C^H (1) n I 2 R1 (式中，R1表示氫原子或碳數爲1〜4之烷基；A1、A2 爲相同或相異，表示2價之有機基；Xl、X2爲相同或相異， 表不氧原子、硫原子、或-NR2-基；R2表示氫原子或碳數爲 201033659 1〜6之烷基；η爲0或1)。 上述纖維素衍生物，較佳爲選自甲基纖維素衍生物、 乙基纖維素衍生物以及乙酸纖維素衍生物之至少1種。 本發明亦提供一種偏光板之製造方法，其特徵在於·· 於偏光鏡之至少一面，塗覆含有纖維素衍生物之活性能量 線硬化性樹脂組成物，然後使該活性能量線硬化性樹脂組 成物硬化而形成保護膜；該纖維素衍生物，其葡萄糖骨架 之羥基之部分，係被含有不飽和羧酸醯基之基所取代。 β發明效果 根據本發明之偏光板，因使用含有特定樹脂之活性能 量線硬化型樹脂組成物之硬化物作爲偏光鏡之保護膜，故 其保護膜爲透明，即使施加應力其雙折射亦不易變化。此 外，雙折射亦小。根據本發明之製造方法，可簡單製造具 備上述優異特性之偏光板。 【實施方式】 ❹ 實施發明之形態 本發明之偏光板，其具有偏光鏡之至少一面係由樹脂 所構成之保護膜所保護之構造。作爲偏光鏡並無特別限 定，可使用摻雜有碘、二色性染料於聚乙烯醇（PVA)、其乙 縮醛化物、乙烯-乙酸乙烯共聚物、其皂化物等之基材，加 以延伸所得之膜、或該等經過交聯處理所得之膜等。該等 之中，又以摻雜有碘之聚乙烯醇加以延伸所得之含碘聚乙 烯醇膜、或該等經過硼酸等交聯而得者特佳。 201033659 本發明中’作爲構成保護膜之樹脂，係使用含有纖維 素衍生物之活性能量線硬化性樹脂組成物之硬化物；該纖 維素衍生物，其葡萄糖骨架之羥基之部分，係被含有不飽 和羧酸醯基之基所取代。葡萄糖骨架之羥基之部分被含有 不飽和羧酸醯基之基所取代之纖維素衍生物可單獨使用或 組合使用2種以上。此外，本說明書中，所謂活性能量線 硬化型樹脂組成物’意指可形成因活性能量線的照射而形 成硬化樹脂之組成物。 作爲葡萄糖骨架之羥基之部分被含有不飽和羧酸醯基 之基所取代之纖維素衍生物，只要爲分子内之葡萄糖骨架 的2位、3位、6位羥基之部分被含有不飽和羧酸醯基之基 所取代之自由基硬化性之纖維素衍生物，則無特別限定。 作爲不飽和羧酸醯基，可列舉丙烯醯基、甲基丙烯醯基、 α -乙基丙烯醯基、α-丙基丙烯醯基、α-丁基丙烯醯基、 丁烯酸醯基等之碳數爲3〜10左右之不飽和羧酸醯基等。 Q 作爲含有不飽和羧酸醯基之基的代表例，可列舉上述 式（1)所表示之基。式（1)中，R1表示氫原子或碳數爲1〜4 之烷基；A1、Α2爲相同或相異，表示2價之有機基；X1、 X2爲相同或相異，表示氧原子、硫原子、或-NR2-基；R2 表示氫原子或碳數爲1〜6之烷基；η爲〇或1。 作爲R1中碳數爲1〜4之烷基，例如可列舉甲基、乙 基、丙基、異丙基、丁基、異丁基、第三丁基等。作爲Ri， 以氫原子或甲基特佳。 -7- 201033659 作爲A1、A2中2價之有機基，可列舉2價之烴基、2 價之雜環基、或該等之基的2個以上直接或藉由1個或2 個以上的連結基而結合之2價之基。 作爲2價之烴基，可列舉亞甲基、伸乙基、伸丙基、 三亞甲基、伸丁基、伸戊基、伸己基、伸辛基、伸癸基、 伸十二基等之直鏈狀或支鏈状之碳數爲1〜20之炔屬烴 基；伸環戊基、伸環己基、伸環辛基、亞戊基、亞己基、 伸金剛院基（adamantanediyl)等之3〜15員之2價脂環式烴 基（伸環烷基、2價交聯脂環式基等）；伸苯基、萘基等之伸 芳基（arylene);該等結合2個以上之2價之基等。 作爲2價之雜環基，可列舉氧雜環乙烷環、氧雜環丁 烷環、氧雜環戊烷環、吡咯啶環、哌啶環、呋喃環、噻吩 環、吡啶環、唾啉環等之含有至少1種選自氧原子、硫原 子以及氮原子之雜原子之由芳香族性或非芳香族性之環去 除2個氫原子後之基等。 2價之烴基、2價之雜環基亦可具有取代基。做爲該取 代基，例如可列舉氟原子、氯原子等之鹵素原子；甲基、 乙基、丙基、異丙基、丁基等之碳數爲1〜6之烷基；三氟 甲基等之碳數爲1〜6之鹵烷基；甲氧基、乙氧基、丙氧基、 異丙氧基、丁氧基等之碳數爲1〜6之烷氧基；乙醯、丙醯 基、苯甲醯基等之碳數爲1〜10之醯基；乙醯氧基、丙醯 氧基、苯甲醯氧基、（甲基）丙烯醯氧基等之碳數爲1〜10 之醯氧基；甲氧基羰基、乙氧基羰基等之碳數爲2〜6之烷[Technical Field] The present invention relates to a polarizing plate used in a liquid crystal display device or the like and a method of manufacturing the same. [Prior Art] A polarizing plate is used as a supply element for polarized light in a liquid crystal display device, and a polarizing detecting element. In the past, a polarizing plate was used for at least one side of a polarizer composed of a polyvinyl alcohol (PVA) film, which was doped with iodine or the like, and adhered to a protective film composed of cellulose triacetate (TAC). Wait. In this case, if the protective film itself has birefringence, the function as a polarizing plate is greatly reduced. Therefore, in order to prevent this, a TAC film having no optical anisotropy produced by a solvent casting method has been used. In the above-mentioned conventional polarizing plate, in order to extend the PV A film at a high magnification, a large stress is generated in the relaxation direction. The protective film needs to have rigidity to withstand this stress. When TAC is used as a protective film, in a large-screen use such as a liquid crystal television, the contraction stress of the polarizer at the peripheral portion of the film sometimes exceeds the rigidity of the TAC and causes deformation. The birefringence of the TAC protective film resulting from this causes fading to occur. In the Japanese Laid-Open Patent Publication No. 2005-92 1-12, a cured product of an active energy ray-curable resin composition has been proposed as a substitute for the TAC protective film. According to this technique, a polarizing plate having a small birefringence and excellent heat and humidity resistance can be obtained. However, only the birefringence is small, and the birefringence at which the contraction stress of the polarizer described above is large is still changed, so that the function as a polarizing plate is impaired. [Patent Document 1] JP-A-2005-92 1 1 2 SUMMARY OF INVENTION Technical Problem An object of the present invention is to provide a protective film which is transparent even if stress is applied thereto. A polarizing plate whose birefringence is also not easily changed and a manufacturing method thereof. In order to achieve the above object, the present inventors have found that at least one side of the polarizer is protected by a protective film composed of a cured product of an active energy ray-curable resin composition containing a specific resin. In the polarizing plate, the protective film is transparent, and the birefringence is not easily changed even if stress is applied, and the present invention is completed. That is, the present invention provides a polarizing plate having a protective film made of a resin on at least one side of the polarizing mirror. The structure to be protected is characterized in that the resin is a cured product of an active energy ray-curable resin composition containing a cellulose derivative, and the cellulose derivative, which is a part of a hydroxyl group of a glucose skeleton, is unsaturated. Substituted by a carboxylic acid thiol group. The above-mentioned group containing an unsaturated carboxylic acid thiol group contains a group represented by the following formula (1): 〇〇〇-CNH-fA^NHC-xHA^X^CC^H (1) n I 2 R1 (formula Wherein R1 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4; A1 and A2 are the same or different and represent a divalent organic group; and X1 and X2 are the same or different, and represent an oxygen atom or a sulfur atom; Or -NR2- group; R2 represents a hydrogen atom or an alkyl group having a carbon number of 201033659 1 to 6; η is 0 or 1). The cellulose derivative is preferably at least one selected from the group consisting of a methyl cellulose derivative, an ethyl cellulose derivative, and a cellulose acetate derivative. The present invention also provides a method of producing a polarizing plate, comprising: coating an active energy ray-curable resin composition containing a cellulose derivative on at least one side of a polarizing mirror, and then forming the active energy ray-curable resin The material hardens to form a protective film; the cellulose derivative, which is a part of the hydroxyl group of the glucose skeleton, is substituted with a group containing an unsaturated carboxylic acid thiol group. According to the polarizing plate of the present invention, since the cured product of the active energy ray-curable resin composition containing the specific resin is used as the protective film of the polarizer, the protective film is transparent, and the birefringence is not easily changed even if stress is applied. . In addition, the birefringence is also small. According to the production method of the present invention, a polarizing plate having the above-described excellent characteristics can be easily produced. [Embodiment] MODE FOR CARRYING OUT THE INVENTION The polarizing plate of the present invention has a structure in which at least one surface of a polarizing mirror is protected by a protective film made of a resin. The polarizer is not particularly limited, and may be extended by using a substrate doped with iodine or a dichroic dye in polyvinyl alcohol (PVA), an acetal, an ethylene-vinyl acetate copolymer, or a saponified product thereof. The obtained film, or the film obtained by the crosslinking treatment, or the like. Among these, the iodine-containing polyvinyl alcohol film obtained by stretching polyvinyl alcohol doped with iodine or the above-mentioned cross-linking with boric acid or the like is particularly preferable. 201033659 In the present invention, 'the resin constituting the protective film is a cured product of an active energy ray-curable resin composition containing a cellulose derivative; the cellulose derivative, which is a part of the hydroxyl group of the glucose skeleton, contains no Substituted by a saturated carboxylic acid thiol group. The cellulose derivative in which the hydroxyl group of the glucose skeleton is substituted with a group containing an unsaturated carboxylic acid thiol group may be used singly or in combination of two or more. Further, in the present specification, the active energy ray-curable resin composition 'is a composition which forms a hardened resin by irradiation with an active energy ray. a cellulose derivative in which a hydroxyl group of a glucose skeleton is substituted with a group containing an unsaturated carboxylic acid thiol group, and a part of a hydroxyl group at the 2, 3, and 6 positions of the glucose skeleton in the molecule is contained in an unsaturated carboxylic acid. The radical-curable cellulose derivative substituted with the thiol group is not particularly limited. Examples of the unsaturated carboxylic acid thiol group include an acrylonitrile group, a methacryl fluorenyl group, an α-ethyl propylene fluorenyl group, an α-propyl acryl fluorenyl group, an α-butyl acryl fluorenyl group, a decyl decenoate group, and the like. The unsaturated carboxylic acid thiol group having a carbon number of about 3 to 10 or the like. Q. A representative example of the group containing an unsaturated carboxylic acid thiol group is a group represented by the above formula (1). In the formula (1), R1 represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4; A1 and Α2 are the same or different and represent a divalent organic group; and X1 and X2 are the same or different, and represent an oxygen atom, a sulfur atom or a -NR2- group; R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and η is ruthenium or 1. Examples of the alkyl group having 1 to 4 carbon atoms in R1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. As Ri, it is particularly preferable as a hydrogen atom or a methyl group. -7- 201033659 The divalent organic group in A1 and A2 may be a divalent hydrocarbon group, a divalent heterocyclic group, or two or more of these groups, or may be linked by one or two or more. Base and combine the base of 2 valence. Examples of the divalent hydrocarbon group include a methylene group, an exoethyl group, a propyl group, a trimethylene group, a butyl group, a pentyl group, a hexyl group, a decyl group, a decyl group, a twelfth group, and the like. a chain or branched acetylene group having a carbon number of 1 to 20; a cyclopentyl group, a cyclohexylene group, a cyclooctyl group, a pentylene group, a hexylene group, an adamantanediyl group, etc. 3~ a 15-membered divalent alicyclic hydrocarbon group (cycloalkylene group, a divalent crosslinked alicyclic group, etc.); an arylene group such as a phenyl group or a naphthyl group; and a combination of two or more valences Base and so on. Examples of the divalent heterocyclic group include an oxocyclohexane ring, an oxetane ring, an oxolane ring, a pyrrolidine ring, a piperidine ring, a furan ring, a thiophene ring, a pyridine ring, and a sormine. A group in which at least one hydrogen atom, a sulfur atom, and a nitrogen atom are contained in a ring or the like, and a hydrogen atom is removed from an aromatic or non-aromatic ring. The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom or a chlorine atom; an alkyl group having a carbon number of 1 to 6 such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group; and a trifluoromethyl group; a halogenated alkyl group having a carbon number of 1 to 6; an alkoxy group having a carbon number of 1 to 6 such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a butoxy group; The carbon number of the fluorenyl group, the benzamidine group or the like is 1 to 10; the carbon number of the ethoxy group, the propenyloxy group, the benzamethyleneoxy group, the (meth)acryloxy group, etc. is 1~ a methoxy group of 10; a methoxycarbonyl group, an ethoxycarbonyl group or the like having a carbon number of 2 to 6
201033659 氧基羰基；硝基；氰基等。 作爲上述連結基，可列舉-0-、-S-、-NR3-、-CO-等。 上述R3表示氫原子或碳數爲1〜6之烷基。 作爲R2、R3中碳數爲1〜6之烷基，例如可列舉甲基、 乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、 已基等。 作爲上述葡萄糖骨架之部分羥基被含有不飽和羧酸醯 基之基所取代之纖維素衍生物，可列舉葡萄糖骨架之剩餘 φ 羥基之一部分或全部經醚化之纖維素醚衍生物、葡萄糖骨 架之剩餘羥基之一部分或全部經有機酸酯化之纖維素有機 酸酯衍生物、葡萄糖骨架之剩餘羥基之一部分或全部經無 機酸酯化之纖維素無機酸酯衍生物、葡萄糖骨架之剩餘羥 基之一部分或全部經胺甲酸酯化之纖維素胺甲酸酯衍生 物、葡萄糖骨架之剩餘羥基之一部分或全部經乙縮醛化之 纖維素乙縮醛衍生物等。 ❹ 纖維素醚衍生物，包含甲基纖維素衍生物、乙基纖維 素衍生物、羧甲基纖維素衍生物、氰乙基纖維素衍生物、 羥乙基纖維素衍生物、羥丙基纖維素衍生物、乙基羥乙基 纖維素衍生物等。纖維素有機酸酯衍生物，包含乙酸纖維 素衍生物、乙酸丙酸酯纖維素、乙酸丁酸酯纖維素、乙酸 苯甲酸酯纖維素衍生物等。無機酸酯纖維素衍生物，包含 硝酸纖維素衍生物、硫酸纖維素衍生物等。胺甲酸酯纖維 素衍生物，可列舉苯基胺甲酸酯纖維素衍生物等。 -9- 201033659 該等之中，又以纖維素醚衍生物、有機酸酯纖維素衍 生物較佳；又以甲基纖維素衍生物、乙基纖維素衍生物、 乙酸纖維素衍生物特佳。 上述葡萄糖骨架之羥基之部分被含有不飽和羧酸醯基 之基所取代之纖維素衍生物中，含有不飽和羧酸醯基之基 的取代度，例如可爲0.1〜1.0、較佳爲0.2〜0.6。此外，上 述葡萄糖骨架之羥基之部分被含有不飽和羧酸醯基之基所 取代之纖維素衍生物中，含有不飽和羧酸醯基之基以外之 Θ 取代基的取代度，例如可爲2.0〜2.9、較佳爲2.4〜2.8。該 等之取代度，係顧及溶劑溶解性、使用性、光學特性等而 加以適當選擇。 上述葡萄糖骨架之部分羥基被含有不飽和羧酸醯基之 基所取代之纖維素衍生物，可藉由習知之纖維素衍生物作 爲原料，利用習知之反應來製造。 例如，葡萄糖骨架之部分羥基被上述式（1)所示之含有 H 不飽和羧酸醯基之基（其中，式中n=l)所取代之纖維素衍生 物，例如可藉由將具有游離羥基之纖維素衍生物、下述式 (2)所表示之聚異氰酸酯化合物、與下述式（3)所表示之不飽 和羧酸衍生物加以反應來製造。 OCN-A^NCO (2) (式中，A1與上述相同） -10- 201033659 ο201033659 oxycarbonyl; nitro; cyano and the like. Examples of the linking group include -0-, -S-, -NR3-, -CO-, and the like. R3 above represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms in R2 and R3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group. The cellulose derivative in which a part of the hydroxyl group of the glucose skeleton is substituted with a group containing an unsaturated carboxylic acid thiol group may, for example, be a part or all of the remaining φ hydroxy group of the glucose skeleton, and an etherified cellulose ether derivative or a glucose skeleton. a part or all of the remaining organic hydroxylated cellulose organic acid ester derivative, one or both of the remaining hydroxyl groups of the glucose backbone, a partially or wholly inorganically esterified cellulose inorganic acid ester derivative, and a part of the remaining hydroxyl group of the glucose backbone Or all of the urethane-derived cellulose urethane derivative, a part or all of the remaining hydroxy group of the glucose skeleton, or the acetalized cellulose acetal derivative.纤维素 A cellulose ether derivative comprising a methyl cellulose derivative, an ethyl cellulose derivative, a carboxymethyl cellulose derivative, a cyanoethyl cellulose derivative, a hydroxyethyl cellulose derivative, a hydroxypropyl fiber A derivative, an ethyl hydroxyethyl cellulose derivative or the like. The cellulose organic acid ester derivative comprises a cellulose acetate derivative, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate derivative and the like. The inorganic acid ester cellulose derivative contains a nitrocellulose derivative, a cellulose sulfate derivative, and the like. The urethane cellulose derivative may, for example, be a phenyl carbamate cellulose derivative. -9- 201033659 Among these, cellulose ether derivatives, organic acid ester cellulose derivatives are preferred; methyl cellulose derivatives, ethyl cellulose derivatives, cellulose acetate derivatives are preferred. . In the cellulose derivative in which the hydroxyl group of the glucose skeleton is substituted with a group containing an unsaturated carboxylic acid thiol group, the degree of substitution of the group containing an unsaturated carboxylic acid thiol group may be, for example, 0.1 to 1.0, preferably 0.2. ~0.6. Further, in the cellulose derivative in which the hydroxyl group of the glucose skeleton is substituted with a group containing an unsaturated carboxylic acid thiol group, the degree of substitution of the hydrazine substituent other than the group of the unsaturated carboxylic acid thiol group may be, for example, 2.0. ~2.9, preferably 2.4~2.8. The degree of substitution is appropriately selected in consideration of solvent solubility, usability, optical properties and the like. A cellulose derivative in which a part of the hydroxyl group of the glucose skeleton is substituted with a group containing an unsaturated carboxylic acid thiol group can be produced by a conventional reaction using a conventional cellulose derivative as a raw material. For example, a part of the hydroxyl group of the glucose skeleton is substituted with a cellulose derivative containing a group of a H-unsaturated carboxylic acid group (wherein n = 1) represented by the above formula (1), for example, by having a free The cellulose derivative of a hydroxyl group, the polyisocyanate compound represented by the following formula (2), and the unsaturated carboxylic acid derivative represented by the following formula (3) are produced and reacted. OCN-A^NCO (2) (where A1 is the same as above) -10- 201033659 ο
HxLa2~x2-C-C=CH (3) R1 (式中’ R1、A2、X1、χ2與上述相同） 作爲具有游離羥基之纖維素衍生物，係取代度低於3 之各種纖維素衍生物，例如可列舉甲基纖維素、乙基纖維 素、羧甲基纖維素、氰乙基纖維素、羥乙基纖維素羥丙 φ 基纖維素、乙基羥乙基纖維素等之纖維素醚；乙酸纖維素、 乙酸丙酸纖維素、乙酸丁酸纖維素、乙酸苯甲酸纖維素等 之纖維素有機酸酯；硝酸纖維素、硫酸纖維素等之纖維素 無機酸酯；纖維素苯基胺甲酸酯等之胺甲酸纖維素；乙縮 薛纖維素等。該等之中’又以纖維素醒、纖維素有機酸醋 較佳；又以甲基纖維素、乙基纖維素、乙酸纖維素特佳。 作爲式（2)所表示之聚異氰酸酯化合物，只要爲於分子 内至少具有2個異氰酸酯基之化合物，則無特別限定。聚 G 異氰酸酯化合物，例如包含脂肪族聚異氰酸酯、脂環式聚 異氰酸酯、芳香族聚異氰酸酯、芳香脂肪族聚異氰酸酯等。 聚異氰酸酯化合物可單獨使用或組合使用2種以上。 作爲脂肪族聚異氰酸酯，例如可列舉1,5-五亞甲二異 氰酸酯、1，6-六亞甲二異氰酸酯、2-甲基-1，5-五亞甲二異氰 酸酯、3-甲基-1，5-五亞甲二異氰酸酯、2,4,4-三甲基-1，6-六亞甲二異氰酸酯、2，2,4-三甲基-1，6-六亞甲二異氰酸酯、 2,6-二異氰酸酯已酸甲酯、離胺酸二異氰酸酯等之脂肪族二 -II- 201033659 異氰酸酯等。 作爲脂環式聚異氰酸酯，例如可列舉1，3 -環.戊烷二異 氰酸酯、1,4-環己烷二異氰酸酯、3-異氰酸酯甲基-3,5，5-三 ，甲基環己基異氰酸酯、4,4'亞甲基雙（環己基異氰酸酯）、 甲基-2,4-環己烷二異氰酸酯、甲基-2,6_環己烷二異氰酸 酯、1,3-雙（異氰酸酯甲基）環己烷、i〆-雙（異氰酸酯甲基） 環己烷、異佛酮二異氰酸酯、降莰烷二異氰酸酯等之脂環 _ 式二異氰酸酯等。 作爲芳香族聚異氰酸酯’例如可列舉間伸苯基二異氰 酸酯、對伸苯基二異氰酸酯、2,4 -甲苯二異氰酸酯、2,6-甲 苯二異氰酸酯、萘-1,4-二異氰酸酯、萘-丨，5_二異氰酸酯、 4，4'二苯基二異氰酸酯、4,4'二苯甲烷二異氰酸酯、2,4' 二苯甲烷二異氰酸酯、4,4'二苯基醚二異氰酸酯等之芳香 族二異氰酸酯等。 作爲芳香脂肪族聚異氰酸酯，例如可列舉ι，3 -苯二甲 〇 基二異氰酸酯、1，4-苯二甲基二異氰酸酯、二異氰 酸酯-1,4-二乙基苯、1,3-雙（1-異氰酸酯-丨-甲基乙基）苯、丨，4-雙（1-異氰酸酯-1-甲基乙基）苯、1，3-雙（α，α -二甲基異氰酸 酯甲基）苯等之芳香脂肪族二異氰酸酯等。 作爲聚異氰酸酯化合物’若使用脂肪族聚異氰酸酯、 脂環式聚異氰酸酯或芳香脂肪族聚異氰酸酯，則可獲得變 色較少之樹脂。此外’本發明中，作爲聚異氰酸酯化合物， 可使用上述例示之脂肪族聚異氰酸酯、脂環式聚異氰酸 -12- 201033659 酯、芳香族聚異氰酸酯、芳香脂肪族聚異氰酸酯之二聚體 或三聚體、反應生成物或聚合物（例如，二苯甲烷二異氰酸 酯之二聚體或三聚體、三羥甲基丙烷與二異氰酸甲苯酯構 成之反應生成物、三羥甲基丙烷與六亞甲二異氟酸酯構成 之反應生成物、聚亞甲基聚苯基異氰酸酯、聚醚聚異氰酸 酯、聚酯聚異氰酸酯等）等。作爲聚異氰酸酯化合物，又以 異佛酮二異氰酸酯等之脂環式二異氰酸酯特佳。 此外’作爲式（2)所表示之聚異氰酸酯化合物，可使用 ❹ _ 多元醇類與聚異氰酸酯進行反應所獲得之兩末端異氰酸酯 胺基甲酸酯預聚物。多元醇類，包含一般之多元醇、聚醚 多元醇、聚酯多元醇、聚碳酸酯多元醇等。 作爲式（3)所表示之不飽和羧酸衍生物，例如可列舉2-羥乙基（甲基）丙烯酸酯、2-羥丙基（甲基）丙烯酸酯、3-羥丙 基（甲基）丙烯酸酯、4-羥丁基（甲基）丙烯酸酯、聚乙二醇（甲 基）丙烯酸酯、聚丙二醇（甲基）丙烯酸酯等之於末端具有羥 Q 基之（甲基）丙烯酸酯；2-胺乙基（甲基）丙烯酸酯等之於末端 具有胺基之（甲基）丙烯酸酯或（甲基）丙烯醯胺；2-硫醇乙基 (甲基）丙烯酸酯等之於末端具有硫醇基之（甲基）丙烯酸酯 等。該等之中，又以2-羥乙基（甲基）丙烯酸酯等之於末端 具有羥基之（甲基）丙烯酸酯較佳。 作爲具有游離羥基之纖維素衍生物、式（2)所表示之聚 異氰酸酯化合物、式（3)所表示之不飽和羧酸衍生物的反應 順序，可採用以下任一方法：（i)具有游離羥基之纖維素衍 201033659 生物與式（2)所表示之聚異氰酸酯化合物進行反應，生成於 末端具有異氰酸酯基之纖維素衍生物之後’再將該反應生 成物與式（3)所表示之不飽和羧酸衍生物進行反應；（ii)式（2) 所表示之聚異氰酸酯化合物與式（3)所表示之不飽和羧酸 衍生物進行反應’生成於末端具有異氰酸酯基之不飽和羧 酸衍生物之後’再將該反應生成物與具有游離羥基之纖維 素衍生物進行反應。U)之方法中因最初反應時有產生膠化 的疑慮，故以（ii)之方法較佳。 此外，具有游離羥基之纖維素衍生物，爲了防止聚異 氰酸酯化合物的失活、以及系統的白濁’於用於反應之前 進行脫水處理較佳。HxLa2~x2-CC=CH (3) R1 (wherein R1, A2, X1, and χ2 are the same as above). As a cellulose derivative having a free hydroxyl group, various cellulose derivatives having a degree of substitution of less than 3, for example Examples thereof include cellulose ethers such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, hydroxyethyl cellulose hydroxypropyl φ based cellulose, and ethyl hydroxyethyl cellulose; Cellulose organic acid esters of cellulose, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose inorganic acid esters such as nitrocellulose, cellulose sulfate, etc.; cellulose phenylaminecarboxylic acid A urethane cellulose such as an ester; Among them, cellulose ketone and cellulose organic acid vinegar are preferred; methyl cellulose, ethyl cellulose and cellulose acetate are particularly preferred. The polyisocyanate compound represented by the formula (2) is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule. The poly G isocyanate compound contains, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, an aromatic aliphatic polyisocyanate or the like. The polyisocyanate compounds may be used alone or in combination of two or more. Examples of the aliphatic polyisocyanate include 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, and 3-methyl-1. , 5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2 , aliphatic di-II-201033659 isocyanate, etc. of 6-diisocyanate methyl acrylate, diazonic acid diisocyanate or the like. Examples of the alicyclic polyisocyanate include 1,3 -cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-tri,methylcyclohexyl isocyanate. , 4,4' methylene bis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanate methyl An alicyclic alicyclic diisocyanate such as cyclohexane, i〆-bis(isocyanatemethyl)cyclohexane, isophorone diisocyanate or norbornane diisocyanate. Examples of the aromatic polyisocyanate include exophenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,4-diisocyanate, and naphthalene-丨, aroma of 5_ diisocyanate, 4,4' diphenyl diisocyanate, 4,4' diphenylmethane diisocyanate, 2,4' diphenylmethane diisocyanate, 4,4' diphenyl ether diisocyanate Group diisocyanate and the like. Examples of the aromatic aliphatic polyisocyanate include iota, 3-phthalic diisocyanate, 1,4-benzyldimethylisocyanate, diisocyanate-1,4-diethylbenzene, and 1,3-double. (1-Isocyanate-丨-methylethyl)benzene, anthracene, 4-bis(1-isocyanate-1-methylethyl)benzene, 1,3-bis(α,α-dimethylisocyanatemethyl) An aromatic aliphatic diisocyanate such as benzene. When an aliphatic polyisocyanate, an alicyclic polyisocyanate or an aromatic aliphatic polyisocyanate is used as the polyisocyanate compound, a resin having less coloration can be obtained. Further, in the present invention, as the polyisocyanate compound, the above-exemplified aliphatic polyisocyanate, alicyclic polyisocyanate-12-201033659 ester, aromatic polyisocyanate, aromatic aliphatic polyisocyanate dimer or the like may be used. a polymer, a reaction product or a polymer (for example, a dimer or trimer of diphenylmethane diisocyanate, a reaction product of trimethylolpropane and toluene diisocyanate, trimethylolpropane and A reaction product composed of hexamethylene diisofluoride, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, or the like. As the polyisocyanate compound, an alicyclic diisocyanate such as isophorone diisocyanate is particularly preferable. Further, as the polyisocyanate compound represented by the formula (2), a two-terminal isocyanate urethane prepolymer obtained by reacting ❹-polyol with a polyisocyanate can be used. The polyhydric alcohols include general polyols, polyether polyols, polyester polyols, polycarbonate polyols, and the like. Examples of the unsaturated carboxylic acid derivative represented by the formula (3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (methyl). a (meth) acrylate having a hydroxyl group at the terminal, such as acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, or polypropylene glycol (meth) acrylate ; 2-aminoethyl (meth) acrylate, etc., such as (meth) acrylate or (meth) acrylamide, having an amine group at the terminal; 2-thiol ethyl (meth) acrylate, etc. A (meth) acrylate having a thiol group at the terminal or the like. Among these, a (meth) acrylate having a hydroxyl group at the terminal is preferably a 2-hydroxyethyl (meth) acrylate or the like. As a reaction sequence of the cellulose derivative having a free hydroxyl group, the polyisocyanate compound represented by the formula (2), and the unsaturated carboxylic acid derivative represented by the formula (3), any of the following methods may be employed: (i) having a free form Hydroxy Cellulose Derivative 201033659 The reaction of the polyisocyanate compound represented by the formula (2) with a cellulose derivative having an isocyanate group at the end is followed by the reaction product and the unsaturated form represented by the formula (3). The carboxylic acid derivative is reacted; (ii) the polyisocyanate compound represented by the formula (2) is reacted with the unsaturated carboxylic acid derivative represented by the formula (3) to form an unsaturated carboxylic acid derivative having an isocyanate group at the terminal. Thereafter, the reaction product is further reacted with a cellulose derivative having a free hydroxyl group. In the method of U), since the gelation is caused by the initial reaction, the method of (ii) is preferred. Further, in order to prevent deactivation of the polyisocyanate compound and the white turbidity of the system, the cellulose derivative having a free hydroxyl group is preferably subjected to dehydration treatment before being used for the reaction.
上述各反應，可利用聚異氰酸酯化合物與具有活性氫 之化合物反應時通常所使用之方法。反應係於乙酸丁酯等 之適當的有機溶劑中進行。反應中亦可使用錫化合物等之 觸媒。反應溫度，例如可爲0〜180°C、較佳爲20〜150°C 左右。 此外，葡萄糖骨架之部分羥基被上述式（1)所表示之含有 不飽和羧酸醯基之基（其中，式中n = 0)所取代之纖維素衍生 物，例如可藉由將具有游離羥基之纖維素衍生物、與下述 式（4)所表示之具有不飽和羧酸醯基與異氰酸酯基之化合 物加以反應來製造。 0 ⑷ 0CN-A2-X2-C-C=CHr -14 - 201033659 (式中’ R1、A2、X2與上述相同） 作爲具有游離羥基之纖維素衍生物可使用上述之物。 作爲式（4 )所表示之化合物的代表例，可列舉2 ·(甲基） 丙烯醯氧乙基異氰酸酯、2-〔2-(甲基）丙烯醯氧基乙氧基〕 乙基異氰酸酯等。 本發明之活性能量線硬化型樹脂組成物中，可僅含有 上述葡萄糖骨架之羥基之部分被含有不飽和羧酸醯基之基 所取代之纖維素衍生物來作爲活性能量線硬化性化合物， 亦可進一步含有其他活性能量線硬化性化合物。作爲上述 之其他活性能量線硬化性化合物，可列舉自由基硬化性化 合物、陽離子硬化性化合物》 作爲自由基硬化性化合物，可列舉於分子内具有至少 1個乙烯性雙鍵、且於聚合起始劑的存在下可藉由活性能 量線（例如紫外線、可見光、電子線、X線等）的照射而聚合 之化合物。作爲上述化合物，例如可列舉（甲基）丙烯酸；（甲 φ 基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲 基）丙烯酸丁酯、（甲基）丙烯酸第三-丁酯、（甲基）丙烯酸2-乙基已酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸苯甲酯、（甲 基）丙烯酸環己酯、（甲基）丙烯酸二環戊烯酯、（甲基）丙烯 酸環氧丙酯、（甲基）丙烯酸甲氧基乙酯、（甲基）丙烯酸乙氧 基乙酯、（甲基）丙烯酸四氫呋喃甲酯、（甲基）丙烯酸2-羥乙 酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸苯氧乙酯、（甲 基）丙烯酸降莰酯、（甲基）丙烯酸異莰酯、（甲基）丙烯醯基 -15- 201033659 嗎啉、τ-(甲基）丙烯醯氧基丙基三甲氧基矽烷等之單官能 (甲基）丙烯酸酯系單體；苯乙烯、α-甲苯乙烯、乙烯基甲 苯、乙酸乙烯酯、乙酸烯丙酯、丙酸乙烯酯、安息香酸乙 烯酯、Ν-乙烯吡咯烷酮、Ν-乙烯咪唑、Ν-乙烯己內醯胺等 之乙烯系單體；1,4-丁二醇二（甲基）丙烯酸酯、1,6-己二醇 二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、乙二醇二 (甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、聚丙二醇二 (甲基）丙烯酸酯、雙酚Α-二環氧丙基醚二（甲基）丙烯酸酯、 ❹ 環氧乙烷改質雙酚Α-二（甲基）丙烯酸酯等之2官能性（甲基） 丙烯酸酯：三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇四（甲 基）丙烯酸酯、季戊四醇五（甲基）丙烯酸酯、季戊四醇六（甲 基）丙烯酸酯、環氧乙烷加成三羥甲基丙烷之三（甲基）丙烯 酸酯、二季戊四醇五（甲基）丙烯酸酯、三聚氰酸三烯丙酯、 異三聚氰酸三烯丙酯、1，3,5-三丙烯醯基六氫二級肼等3官 能以上之多官能性單體。該等之中，以2官能以上之多官 Q 能性單體較佳。該等之自由基硬化性化合物可單獨使用或 組合使用2種以上。 此外，作爲自由基硬化性化合物，可使用（甲基）丙烯 酸酯、（甲基）丙烯酸胺基甲酸酯、（甲基）丙烯酸環氧酯、（甲 基）丙烯酸丙烯酸酯等之（甲基）丙烯酸酯寡聚物。 作爲陽離子硬化性化合物，例如可列舉乙烯醚系化合 物、環氧系化合物、氧雜環丁烷系化合物等。 作爲乙烯醚系化合物，例如可列舉環氧乙烷改質雙酚 -16- 201033659 A -二乙烯醚、環氧乙烷改質氫醌二乙烯醚等。 作爲環氧系化合物，例如可列舉1,2-環氧環己烷、檸 檬烯二環氧化合物、3,4-環氧環己基甲基.3’ ，4’ -環氧環己 烷羧酸酯、1，4-丁二醇二環氧丙基醚、三羥甲基丙烷二環氧 丙基醚、雙（3,4-環氧基-6-甲基環己基甲基）己二酸酯、聯苯 A -二環氧丙基醚、聯苯F -二環氧丙基醚、聯苯S-二環氧丙 基醚、氫化聯苯A -二環氧丙基醚等。 作爲氧雜環丁烷系化合物，可列舉3 -乙基-3-羥甲基氧 〇 雜環丁烷、3-乙基- 3-(苯氧基甲基）氧雜環丁烷、二〔（3-乙基-3-氧雜環丁基）甲基〕醚等》 本發明之活性能量線硬化型樹脂組成物中，除了活性 能量線硬化性化合物之外，亦可含有熱硬化性化合物。 活性能量線硬化型樹脂組成物中之總硬化性化合物中 所佔有之上述葡萄糖骨架之部分羥基被含有不飽和羧酸醯 基之基所取代之纖維素衍生物的比例，例如可爲30重量％ Q 以上、較佳爲50重量％以上、更佳爲70重量％以上、特 佳爲90重量％以上。 此外，活性能量線硬化型樹脂組成物中，除了上述硬 化性化合物之外，亦可配合光聚合起始劑，以及視需要亦 可配合、光增感劑、光陽離子聚合起始劑、熱陽離子聚合 起始劑、熱自由基聚合起始劑、光促進劑、光安定劑、紫 外線吸収劑、調平劑、消泡劑等。 作爲光聚合起始劑，可視硬化手段之活性能量線的種 -17- 201033659 類加以適當選擇。作爲光聚合起始劑之例，可列舉苯乙酮、 3 -甲基苯乙酮、二苯基酮、4-氯二苯基酮、4,4 -二胺基二苯 基酮、1-羥基-環己基-苯基-酮、2,2-二甲氧基-2-苯乙酮、 岫弗嗣（Xanthone fluorenone)、苯甲醒、蒽_、安息香乙 醚、安息香丙醚、苯甲基二甲基縮酮、1-(4-異丙基苯基）-2-羥基-2-甲基丙烷-1-酮、4 -印黃酮、樟腦醌、2 -甲基-1-〔 4-(甲 硫基）苯基〕-2-嗎啉基丙烷-1-酮等。 上述葡萄糖骨架之部分羥基被含有不飽和羧酸醯基之 ❹ 基所取代之纖維素衍生物於活性能量線硬化型樹脂組成物 中的含量，相對於活性能量線硬化型樹脂組成物中固體成 分全體（包含因硬化而固化之成分），例如可爲30〜99.9重 量％、較佳爲50〜99.5重量％、更佳爲70〜99重量％、特 佳爲90〜99重量％。 光聚合起始劑於活性能量線硬化型樹脂組成物中的含 量，相對於活性能量線硬化型樹脂組成物中固體成分全體 Q (包含因硬化而固化之成分），例如可爲0.1〜10重量％、較 佳爲1〜8重量％左右。 本發明之偏光板，係藉由以下方式製造：於偏光鏡之 至少一面，塗覆上述活性能量線硬化型樹脂組成物，然後 使該活性能量線硬化型樹脂組成物硬化而形成保護膜。 作爲活性能量線硬化型樹脂組成物之塗覆方法，並無 特別限定，可利用刮刀塗佈、線棒塗佈、狹縫塗佈、凹板 塗佈等各種的塗覆方式。於塗覆時亦可使用溶劑來調整硬 -18 - 201033659 化型樹脂組成物的黏度。 . 由活性能量線硬化型樹脂組成物所構成之塗膜，係藉 由照射活性能量線進行硬化，以形成保護膜。作爲活性能 量線，可列舉紫外線、可見光、電子線、X射線等。該等 之中，又以使用紫外線較佳。作爲紫外線的產生源，可列 舉低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、 化學燈、氙燈、黑光燈、金屬鹵素燈等。 保護膜的厚度，由薄型輕量性、保護性、處理性等之 〇 觀點來看，例如可爲10〜200/zm、較佳爲30〜100/zm。 本發明之偏光板，因使用含有具備不飽和羧酸醯基以 及脂環式骨格之化合物與纖維素衍生物之活性能量線硬化 型樹脂組成物之硬化物作爲偏光鏡之保護膜，故具有保護 膜爲透明，即使施加應力其雙折射亦不易變化之主要好處。 實施例 以下，根據實施例對本發明進行更詳細的説明，但本 〇 發明並未限定於該等實施例中。此外，藉由以下方法進行 硬化膜之光彈性係數以及相位差的測定、與玻璃轉移溫度 的測定。 〔光彈性係數以及相位差的測定〕 製作厚度100//Π1的硬化膜，使用王子計測機器股份有 限公司製之三維雙折射計（「KOBRA-WR」）進行測定。 〔玻璃轉移溫度的測定〕 於冷壓延鋼板（厚度〇.3mmx寬20mmx長50mm)上、塗佈 -19- 201033659 活性能量線硬化型樹脂組成物（厚度40 a m)、利用小型UV 照射機（EYE GRAPHICS股份有限公司製、「ECS-401GX」、 額定電壓200V、高壓水銀燈）自11cm的距離照射累計光量 3 5 0m〗/cm2的紫外線，製得活性能量線硬化型樹脂組成物 的硬化膜。對該膜利用剛體振子型黏彈性測定裝置（A&D股 份有限公司製、「RPT-3000W」）、自25°C升溫至200°C， 測定玻璃轉移溫度（Tg)。 合成例1 ❹ 將羥基價32.9mgKOH/g的乙基纖維素80.4重量份溶 解於乙酸丁酯72 3.6重量份中，並一邊以128 °C餾出乙酸丁 酯一邊進行乙基纖維素的脫水。餾出124.8重量份的乙酸 丁酯與水的混合溶液之後、利用卡爾費雪水分測定儀（Karl Fischer Moisture Titrator)對乙基纖維素之乙酸丁醋溶液中 的水分進行測定，結果水分爲0.025重量％。此外，脫水 後、於乙基纖維素之乙酸丁酯溶液中添加餾出之部分的乙 φ 酸丁酯，將乙基纖維素的濃度調整爲10重量％。 於混合有氮與氧之雰圍下（氧濃度5%)、將乙酸丁酯 38.06重量份、異佛酮二異氰酸酯（IPDI)IOO重量份、二月 桂酸二丁基錫0.046重量份〔相對於IPDI與2-羥乙基丙烯 酸酯（HEA)的反應物之濃度爲300重量ppm的量〕裝入燒瓶 中混合，並升溫至40°C。此時，歷經1小時滴加HE A 52.25 重量份。當異氰酸酯濃度（溶液中之NC 0濃度）爲9.94重量 %之時，冷卻至室溫，製得含有（甲基）丙烯酸酯（異佛酮二 -20- 201033659 異氰酸酯1莫耳與2 -羥乙基丙烯酸酯1莫耳反應後於末端. 具有異氰酸酯基）之溶液。 於混合有氮與氧之雰圍下（氧濃度5%)，將經脫水處理 後之羥基價32.9mgKOH/g的乙基纖維素之乙酸丁酯溶液 (10重量％溶液）67 9重量份、二月桂酸二丁基錫0.0282重 量份裝入燒瓶中攪拌，並升溫至100 °C。將經調製後之含有 (甲基）丙烯酸酯（於末端具有異氰酸酯基）之溶液19.42重量 份歷經1小時滴加。之後，進行熟化，當異氰酸酯濃度爲 0.1重量％以下之時，冷卻至室溫，製得含有纖維素衍生物 (乙基纖維素之羥基被含有丙烯醯基之基取代）之溶液（固體 成分16.4重量％)。 合成例2 將乙酸纖維素（Daicel化學工業製、L-20)於150°C乾燥 24小時，使乙酸纖維素中的水分成爲0.86重量％。此時之 羥基價爲97.13mgKOH/g。此乾燥之乙酸纖維素35重量份 與環己酮316重量份、甲苯65重量份混合’以155 °C餾出 環己酮、甲苯、與水的混合液之後，利用卡爾費雪水分測 定儀（Karl Fischer Moisture Titrator)對乙酸纖維素之環己 酮溶液中的水分進行測定’結果水分爲0.015重量％。此 外，脫水後、將乙酸纖維素的濃度利用環己酮調整爲10.9 重量％。 混合有氮與氧之雰圍下（氧濃度5%)、將經脫水處理後 之羥基價97.13 mgKOH/g的乙酸纖維素之環己嗣溶液（10.9 201033659 重量％溶液）2 11重量份裝入燒瓶中攪拌，並升溫至70 °C。 到達70°C後，添加異氰酸酯丙烯酸酯（2-丙烯醯氧基乙基異 氰酸酯；昭和電工製、AOI-VM)4.6重量份。AOI-VM添加2 小時後，將二月桂酸二丁基錫0.0 8重量份裝入燒瓶中攪 拌，持續進行反應。之後，進行熟化，當異氰酸酯濃度爲 0.1重量％以下之時，冷卻至室溫，製得含有纖維素衍生物 (乙酸纖維素之羥基被含有丙烯醯基之基取代）之溶液（固體 成分12.8重量％ )。 〇 實施例1 於合成例1所製得之含有纖維素衍生物（乙基纖維素之 羥基被含有丙烯醯基之基取代）之溶液100重量份中，混合 ' 、1-羥基-環己基-苯基-酮0.82重量份，獲得活性能量線硬化 型樹脂組成物1。使用塗佈器將活性能量線硬化型樹脂組 成物1於玻璃板上塗布600 //m的膜厚，再以80°C乾燥1 小時之後，使用小型UV照射機（EYE GRAPHICS股份有限 0 公司製、「ECS-401GX」、額定電壓200V、高壓水銀燈） 自11cm的距離照射3次累計光量500m】/cm2的紫外線， 獲得活性能量線硬化型樹脂組成物1的單獨硬化膜（厚度98 V m)。將所得之硬化膜的外觀以目視進行觀察，並測定光 彈性係數以及相位差》 實施例2 於合成例2所製得之含有纖維素衍生物（乙酸纖維素之 羥基被含有丙烯醯基之基取代）之溶液1〇〇重量份中，混合 201033659 1-羥基-環己基-苯基-酮0.82重量份，獲得活性能量線硬化 型樹脂組成物2。使用塗佈器將活性能量線硬化型樹脂組 成物2於玻璃板上塗布600 /zm的膜厚，再以80°C乾燥1 小時之後，使用小型UV照射機（EYE GRAPHICS股份有限 公司製、「ECS-401GX」、額定電壓200V、高壓水銀燈） 自11cm的距離照射3次累計光量50 0m J/cm2的紫外線， 獲得活性能量線硬化型樹脂組成物2的單獨硬化膜（厚度77 从m)。將所得之硬化膜的外觀以目視進行觀察，並測定光 〇 彈性係數以及相位差。 比較例1 將10重量％之羥基價32.9mgKOH/g的乙基纖維素之 ' 乙酸乙酯溶液500重量份、季戊四醇三丙烯酸酯50重量 份、1-羥基-環己基-苯基-酮5重量份進行混合，獲得活性 能量線硬化型樹脂組成物3»使用塗佈器將活性能量線硬 化型樹脂組成物3於玻璃板上塗布55 0 y m的膜厚，再以 Q 8〇°C乾燥1小時之後，以與實施例1相同的方式照射紫外 線，獲得活性能量線硬化型樹脂組成物3的單獨硬化膜（厚 度1 00 /z m)。將所得之硬化膜的外觀以目視進行觀察，並 測定光彈性係數以及相位差。 比較例2 將10重量％之羥基價32.9mgKOH/g的乙基纖維素之 乙酸乙酯溶液5 00重量份、二季戊四醇六丙烯酸酯50重量 份、1-羥基-環己基-苯基-酮5重量份進行混合，獲得活性 -23- 201033659 能量線硬化型樹脂組成物4。使用塗佈器將活性能量線 . 化型樹脂組成物4玻璃板上塗布5 50 μιη的膜厚，再以 t乾燥1小時之後，以與實施例1相同的方式照射紫外箱 獲得活性能量線硬化型樹脂組成物4的單獨硬化膜（厚 1 00 Μ m)。將所得之硬化膜的外觀以目視進行觀察，並測 光彈性係數以及相位差。 比較例3 將10重量％之羥基價32.9mgKOH/g的乙基纖維素 〇 乙酸乙酯溶液500重量份、季戊四醇乙氧基四丙烯酸酯 重量份、1-羥基-環己基-苯基-酮5重量份進行混合，獲 活性能量線硬化型樹脂組成物5。使用塗佈器將活性能 ' 線硬化型樹脂組成物5於玻璃板上塗佈550 // m的膜厚， 以80°C乾燥1小時之後，以與實施例1相同的方式照射 外線，獲得活性能量線硬化型樹脂組成物5的單獨硬化 (厚度100 V m)。將所得之硬化膜的外觀以目視進行觀察 Q 並測定光彈性係數以及相位差。 實施例以及比較例所得之硬化膜的外觀、玻璃轉移 度、光彈性係數以及相位差的測定結果示於表1。表中 「一」表示無法測定。 硬 80 [» 度 定 之 50 得 量 再 紫 膜 溫 201033659 表1 實施例 比較例 1 2 1 2 .3 外觀 透明 透明 塗膜於彎曲、打孔時有裂痕 白濁 白濁 Tg(°C) 140 160 146 152 142 光彈性係數 (xlO^Pa1) 16.7 14.1 — — — 相位差(nm) 13.6 0.4 — — — 【圖式簡單說明】 te 〇 【主要元件符號說明】 並〇For each of the above reactions, a method generally used in the reaction of a polyisocyanate compound with a compound having active hydrogen can be used. The reaction is carried out in a suitable organic solvent such as butyl acetate. A catalyst such as a tin compound can also be used in the reaction. The reaction temperature can be, for example, from 0 to 180 ° C, preferably from about 20 to 150 ° C. Further, a part of the hydroxyl group of the glucose skeleton is substituted with a cellulose derivative having a group of an unsaturated carboxylic acid thiol group (wherein n = 0) represented by the above formula (1), for example, by having a free hydroxyl group. The cellulose derivative is produced by reacting with a compound having an unsaturated carboxylic acid sulfhydryl group and an isocyanate group represented by the following formula (4). 0 (4) 0CN-A2-X2-C-C=CHr -14 - 201033659 (wherein R1, A2, and X2 are the same as described above) The above-mentioned one can be used as the cellulose derivative having a free hydroxyl group. Representative examples of the compound represented by the formula (4) include 2 (meth)acryloyloxyethyl isocyanate and 2-[2-(methyl)acryloxyethoxyethoxy]ethyl isocyanate. In the active energy ray-curable resin composition of the present invention, only a part of the hydroxyl group of the glucose skeleton may be substituted with a cellulose derivative substituted with a group of an unsaturated carboxylic acid thiol group as an active energy ray-curable compound. Other active energy ray-curable compounds may be further included. Examples of the other active energy ray-curable compound include a radically curable compound and a cationically curable compound. Examples of the radical curable compound include at least one ethylenic double bond in the molecule and initiation of polymerization. A compound which can be polymerized by irradiation with an active energy ray (for example, ultraviolet light, visible light, electron beam, X-ray, etc.) in the presence of the agent. Examples of the compound include (meth)acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (methyl). Third-butyl acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Dicyclopentenyl ester, glycidyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, (methyl) ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (methyl) Acryl fluorenyl-15-201033659 monofunctional (meth) acrylate monomer such as morpholine, τ-(methyl) propylene methoxy propyl trimethoxy decane; styrene, α-methyl styrene, ethylene Toluene, vinyl acetate, allyl acetate, vinyl propionate, benzoic acid B a vinyl monomer such as an enester, a fluorene-vinylpyrrolidone, a fluorene-vinylimidazole or a fluorene-ethylene caprolactam; a 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Bifunctional (meth) acrylates such as esters, bisphenol oxime-diepoxypropyl ether di(meth) acrylate, oxime ethylene oxide modified bisphenol quinone-di(meth) acrylate: Trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol hexa(meth)acrylate, ethylene oxide addition trimethylol Propane tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, triallyl cyanurate, triallyl cyanurate, 1,3,5-tripropenyl fluorenyl A trifunctional or higher polyfunctional monomer such as hydrogen secondary hydrazine. Among these, a polyfunctional monomer having two or more functional groups is preferred. These radical curable compounds may be used singly or in combination of two or more. Further, as the radical curable compound, (meth)acrylate, (meth)acrylic acid urethane, (meth)acrylic acid epoxy ester, (meth)acrylic acid acrylate or the like (methyl group) can be used. ) acrylate oligomers. The cation-curable compound may, for example, be a vinyl ether compound, an epoxy compound or an oxetane compound. Examples of the vinyl ether-based compound include ethylene oxide-modified bisphenol-16-201033659 A-divinyl ether, and ethylene oxide-modified hydroquinone divinyl ether. Examples of the epoxy compound include 1,2-epoxycyclohexane, limonene diepoxide, and 3,4-epoxycyclohexylmethyl.3',4'-epoxycyclohexanecarboxylate. , 1,4-butanediol diepoxypropyl ether, trimethylolpropane diepoxypropyl ether, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate , biphenyl A-diepoxypropyl ether, biphenyl F-diglycidyl ether, biphenyl S-diepoxypropyl ether, hydrogenated biphenyl A-diepoxypropyl ether, and the like. Examples of the oxetane-based compound include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, and (3-ethyl-3-oxetanyl)methyl]ether, etc. The active energy ray-curable resin composition of the present invention may contain a thermosetting compound in addition to the active energy ray-curable compound. . The ratio of a part of the hydroxyl groups of the above-mentioned glucose skeleton which is contained in the total curable compound in the active energy ray-curable resin composition to the cellulose derivative substituted with a group containing an unsaturated carboxylic acid thio group, for example, may be 30% by weight Q or more, preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. Further, in the active energy ray-curable resin composition, in addition to the above-mentioned curable compound, a photopolymerization initiator may be blended, and if necessary, a photo-sensitizer, a photocationic polymerization initiator, or a thermal cation may be blended. A polymerization initiator, a thermal radical polymerization initiator, a light accelerator, a photostabilizer, a UV absorber, a leveling agent, an antifoaming agent, and the like. As the photopolymerization initiator, the active energy ray of the visible hardening means -17-201033659 is appropriately selected. Examples of the photopolymerization initiator include acetophenone, 3-methylacetophenone, diphenylketone, 4-chlorodiphenyl ketone, 4,4-diaminodiphenyl ketone, and 1- Hydroxy-cyclohexyl-phenyl-one, 2,2-dimethoxy-2-acetophenone, Xanthone fluorenone, benzophenone, hydrazine, benzoin ethyl ether, benzoin propyl ether, benzyl Dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-inflavone, camphorquinone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinylpropan-1-one and the like. a content of a part of the hydroxyl group of the glucose skeleton substituted with a thiol group containing an unsaturated carboxylic acid thiol group in an active energy ray-curable resin composition, and a solid content in the active energy ray-curable resin composition The whole (including a component which is cured by hardening) may be, for example, 30 to 99.9% by weight, preferably 50 to 99.5% by weight, more preferably 70 to 99% by weight, particularly preferably 90 to 99% by weight. The content of the photopolymerization initiator in the active energy ray-curable resin composition is, for example, 0.1 to 10 by weight based on the total solid content Q of the active energy ray-curable resin composition (including a component which is cured by hardening). %, preferably about 1 to 8% by weight. The polarizing plate of the present invention is produced by coating the active energy ray-curable resin composition on at least one surface of a polarizing mirror, and then curing the active energy ray-curable resin composition to form a protective film. The coating method of the active energy ray-curable resin composition is not particularly limited, and various coating methods such as blade coating, wire bar coating, slit coating, and gravure coating can be used. Solvents can also be used to adjust the viscosity of the hard -18 - 201033659 resin composition during coating. A coating film composed of an active energy ray-curable resin composition is cured by irradiation with an active energy ray to form a protective film. Examples of the active energy line include ultraviolet rays, visible light, electron beams, and X-rays. Among these, it is preferred to use ultraviolet rays. As a source of ultraviolet rays, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a xenon lamp, a black lamp, a metal halide lamp, or the like can be listed. The thickness of the protective film may be, for example, 10 to 200 / zm, preferably 30 to 100 / zm, from the viewpoints of thinness, lightness, protection, handling, and the like. The polarizing plate of the present invention is protected by using a cured product of an active energy ray-curable resin composition containing a compound having an unsaturated carboxylic acid sulfhydryl group and an alicyclic skeleton and a cellulose derivative as a protective film for a polarizer. The film is transparent, and its birefringence is not easily changed even if stress is applied. EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the invention is not limited to the examples. Further, the photoelastic coefficient and the phase difference of the cured film and the measurement of the glass transition temperature were measured by the following methods. [Measurement of Photoelastic Coefficient and Phase Difference] A cured film having a thickness of 100//Π1 was produced and measured using a three-dimensional double refractometer ("KOBRA-WR") manufactured by Oji Scientific Instruments Co., Ltd. [Measurement of glass transition temperature] On a cold-rolled steel sheet (thickness 〇.3 mm x width 20 mm x length 50 mm), coated -19-201033659 active energy ray-curable resin composition (thickness 40 am), using a small UV irradiation machine (EYE) GRAPHICS Co., Ltd., "ECS-401GX", rated voltage 200V, high-pressure mercury lamp) irradiated ultraviolet rays having a cumulative light amount of 305 m/cm2 from a distance of 11 cm to obtain a cured film of an active energy ray-curable resin composition. The film was heated to 25 ° C from 25 ° C using a rigid-body viscoelasticity measuring apparatus ("RPT-3000W" manufactured by A&D Co., Ltd.), and the glass transition temperature (Tg) was measured. Synthesis Example 1 8 80.4 parts by weight of ethyl cellulose having a hydroxyl value of 32.9 mgKOH/g was dissolved in 3.6 parts by weight of butyl acetate 72, and dehydration of ethyl cellulose was carried out while distilling off butyl acetate at 128 °C. After distilling 124.8 parts by weight of a mixed solution of butyl acetate and water, the moisture in the ethyl acetate acetic acid solution was measured by Karl Fischer Moisture Titrator, and the moisture was 0.025 by weight. %. Further, after dehydration, a distillate portion of butyl citrate was added to a solution of ethyl cellulose in butyl acetate to adjust the concentration of ethyl cellulose to 10% by weight. In an atmosphere mixed with nitrogen and oxygen (oxygen concentration 5%), butyl acetate 38.06 parts by weight, isophorone diisocyanate (IPDI) 100 parts by weight, dibutyltin dilaurate 0.046 parts by weight [relative to IPDI and 2 The concentration of the reactant of hydroxyethyl acrylate (HEA) was 300 ppm by weight. The mixture was placed in a flask and heated to 40 °C. At this time, 52.25 parts by weight of HE A was added dropwise over 1 hour. When the isocyanate concentration (NC 0 concentration in the solution) was 9.94% by weight, it was cooled to room temperature to obtain a (meth) acrylate (isophorone -20-201033659 isocyanate 1 mol and 2- hydroxy b) The acrylate 1 molar reaction is followed by a solution having an isocyanate group. In a mixed nitrogen and oxygen atmosphere (oxygen concentration 5%), the butyl acetate solution (10% by weight solution) of ethyl cellulose having a hydroxyl group content of 32.9 mgKOH/g after dehydration treatment is 67 9 parts by weight, 0.0282 parts by weight of dibutyltin laurate was placed in a flask and stirred, and the temperature was raised to 100 °C. 19.42 parts by weight of the prepared solution containing (meth) acrylate (having an isocyanate group at the terminal) was added dropwise over 1 hour. Thereafter, the ripening is carried out, and when the isocyanate concentration is 0.1% by weight or less, the mixture is cooled to room temperature to obtain a solution containing a cellulose derivative (the hydroxyl group of the ethyl cellulose is substituted by a group containing an acrylonitrile group) (solid content 16.4) weight%). Synthesis Example 2 Cellulose acetate (manufactured by Daicel Chemical Industry Co., Ltd., L-20) was dried at 150 ° C for 24 hours to make the water content in the cellulose acetate 0.86 wt%. The hydroxyl value at this time was 97.13 mgKOH/g. 35 parts by weight of this dried cellulose acetate was mixed with 316 parts by weight of cyclohexanone and 65 parts by weight of toluene', and a mixture of cyclohexanone, toluene, and water was distilled off at 155 ° C, and then a Karl Fischer moisture meter was used ( Karl Fischer Moisture Titrator) measures the moisture in a solution of cellulose acetate in cyclohexanone. The result is a moisture content of 0.015 wt%. Further, after dehydration, the concentration of cellulose acetate was adjusted to 10.9% by weight with cyclohexanone. In a mixture of nitrogen and oxygen (oxygen concentration 5%), the dehydrated hydroxyvalent 97.13 mg KOH/g cellulose acetate cyclohexane solution (10.9 201033659 wt% solution) 2 11 parts by weight was placed in the flask. Stir in and warm to 70 °C. After reaching 70 °C, 4.6 parts by weight of isocyanate acrylate (2-propenyloxyethyl isocyanate; manufactured by Showa Denko, AOI-VM) was added. After 2 hours from the addition of AOI-VM, 0.08 parts by weight of dibutyltin dilaurate was placed in a flask and stirred to continue the reaction. Thereafter, the aging is carried out, and when the isocyanate concentration is 0.1% by weight or less, it is cooled to room temperature to obtain a solution containing a cellulose derivative (the hydroxyl group of cellulose acetate is substituted by a group containing an acrylonitrile group) (solid content 12.8 by weight) %). 〇 Example 1 In 100 parts by weight of a solution containing a cellulose derivative (the hydroxyl group of ethyl cellulose was substituted by a group containing an acrylonitrile group) prepared in Synthesis Example 1, a '1-hydroxy-cyclohexyl group was mixed. The active energy ray-curable resin composition 1 was obtained by 0.82 part by weight of phenyl-ketone. The active energy ray-curable resin composition 1 was coated on a glass plate with a film thickness of 600 //m using an applicator, and then dried at 80 ° C for 1 hour, and then a small UV irradiation machine (EYE GRAPHICS CO., LTD. "ECS-401GX", rated voltage: 200V, high-pressure mercury lamp) Irradiation of ultraviolet light of a cumulative light amount of 500 m]/cm2 from a distance of 11 cm to obtain a single cured film of the active energy ray-curable resin composition 1 (thickness: 98 V m) . The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and the phase difference were measured. Example 2 The cellulose derivative obtained in Synthesis Example 2 (the hydroxyl group of cellulose acetate was contained in the base of the propylene group) In a 1 part by weight of the solution of the substituted), 0.82 parts by weight of 201033659 1-hydroxy-cyclohexyl-phenyl-ketone was mixed to obtain an active energy ray-curable resin composition 2. The active energy ray-curable resin composition 2 was applied to a glass plate to a film thickness of 600 /zm using an applicator, and then dried at 80 ° C for 1 hour, and then a small UV irradiation machine (manufactured by EYE GRAPHICS Co., Ltd., " ECS-401GX", rated voltage: 200 V, high-pressure mercury lamp) The ultraviolet light of the cumulative light amount of 50 0 m J/cm 2 was irradiated three times from a distance of 11 cm to obtain a single cured film of the active energy ray-curable resin composition 2 (thickness 77: m). The appearance of the obtained cured film was visually observed, and the optical elastic modulus and the phase difference were measured. Comparative Example 1 500 wt% of an ethyl acetate solution of 10 wt% of a hydroxyl group of 32.9 mgKOH/g of ethylcellulose, 50 parts by weight of pentaerythritol triacrylate, and 1 weight of 1-hydroxy-cyclohexyl-phenyl-ketone The mixture was mixed to obtain an active energy ray-curable resin composition. 3» The active energy ray-curable resin composition 3 was coated on a glass plate with a film thickness of 55 0 μm using an applicator, and dried at Q 8 〇 ° C. After the lapse of the same period, ultraviolet rays were irradiated in the same manner as in Example 1 to obtain a single cured film (thickness: 100 Å / zm) of the active energy ray-curable resin composition 3. The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and the phase difference were measured. Comparative Example 2 500 parts by weight of an ethyl acetate solution of 102.9 mg KOH/g of ethyl cellulose, 50 parts by weight of dipentaerythritol hexaacrylate, and 1-hydroxy-cyclohexyl-phenyl-ketone 5 The parts by weight were mixed to obtain an active -23-201033659 energy ray-curable resin composition 4. The film of the active energy ray-forming resin composition 4 was coated with a film thickness of 5 50 μm using an applicator, and after drying for 1 hour at t, the ultraviolet ray was irradiated in the same manner as in Example 1 to obtain active energy ray hardening. A separate cured film of the resin composition 4 (thickness 100 Μ m). The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and the phase difference were measured. Comparative Example 3 500 parts by weight of an ethyl ethyl hydrazine ethyl acetate solution of 10% by weight of a hydroxyl group of 32.9 mgKOH/g, pentaerythritol ethoxytetraacrylate by weight, 1-hydroxy-cyclohexyl-phenyl-ketone 5 The parts by weight are mixed to obtain an active energy ray-curable resin composition 5. The active energy 'wire-curable resin composition 5 was coated on a glass plate with a film thickness of 550 // m using an applicator, and dried at 80 ° C for 1 hour, and then irradiated with an outer line in the same manner as in Example 1. The active energy ray-curable resin composition 5 is individually hardened (thickness 100 V m). The appearance of the obtained cured film was visually observed Q and the photoelastic coefficient and the phase difference were measured. The appearance, glass transition degree, photoelastic coefficient, and phase difference measurement results of the cured films obtained in the examples and the comparative examples are shown in Table 1. The "one" in the table indicates that it cannot be measured. Hard 80 [» Degree of 50% of the amount of purple film temperature 201033659 Table 1 Example Comparative Example 1 2 1 2 .3 Appearance transparent transparent coating film when cracked, perforated cracked white turbid white Tg (°C) 140 160 146 152 142 Photoelastic coefficient (xlO^Pa1) 16.7 14.1 — — — Phase difference (nm) 13.6 0.4 — — — [Simple diagram] te 〇 [Main component symbol description]