TW201788B - - Google Patents
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- TW201788B TW201788B TW080101945A TW80101945A TW201788B TW 201788 B TW201788 B TW 201788B TW 080101945 A TW080101945 A TW 080101945A TW 80101945 A TW80101945 A TW 80101945A TW 201788 B TW201788 B TW 201788B
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- 125000001624 naphthyl group Chemical group 0.000 description 1
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
- D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
- D06M15/432—Amino-aldehyde resins modified by phosphorus compounds by phosphonic acids or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
- D06M13/447—Phosphonates or phosphinates containing nitrogen atoms
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
五、發明說明(1 ) —— 本發明係關於阻伊刹組A料π 纽。物及以阻燃減理Μ品受理 足万法〇 7品料人較各類化学^其岐使其 ,因而提供耐久或不耐久阻 燃次果 _ c二曱•板作用。其中此種化学品係3 一甲瞵酸j丙酸羥甲基 酸系條件下加熱固化,將此汉:參至織物内且在 ^ ^ 、 通布係與共反雎物如三聚來胺甲 ㈣合物-起進行以提辦 η甲 特m聚Sen 梯蛛物亚具某些程度耐清洗 ^ ^ ίρ織掬而詳細言之交織織物比棉織# # 難於使波等具阻煨效 饰織物更 俄效果,郎使半耐久性亦如此。 我們已發現阻燃 及其它材料上之合物及將彼等施用至織維素系織物 士 不法使織物增加阻燃及其耐久性。 本發明所提供阻, 劑組合物包括: J至V —種式c
- A J之環系隣酸踣C I J {請先聞讀背面之注意事項再填寫本買) •策· 0 R2 •打· 0 och2 — c ’
RJ CR): CH, 0 •爆…, 其中a係〇、 且a 東基、芳基 '芳氡基、 b係〇、1或2 ; c係1、2或3 R及R1可相同羌不同且禹烷基、 坡芳基、烷芳象基、芳烷基、芳灰 肀 4 (210X297 公飧)
、發啁說明(2 ί修王 至少士種二氧基’ Μ 9這些基圈之烷基部份可含有漠、或經基團;…二含有至少一種氣、 竣院基c例:… 院基或芳基…3係低或式(B)、r& 1 < ),或羥烷基c例如Ci至c4 );'㈤文振系磷酸醑 (B) 0JIr4oc 〇 R2 ch2o R5 coch2c
、ch2o 其中d係ο、i 係如上面定差_ ;e係1、2或3 ;d + e為3 ;R 院芳基、奸h 義;R4㈣基、芳基 少一種濟、^芳氧烷基,其中芳基部份可選用含有_ 羥基,則ϋ:基;Μ6係三償羥基,若R6係芳; ii)至少一嫌曰至少一種溴、氣、烷基或羥基困;且 ""具下式之膦醯胺 R8〇 · ......................................................«-..............................打..............................**. f請先¾¾背面之注意事項再填考本頁) r7o CH2 - CH - CO - NH - CH2〇Re 其中R6代表 氩原于或有機基, 同時R7及R8之每一種可 甲 4(210X297 公沒) 一斗-
L0176S
五、發明說明( 相同或不同而代表有機基1 R9 * 31 ΓΗ η 代表也原子、由索原子、 從基團或式CH*C〇NHCHa〇Re基圏 f請先聞續背面<注意事項再填寫本霣) 本發明亦提供阻燃織物之方 、 _ ’此万法包括以含有本發 明阻燃組合物之水性介jg•洛本 贫 介質是凊具有孅維索系及朴缴維 纖維之織物,且然凌在至少 、、 川0 c之A度及在醭p(i條件 下將經漫渍織物進行熱處理。 壤系腾酸除I在基圃立4丨丨 '專利38沾368及3789091號中有説明 ,其所揭示内容倂於本文供東· 又供麥考。如在這些專利中説明, 彼可籍以下列二者起反應 久艰文不式氣成,卽以不含自素之亞
填酸、叛酸或横酸炫I 尤岈與一環系亞磷酸聒起反想,漾者如 1-炫蟇—4-填嫌— 3,5,8一三噁二瓖并〔2,2 •打. .線. ,2〕辛烷。用於厌和『至民,之烷基、烷氧基或含取代 烷基困可含有1至6個硖原子,同時芳基團可爲芳杳熳基 ®並可含6至19悃硖原子,芳烷基團可禹理基團且可含 7至19個破原子。R及Rl之實例係…-•烷基、茉基 、由采基、羥笨蟇、甲笨基、二甲笨基、爷基、茉I基、 裡G基、茉氣蟇及二溴茉氧甲基e R4之賁例係Ci-4 炫基、笨基、由笨基、羥笨基、mu基、笨氧I基、二溴 采氧I基、甲笨蟇、二甲笨基、苄蟇或笨1蟇,同時厌, 之實例係C » - ·炫-或三取代烷基團及衍自笨之三償基, 選用以一個、二個或三個溴或氯原子取代,一個或二個 ct -‘炫基,例如甲基困或羥蟇團,或浞落之三償基類。 在式I内較佳的化合物類係一種其中!{及R»之每—種可 相同或不同而代表低破烷基或低破烷氧蟇團,例如i至6 甲 4(210X297 公潘) 5 L01768 五、發明說叼(4 個破原子,样細言之,i至3個破原予,詳麵言之指甲基 {請先閱讀背面之注意事項再填寫本霣) 、。基 '甲氧基及。氧基。同時y及以每一種可相同或 不同,以代表炫蟇團較佳,例如具i至6烟硖原子,諸如 甲基或L基團。可使用瓖系隣酸進,*具有% : 5至5 :跖中之一種,例如以25 : 75至花:25作烏二種磷 醚塩之比年’詳麵言之’第m壤其中a、…各 …且第二種眺歧塩其中a",…且…,在 其一種碟联·旗·中各禮R、R* β |?3 f如 及8基圏可單獨烏相同如在 其它瞵駿塩中之相當蟇困。 最佳的況合物係這二《磷蜓塩類之40 :叨至册:奶 •打· 的混合物,其中R、R»^r9各代表甲基或I基團且R1 代表甲氣基或L氣蟇如其國專Μ 3843368丨之實例以中 ,詳相言之,其中R及R,係甲基,R,係匕基且R1係 甲氧基;此種洗合物之f例係5〇 : 5〇重量/重量淡合物 〔其中R 、係甲基,R1爲甲氣基且R,係匕基】, 由美國阿白特C A1_t )及成(遵(州咖〕公司以 線. 麗BL卿之註册商品名稱出售或由阿白特及成爾遵肢 份有限公司以AMGARD CU.之註册商品名心售。 膦C酸胺島已知尤其(見例如九英两協專利⑶如 細72及U39380 R,所揭示内容倂於本文供麥考卜在 _…基圏以…較隹,但可代表有機基例如 具1至10個碳原子,如烷基或破埽基困,詳細十之具 1至4個破原子炫基困,如甲基、 埽丙基團^及^…種以相同牧僅而代表有機基圏 甲 4(210X297 公羶) LOraib 五'發明説明( ,例如具1至13俑破原子,諸钻 ^ _ 311用含取代之炫基®或 基團,例如各具1至6個碳原子:芳基園,如具6至 13個破原子;或脂壤m〜5至7個破原子。此 種較佳基團之货例係甲基或i基’― 般而言,杈佳者係丙 丞及丁基團和炫基團之軍氣、技、 一 ’吳或氣澳化衍生物,詳細 =之,此種較偟基圏之衍生物’及最多4個破原子之由破 稀基困和禹笨蟇團’例如氣笨基或澳策基。r•…原 子或由素,例如氟原子或炫基團,倒如具i至6個破原子 者如甲基或L基或式CH2C〇NHCHa〇R·基明,其中Re如 上、面定義;較僅的R*代表&原子。較佳的膜随按係3_ 【二甲基瞵酸)·丙酸,經甲基醯按而具式(CH3〇jap〇CH2 CHjCONHCHjOH ο 在狃合物中瑗系膦蜓塩對瞵醯按之重量比年通常為oa 至2 : 1,例如0.2至1 : 1。 阻燃扭合物以含有用於瞵(酸)醯胺之共固化剞較佳。 共固化劑,通常爲熱可固化的,而較佳者為甲眵與具有至 7 2俚NH基團之含表多官低基化合物之缩合物,如腺或 胺基三嗪如三聚采胺,或瑗系化合物類如伸I基脲或I快 一腺’及/或本身係含良化合物;缩合物可選用瞇化之。 較隹的共固化劑係具3至6個羥甲基困之瞇化的羥甲蟇三 歌机胺C或其醚顴j或選用醚化的羥甲基0伸1炔二腺。 以隣边胺固《乾重爲基準,共固化劑用量通常佔5至30 %,例如10至25 %。 選用謎化或部份烷化的羥甲基三浓氰桉共固化劑(此泛
f請先閃續背面之注意事項再壤寫本買) 叙· •打· •線· 甲 4 (210X297 公潘) 7 ΟΙϊο» A6 B6 五,發明説明(6) 亦稱鳥一嗪J具有1 3,5三嗪核且其三個按蟇困中係 在2 ’ 4 ’ 6位I,通常蒂有平均3至6 (例如3·5至6 且詳細言之4至5.5 里羥基困,且這些羥甲基阐可至少 部份具有波等烷蟇醚類之形式。三嗪在7〇 ,c通常具有固 化時W禹至少15分鉉,例如至少40分鐘,此係以下列 方式測定:- 以2〇克含80 %具反羝性固後之三嗪水溶液而在一種 容器中,加入0.8克(·以重量計)5〇 %硝酸辞六水合物 之水溶液兹梘拌之i到得到澄清溶液岛止且然裘藉著恒瀛 浴維抟在容器中的溶液在70 ·(: ii[到已發生固化之時禹止 C此ί!稱岛固化時M J /其所達到程度禹固化扨質可冗全 抵抗全屬匙之任何攪動。澄清溶液之起始pH通常* 5.8 至6.2。祝情沉需要,三唪水溶液或澄清溶液之pH可籍 加入硝酸或氬氧化鈉調整因此澄清溶液之最终pH係5.8 至 6.2 〇 在70 ·<:之固化時Μ通常爲 15 .分鐘至10」、時,如40 分饉至10山時,例如40分鍾至6 4、時,諸如40至200 或40至140分鍾,1L詳知言之,40至75分鍾或70至140 分鐘。在三唤中,以至少某些羥甲蟇困類祓烷蟇團鰱化牧 佳,例如遠10至100 %之程度,且詳细言之,遠30至80 %或達30至60 %之程度,而此種烷蟇團例如具1至10 又如具1至5個硖原子,例如甲基、、或丁基®额。 若每三嗪核增加段甲蟇團數目,則通常可增加韃化作用程 度》因此,以平均4.5至5.5羥甲基團而言,則烷化度苛 {請先閲讀背面之注意事項再填寫本貰) •裟· •打· •線· 甲 4(210X297 公廣) 8 Α6Β6 五、發明説明(7 遠30至60 %且以平均5·5至6個羥甲基困而言,則烷化 度可達60至90%。以每三嗪分子所含烷氧甲基及羥甲基 困之違數目而言,平均含3至6或3.5至6個,以4至5·5 個較僅;卸平均每分子含W至4 , * 〇5至2或ι至以 且詳细言之1.5至3·5個羥甲基團;且平均每分子含有^ 至5.9 4至5.9或1.5至5,而以L5至3 5個較佳 之炫氧甲基團。每三嗪核之羥甲基困數目及將彼等瞄化程 度通常係以在彼等製程中分別使用之甲搭及轉之其耳數烏 基準,但亦可贛物理或化学分析方法測定。瞇化作用可藉 m'甲基二聚机胺與合宜的烷薄在酸催化劑之存在下起反懕 之方式進行'三嗪化合物以县單理物質之形式較佳,但亦 可少量含有低分子量單《自身縮合物之形式:較佳的化合 物係圣55至1〇〇 % i例如7〇至9〇 % )軍鼉形式且含有 45至〇%〔例如30至1〇%)自身缩合物。市售選用郅 份烷化羥甲基三聚氰胺之實例係由英國工業塑疹公司所出 售之ΒΤ370而發现其在7〇 .c之固化時間係沉4分鐘及邶 份甲蟇化的六羥甲基三聚舐胺類如由汽巴嘉蟇公司所出隹 Cibamin ML1000GB而發現其所具固化時閡為29〇分艟 ^ 是較傕的部份甲基化m甲基三聚珉類係由英國工業塑繆出 售之BT 336、BT 338或BT 309而發現其在70 .C之囷化 時Μ分別烏50、25及23分鍾,或由汽巴嘉基公司所出隹 之Lyofix CH ,而發現其在70 *C之固化時Μ烏108分餚 Ο 在治療一開始扣可使用之組合物係在pfI、4、於3,以 甲 4 (210X297公灃) (請先«讀背面之注意事項再琪寫本貰) .裟. •打. 9
五、發明說明(8 ) 至2.5較法。以可提供此種pH值而言,以强礦物酸較佳 如疏酸或氪氟酸但以磷酸更佳,伹代用化合物係在水性组 合物中可形成酸者,如具酸反逯之進類,.如氟化按或可水 解成級之化合物,如無機酸或有檄酸氯化物類。 阻燃組合物亦可含有氱破歡合物散劑Q在超遇1QQ.C, 如160 ·(:至200 .C可加熱固化前J。氱破聚合物係一種在 阻燃扭合物中可形成散劑者,此通常歷至少若千天〔例如 至少2天)係安定的β氟蒎合物與瞵醯胺及壤系膦黢农溶 液係不相容且一旦泷合會形成沉激物,故想避免之。合宜 水性2分散聚合物類通常具有全氟烷基惻鏠類,倒如,具有 全氟一釀基、-磺釀基或-磺醯胺基困,烊麯言之,在全 氟炫基困中具3至12愐碳原子之一種;此可存在狡基困 。氟碳聚合物類以衍目含全氟烷暴團羥化合物额之丙烯酸 除或具丁场級路,但可衍自具有全氱-炫基惻鍵之I释抵 、1坤醚、蟬丙鰱或硫代異丁蝉酸輅類。尤锉的聚合物额 係一種含C N -烷基Ν -全氣烷礅Λ胺基j伸烷基側缱顴 ,例如2—(Ν-丙基Ν-全氟辛基磺醯胺基)一伸〇基 側鏠類而具丙蟬醚畤或異丁蝉醆难主幹。此種聚合物僅從 含全氟炫基困之翠β裝得。代脅方式係這些箪禮類可巳經 以其它可共聚合單獲共聚合,特定言之,—種不含氟者, 例如’含有一種或二種婦埋双楗者,例如,由基丁二蜂, 如2 —氣—j , 3_ 丁二烯。在浓合物中可存在烯理單獲 翠元而含羧酸蟇明者,例如,丙烯酸系,異丁烯致系或順 丁缔二酸基團。氣聚合物類通常以水性散劑之形式出售, 甲 4(210X297 公廣) 10 ...................................................It..............................*r.....................................«. (請先《讀背面之注意事項再填寫本賣) A6 B6 L〇i彻 五、發明説明(9 ) 例如用於栽物之氟裝合物污物驅除精整劑。 {請先閲讀背面之注意事項再填寫本1 ) 聚合物散劑可爲祚難子系但以陽難子系較佬或詳细言之 指梭·濰子系。氟聚合物散劑亦可含有少量與水可混合有機 溶劑類,例如,丙酮,MI.BK或I二酵。較佳的氟蒎合物 散劑係由3 Μ公司出售而商品名禹SCOTCHGARD 270或4J汽 巴嘉基出售而商品名禹SCOTCHGARD FC 451 。咸信此種聚 合物係2 - C Ν -烷基Ν -全氱辛基磺醯按基基丙烯 酸聒及共單tt (以2 -氯-1,3 -丁二烯較佳J之共聚 合物。其它較佬氣聚含物散劑係由赫斯特C Hfechst J AG 公、司出售而商品名烏NUVA FH或NUVA F。由Atochem SA 公司出售而商品名鳥FORAPERLE *詳As言之,FORAPERLE 145及344,或Texchem +UK股份有眼公司C英國曼歡斯 特城J而以TEXFIN CPC之商品名出售等之氟紧合物亦可 使用》在隣酿胺中若存在氟紧合物(·固,則其重量百 分比通常爲0·1至5%,詳细言之,0.2至2% »然而在 本發明洱燃狙合物及介質中於1Γ1Γ上以不存在此種氟破聚 合物較佳》 狙合物亦可含有朴_再吸滠劑,倒如,具撣發堆吸滠劑 如醇或由Warwick化學公司出售而商品名爲MYKON NRW試 劑。然而,若欲使具有阻燃性之受tt已洗淨或係已經處理 以協助漫洚液《,則ϋ不需要此種試劑,但祝情況需‘要而 可存在一種。特定言之,若存在氟聚合物,則水性介貫通 常不含展延劑或除難子系聚合物類,如陽離子系合成樹脂 蠟,如售自山度士 C Sandoz J公司而商品名禹CER0L,且 11 甲 4(210X297 公廣) 01765
五、發明説明(10) 通常在f質上不含二 __ 二或四償金屬选翔。例如這些之銘 塩或其飴塩。所出隹 (請先聞讀背面之注意事項再填寫本夏) 些氟浓合物散劑類亦含有展延劑或 陽離子系聚合物;这此, 違些以不用杈隹。所出售之氟聚合物散 剤主要係提供驅除污 物,但朴用以除污物及水較佳,因 爲遣者傾向於含有陽雜之〃,, 两雕子系聚合物且不可與水性阻燃剩組 合物相容。 苦氟中衆合物係故存在組合物中則將氣聚合物散劑加至 組合物較佳,苦坡係卸用於漫參且以在若千天内將組合物 用於浸·涛·作用較僅,一 細g之,在樓難子系氟聚合物散劑 之情況下’狙合物以歷至少。遇【例如至少—個月)係安 定爲宜。 \ •打· 水性狙合物亦可含有其它天煞紡栽品輔助劑且其用量係 使彼等可與&合物之其它成份相容^相捧合〕,且對熱固 化處理並無顧普影響,例如造成玩色或散失故想。此種試 劑之實例係軟化剤或調理劑,此可烏陽離子系、险離子系 、朴難子系、兩性系或具反懕性,觅通常含有至少—個而 經常烏一個烷基缒並旦具至少10個破原子。 •線· 陽難子系軟化劑之賞例係雎昉四级銨塩類、胺瞄類及按 基趄胺類和四級N_tt基N -聚氧化烷烯聚胺類》飨離子 系软化«之實例係脂昉酸埴類、肥皂、磺酸化脂類及油類 ,知昉烷基硫酸塩及脂昉酸缩合產物、磺丁二醚塩及磺丁 醯胺駿坺類β兩性試劑之货例係烷基味唑咻類及甜策鹼類 及其塩類和其它聚氧化烷烯缩合產物類,與石蠟垤蠟或聚 I烯蠟,波二者係與朴離子系、降濉子系或险離子系但詳 - —— 圓 _ 甲4(210X297 公身) ζ 01768
五、發明説明(11) 細言之兩性系散劑類而使用於水性散劑或乳劑中。具反想 性軟化剩之實例係脂昉酸醯按之N _羥甲 公14玉物類,例 如Ν -羥甲基硬脂酸醯胺或脂昉酸Ν_ 况〒丞%生物類與 脲之缩合物類。較佳的軟化劑類係朴離子系改良的二聚采 胺甲塔梅合作用產物軟化剤類·。以總水性漫滲介質之重量 計,軟化剩或其散劑之用量係〇·〇1至5 %,例如〇 5至 3 %。 存在軟化劑可讓熱固化槳程產裝經處理織物具有改良的 阻燃性益具有其它性質,例如强度,詳細言之,抗扯强度 ,'且颜色在實質上如這些未處理織物;更可改進其强度。 經施用扭合物之受可經编織或未經编織。彼等係以孅 維索爲底之受《,例如紡織織物,如棉布、亞麻布、黃麻 布、海赛C hessian )布或再生纖維紫材料,如雷榮或雷榮 絲布(ViSC〇Se j ,與随炸可共摻合或可混合之其它殲維 ,例如紧時或尼税、丙烯酸系、1駿蜡、聚丙烯、絲或羊 毛。這些織維掺合物或其混合物可含雄維索系讨料遠至少 30 % ,如30至100 %或30至90 %,但以至少4〇 %較 任,如40至75 %’且詳納言之,至少go% ,如50至 90 %,50 至 80 % 或 70 至 90 %。 較隹的織物係從4卜捧合之嫌維索系材料混合物,例如梯 織物,及合成聚合物,例如聚S&或尼龍。用以形成至少邶 伤織物之嫌維祝情’Λ需要可烏核心稍層结構值以不具此種 结構較佬。殲維係浪妨結構,例如具有至少一種緯紗且詳 细言之,以經紗禹主(例如50至100 %〕,詳細言之,在
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五、發明説明(12) A6B6 基本上全烏合成聚合物纖 ••較佳者係緊蜡或尼税續炒日,具有以歡賠爲主之經紗起…… 梯戴緯紗,詳细言之,具浮 起棉織化没圖案。若不存在 會使裂時梅田且從棉紙物且則火燒品妨織物 使用於家俱㈣業方面,則降炎燃繞’因此,… 本發明之阻燃組合物及本發3::阻燃戴物之總故度。_ g. ^ ^ X , 万去使此種混鲂織物更均句-致地阻燃而至少達半耐久, „ 此種紙物以具浮起C浮凸織 之一種杈佳,但詳細古. 怒一令 β之,具有补均句一致分佈合成 聚合物之一種且在其表面上 之縱維索系材料此ί!稱爲 異性C足以區別)表面織物”。 特別重要而具i異性之表 ^ ^ ^ A ' 紙物類係一種而其前面所具 有級維索材料對合成材料之 千係不同於(通常低於)背 视面所具有比年,以及通當釕办 1宠“ 及通常包含-面或前面而在其表面上 具有顯著區域主要禹c例如5〇 ^ ^ 主100 合成聚合物織維 ,以及通常作烏顯著區域者係 视青而【例如50至1〇〇 殲維素材料殲維。此種足以區 ^ , 表由紙物之實例係具有聚 蛞經紗及上柰的棉緯紗之一種, 砰细g之,具有超遏—艚 不同顏色的棉緯紗,此種經编備 經編織&物在聚《*經紗背層上之前面具有此種上梁棉花之花型顧 把案a在朴花型圓案背面在 f質上係具棉花表面。可使 R用此種足以區別之表面織物作 烏豕俱裝飾織物。 織物重量可烏_至】.〇公斤/平方米,例如,_ 至0.500公斤/平方米。 種織物成份可烏平紋、未上 已上梁色,詳相言之,具白色或彩色影子。於漫 甲 4(210X297 公廣] —— 漆前 (請先聞讀背面之注意事項再填寫本頁) •51· •打· •線· Ό17&8
五、發明說明(13) ’織物通常係不含污物、疹料、 天然石蠟且經由含有尤學 亮光制而施以精整0 以乾垛固®爲基準,阻燃劑 88«物通常含有下列成份, 10至300克/幵,以5〇至1〇〇 . 兄/幵杈佳之瑗系膦酸聒; 50至600克/幵而以1〇〇至 υ尤/升杈佳之膦醢胺;壤 用但以5至1〇〇克,升較隹( J如15至60克/幵j共固 化劑;10至50克/开酼〔足以使 氏ρϋ連1.5至3 J ;壤 用5至50克/升软化剤,祖. 叮祆阳砰細s之,具反想性軟化劑; 及1至20克/幵例如μ至 ^ 3兄/开朴—再吸濕試划 Ο 在水溶液中之阻燃劑•組合物本身或祝情況需要於以水稀 释改所具pH是小於3而籍習用方法施用至受理上,例如 整墊、漫潰或噴灑而通常水戴取度達5〇至15〇 %,例如卯 至110 %。於乾燥前且於擠鋈出剩绘液禮裘蟪加入固煜量 通常佔10至35 %,例如10至2〇 %或13至25 % (以璣 物乾燥起始重量爲基準j。 於漫清波,蚝漾將受禮乾化,例如60至MO .C ,又如在 90至130 *C ,歷0.5至20分鍾,例如1〇至〇 5分鍾。乾化 可在妊何翟用乾烯器中進行,例如,在慇縮空氣乾燥器或 拉格機中進行。於乾燁波之固禮戴肷量係通常烏8至25 %,如10至20 %(以織物原先重量禹基準j 〇 煞泛將經乾燥受β固化,例如籍在至少i〇0 .c之溫度加 熱,如在至少130 *C,例如130至200 X:,此諸如140至 170 *C,例如歷10至0.5分鉉,避免使用校長時間及較 肀 4(210X297公簷) 15 (請先閱續背面之注意事項再填寫本霣) .装· •打. -線. L017B3 五、發明說明(工4) 溫度之結合才可降低妊何脱 叮靶色傾向。因此較佳條件係15〇 至170 *C歷2至5分鍾。若其,名-本八你 ^ 料質中存在任何氟聚合 物,則絨物可增加其抗圬梁性。 固化通常係持續的而以下列, •列不式進打:以輻射線,例如 外光加熱或藉注射萘氣加教及& _ "、夂/或以熱空氣通遏受煜, 或覉著受理與在委j|[堆栾中受舐 冬…、的金屬轉筒相接觸,但較 佳的固化係藉熱空氣衝擊受獲表 衣由之不式加熱,以作用在 二種表面上較佳方可苇保均句·— J 致加熱。因此較佳方式係 在拉幅機上將受s持續通遏恒^ 相具中將受熱空氣流 通遇而達受《頂處及底部表面。拉 ^ 拉搭機给予最均匀一致固 化以及最低燒焦程度 '在拉核機烘箱的情況中受理之固 化溫度在基本上如同受熱的空氣流之溫度。在固化终了, 通常麝將冷空氧通遏或ί丨入經遇受β之方式而加以快速冷 却》於固化(1,栽物通常係先遣以鹼性水溶液及水清洗。 經固化絨物於清洗《_,通常所具有含量爲6至25% ,如8至20 % ,乱通常含有〇·5至4 %,較僅者係工至 3 %,1.5 至 2·5 % ,或 2 至 4 % β 與未處理受《相比較,織物具有降低可燃性见可通遏 B S 5852试驗並具點燃源烏〇及j。具降低可燃性之精整 物通常在實質上係砑清洗的。以操作難易度而言,此織物 與未處理我物通常無顧著改變。 C 1J瑗系膦鷇時及Cnjffig^按之增强性结合使經處 理織物具有改良的燃燒性及耐久性而此烏以(丨)或(u J單獨處理之織物未具有之性質。 16 (請先聞讀背面之注意事項再填寫本買) •打· •線· 甲 4(210X297 公廣) A6 B6
LOrVCS 五、發明說明(15 ) 本發明以下列實例説明。 賁例1 水性漫冬液煜係依照下列順序而以所給予數量混合下列 成份而製得:225克/升之80%· 3 - t二甲隣酸J -丙 酸裡甲基醯胺之80%水溶液,40克/升產目英國工業 塑疹公司而以BT338商品名出售部份醚化三紧來胺甲醛缩 合物溶液之80%水溶,25克/升磷酸C 88%J,15 克/幵產自汽巴嘉基公司而以TURPEX NPF商品名稱出售 之朴離子系經改良三聚采胺甲醛缩合物軟化劑,1克/升 產自蓽成克C Warwick J化學品公司而以MYKUM NRW商品 名稱出售之朴-再吸濕性試劑及70克/升瑗系隣酸龄而 k 此係以ANTI BLAZE 19或AMGARD CU Q如上述J出售之50 :50環系膦酸醏混合物。 將具有聚躲經紗編織而稱重0.335公斤/平方米之65 :35 棉聚聒泷紡織物在整墊輾壓機中以水性液值浸渗且 拼壓·使得到具水戴取量爲95%之經漫渗織物。将經漫渗 織物在100 Ό磬缩空氟拉梅機中乾煉歷2分鍾。然遣將經 乾燥織物在拉播機上緩慢而持續地移動通遏悝温賓士 C Benz )乾燥器而此係以受熟空軋泚浞頂部及底4部衡擊織物 :在160 X:之固化時W係3分錄。 經固化織物然洗以20 : 1桶内物:母液比年而依順序 以30克/升水性破酸钠、1〇克/升水性硖酸鈉、熱水 及冷水清洗。然泛將絨物乾燥且根據BS 5852 第1部份C 1979 J之試驗方法試驗,此具有點燃源扃0及1 t用於可 甲 4 (210X297 公廣) (請先聞讀背面之注意事項再填襄本頁) •装· •打· •線· 17 A6 B6 L01768 五、發明説明(16) {請先聞碛背面之注意事項再填寫本頁) 燃性試驗J且根據B S 5651笫1部份之方式於40 ’C在硬 水中浸漶I次漾益不具最終衡薄故懕。織物在漫漶前及浸 漶泛皆通過試驗。 比較性實例 在比較性1Γ例中,除了不用瓖系隣酸躲以外,實例1 C 上J之方法係以相同浴重覆進行。此織物於漫漶前及浚皆 無法通過可燃性試驗。 實例2及3 在棉/紧蜡家俱装飾用成物上進一步洱燃處理之實例係 使角货例1之方法,而在稱重0.330公斤/平方米之55 : 45棉/聚躲混紡織物上進行。 % •打· 依照實例1之方法,但未加入AMGARD CU : -225克/开3 - Q二甲基膦醍醯J -丙酸羥甲基醯胺C 80 % ; 40 克 / 幵 BT338
15 克 / 开 TURPEX NPF 25克/幵磷酸Q 88%) •緣.
1克/幵MYKON NRW C扭合物A J 使用上驵合物A作禹一系列3項f驗之基破,此包括以 AMGARD CU取代50 克/幵及100克/幵驵合物A可得到 驵合物B及C。 於乾燥及試驗之前,漫渗、乾燥、固化及洗除方法係以 如f例1中所説明方式進行。 試驗結果 甲 4(210X297 公簷) 18 LOi财 A6 B6 五、發明説明(17 ) 以驵合物B及C處理過之樣品,苦根據BS 5852笫1部 份之試驗方法試驗,而於如在BS 5651中所説明方式進行 硬水浸漶前及泛,其具點燃源爲.〇及1 C用於可燃性試驗 J ϋ通過此項試驗,也不會具最終衡薄故應。 若以組合物Α處理之樣品.,.則無法通過可燃性試驗。 (請先聞讀背面之注意事項再填寫本霣) 51· •打· .綵· 甲 4 (210X297 公角) 19
Claims (1)
- 六、申請專利範® 1.—程P且燃組合物,其特點為 〔i〕一或多個 式〔A〕之環系膦酸醏 〇 R2 〇其中a係〇、1或2 ; b係〇 、1或2 ; c f系1、2或 I 3且C a + b + c )岛3 ; R及R1各單獨 基或烷氧基;R2及R3 各單獨爲Ci_e烷基;或 式〔B〕之環系膦酸醏:甲4(210X297 公发) 一 1 一 (請先閑讀背面之注意事項再填寫本頁) .装· •訂. .線· 經濟部中央搮準局印製 A7 B7 C7 D7_ 六、申請專刊範ffi -其中 d 係 Ο、1 或 2 ; e 係 1、2 或 3 ; C d + e )¾ 3 ; R2係如上面定義;;R3 係如上面定義;R 4係烷 蟇、芳基、烷芳蟇、芳烷基、或芳氧烷基,其中芳基部 份玎選用含有一或多個溴、氨或羥基;且R5係四價烴 基,若此禹芳杳烴,則可.選用含有一或多個溴、氛、烷 蟇或羥基图;及 〔ii〕一或多個下式之膜隨胺 R80 I r7o - p - ch2 - CH - CO - nh - ch2or5 fl ^ I 0 R9 .·- : . 其中R6代表氮原子或C!至〇!。烷基或烯基,同時R7及R8各單 獨禹選用經取代Ci-u烴基困,例如Cl — 4 烷基、 C2-·*破缔基或笨基’選用以·一種或更多種鹵常原子取 代且R9代表氮原子、鹵素原子、烷基困或式CH2CONHCH2ORe 之基困; 其中成份C i〕對成份〔ii〕、羌重量比率係 〇.1 : 1 至 2 : 1 ° L0V似 (請先閑讀背面之注意事項再填宵本頁) •裝· •訂· .線· 甲4(210X 297 公沒) —2 一 -017C8 A7 B7 C7 D7六'申請專利範面 1根抵·中請專利範圍、第1項之組合物,其特點在於成份 包括環系隣酸g穿例如式〔A〕之一種 一1種隣酸能,其中 1及其它式〔A〕膦醍莳之混合 據申請專利範圍笫2項之驵合物,其特點在於式〔a <成份内所具重量比率爲40 : 60至60 : 40且R、p 2 Λ』 *〒蟇汽I基且R1係甲氧基或匕氧基。 月沪範圍第3項之組合物,其特點在於其比早 為50 . 50 ’ R及R3係甲基,r 乙基。 · 根據申請専利範圍第i項之組合物 Cl~4烷基或蟀丙基。 1 b 係甲氡基且R 其特點在於R 經 濟 6·根據申. 叹寻則範圍第1項之驵合物,其特點在於R9 见原子、点& 均京、C 1 «烷蟇或CH*CONHCH2〇R« ,例如 基或乙基。 7·根據中%*. i - . 吼寻利範圍第1項之組合物,其特點在於成份 i i 3 <% r ra ^ ^H30 J2p〇CH3CH2C〇NHCHa〇H 0 8·根據申译必 ,利範固第〗項之組合物,其特點在於彼亦, 有用於成份「.. ^ 歸脲、乙炔11孓共固化劑,例如脲、按基三嗪、乙 说合物。二腺、其選用艇化甲搭縮合物或佐何這^甲 4(21〇χ297 公廣) .................................二................装..............................*Γ……·. ...................^ 先5-#背面<注%事項再磷考本頁) 3 一 3 一六、申請專利範園 經濟部中央橾準局印¾ 9-根據申請專利範圍第8項 固化劑所具固化時間係大於15 ^物,其特點在於共 1〇·裱據申請專利範圍第i项 ^ 亦含有氟緊合物。 、组合物,其特點在於彼 11-根據申請專利範園第1〇項之B 合物含有C N-炫蟇 — N—全。物’其竹點在於氣緊 “而ceFi7s02NH_。-垸基;磺短按基團,例 12·根據申請專利範圍第i项 亦含有朴-再吸洛劑及…其特點在於彼 子李^ 雞子系、熗離子系、此# 于系、兩性系或具反懕性软化 ·乎非難 η趙叹亿則表調理劑。 u 申请專利範圍第1項之狙入物,兄接 具有ΡΗ值爲小於3。 。物’其特點在於彼 .-種阻賴物之方法,其特點在於以包含如 利 1 jli 、 τ β寻利範圍第 貝芡阻燋組合物之水性介質、3 具有織维索足朴級維索系殲維之絨物,且將:( i5。…〜下進行熱處理二 /、中该織物之最終磷含量為0·5至4%。 々里’ 15·ίϊί請專利範圍第14項之方法,其特點在於以重五針 ,織物包括50至90 % (例如70至9〇 % )之纖維素系^ 瓜根據中請專利範圍w項之方法,Wm 物係混紡的織物C例如’其中,經紗或緯 六 裡爲 74(210X297 公沒) 一 4 — ..................................................3t..............................打..........................if {請先«I讀背面之注意事邛再填^本耳) A7 B7 ^ ^ C7 __D7 六、申請專利範ffi 棉織品而其它種係聚ϋ或尼龍J。 17·根據申請專利範圍第14項之方法,其特 點在於織物係具差異性表面織物。 18.根據申請專利範圍第14項之方法,其特 點在於浸渗结果所產生水載取量爲50至150 %,或加入 固煜量禹10至35 %。 ..................................................¾..............................4?..........................sf (請先聞讀背面之注意事項再嗔需本百) 經濟部中央標準局印製 —5 甲 4(210X 297公沒)第80101945號專利申請案 中文補充說明書(30年12月) 依賁冽1之步驟處理重〇. 330 kg/,m2之棉/聚銪混纺織物(55份棉與 45份聚酯)。 進行以下兩實驗: (i )硌去實洌1之,鱗醯胺,簧例1之浸濱液以濃度為100 s/ 1之環 系膦酸酯被取代,並用以處理一前述之織物試樣° (ϋ)濃度1〇〇 s/丨之環系膦酸酯,但無其它成汾,用以處理前述織 物之第二個試揉3 試樣(ί )及Ui)均不能通過英國標準5352第一部分(1979)以點燃源 0與1 ,在硬水浸濾前及某後,之可燃性試驗。 w a \ 0 11 〇 . g
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909004633A GB9004633D0 (en) | 1990-03-01 | 1990-03-01 | Flame retardant composition and method of use |
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| Publication Number | Publication Date |
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| TW201788B true TW201788B (zh) | 1993-03-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| TW080101945A TW201788B (zh) | 1990-03-01 | 1991-03-12 |
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| US (1) | US5126387A (zh) |
| EP (1) | EP0444647B1 (zh) |
| JP (1) | JPH05279665A (zh) |
| KR (1) | KR0171899B1 (zh) |
| AT (1) | ATE125317T1 (zh) |
| AU (1) | AU642465B2 (zh) |
| DE (1) | DE69111263T2 (zh) |
| DK (1) | DK0444647T3 (zh) |
| ES (1) | ES2077699T3 (zh) |
| GB (2) | GB9004633D0 (zh) |
| GR (1) | GR3017569T3 (zh) |
| LT (1) | LT3752B (zh) |
| LV (1) | LV11198B (zh) |
| MD (1) | MD940401A (zh) |
| PL (1) | PL166297B1 (zh) |
| TW (1) | TW201788B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5855983A (en) * | 1995-02-03 | 1999-01-05 | Minnesota Mining And Manufacturing Company | Flame retardant ultraviolet cured multi-layered film |
| WO2004001121A2 (en) * | 2002-06-20 | 2003-12-31 | University Of Georgia Research Foundation, Inc. | A durable flame retardant finish for cellulosic materials |
| US7067076B2 (en) * | 2003-08-01 | 2006-06-27 | Rhodia Inc. | Flame retardant phosphonate additives for thermoplastics |
| JP4667935B2 (ja) * | 2005-04-07 | 2011-04-13 | 明成化学工業株式会社 | 繊維構造物の撥水加工方法および当該方法により撥水加工された繊維構造物 |
| JP5075419B2 (ja) * | 2007-02-05 | 2012-11-21 | 日華化学株式会社 | ポリエステル系繊維用難燃加工剤、難燃加工方法、及び難燃性ポリエステル系繊維 |
| EP2178962A2 (en) * | 2007-08-07 | 2010-04-28 | Albemarle Corporation | Flame retarded flexible polyurethane foams and flexible polyurethane foam formulations |
| CN101772536B (zh) * | 2007-08-07 | 2012-06-27 | 雅宝公司 | 阻燃硬质聚氨酯泡沫和硬质聚氨酯泡沫制剂 |
| KR20140020229A (ko) | 2010-09-23 | 2014-02-18 | 아이씨엘-아이피 아메리카 아이엔씨. | 폴리하이드록시 포스포네이트가 실질적으로 없는 모노하이드록시 사이클릭 포스포네이트, 이의 제조방법 및 이로부터 제조되는 난연성 플렉시블 폴리우레탄 포움 |
| TWI445755B (zh) * | 2012-06-27 | 2014-07-21 | Ind Tech Res Inst | 阻燃性熱可塑性澱粉材料、生質複材及其製備方法 |
| CN103789999A (zh) * | 2013-11-30 | 2014-05-14 | 常熟市亚欧进出口贸易有限公司 | 涤纶织物的阻燃整理方法 |
| US9732193B1 (en) | 2016-03-23 | 2017-08-15 | International Business Machines Corporation | Flame-retardant polyhydroxyalkanoate phosphonate materials |
| US10072120B2 (en) | 2016-12-02 | 2018-09-11 | International Business Machines Corporation | Functionalized polyhydroxyalkanoate materials formed from an unsaturated polyhydroxyalkanoate material |
| US10081706B2 (en) | 2017-01-03 | 2018-09-25 | International Business Machines Corporation | Side-chain-functionalized polyhydroxyalkanoate materials |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL124172C (zh) | 1959-10-05 | 1900-01-01 | ||
| BE647376A (zh) * | 1963-05-03 | |||
| CH473937A (de) * | 1966-06-01 | 1969-07-31 | Ciba Geigy | Verfahren zum Flammfestmachen von cellulosehaltigen Textilmaterialien |
| US3763283A (en) * | 1969-10-17 | 1973-10-02 | Patrick & Co Inc C | N hydroxymethylated dialkyl phosphonoalkyl carbamates |
| US3969437A (en) * | 1971-02-23 | 1976-07-13 | Stauffer Chemical Company | Cyclic phosphorus esters |
| US3789091A (en) * | 1971-11-15 | 1974-01-29 | Mobil Oil Corp | Cyclic phosphonate esters and their preparation |
| US4068026A (en) | 1972-04-17 | 1978-01-10 | Hooker Chemicals & Plastics Corporation | Process for flame retarding cellulosics |
| US4078101A (en) | 1972-08-11 | 1978-03-07 | Albright & Wilson Ltd. | Flameproofing of textiles |
| ZA826861B (en) | 1981-09-28 | 1983-07-27 | Albright & Wilson | Flameproofing textiles |
| JPH0651946B2 (ja) * | 1985-06-25 | 1994-07-06 | 丸菱油化工業株式会社 | セルロ−ス系繊維材料の防炎加工法 |
| US4748705A (en) * | 1986-06-05 | 1988-06-07 | Burlington Industries, Inc. | Flame resistant polyester/cotton fabric and process for its production |
-
1990
- 1990-03-01 GB GB909004633A patent/GB9004633D0/en active Pending
-
1991
- 1991-02-27 ES ES91102951T patent/ES2077699T3/es not_active Expired - Lifetime
- 1991-02-27 DE DE69111263T patent/DE69111263T2/de not_active Expired - Fee Related
- 1991-02-27 EP EP91102951A patent/EP0444647B1/en not_active Expired - Lifetime
- 1991-02-27 AT AT91102951T patent/ATE125317T1/de not_active IP Right Cessation
- 1991-02-27 DK DK91102951.0T patent/DK0444647T3/da active
- 1991-03-01 PL PL91289263A patent/PL166297B1/pl unknown
- 1991-03-01 US US07/663,403 patent/US5126387A/en not_active Expired - Fee Related
- 1991-03-01 JP JP3036211A patent/JPH05279665A/ja active Pending
- 1991-03-01 GB GB9104330A patent/GB2241515B/en not_active Expired - Fee Related
- 1991-03-01 AU AU71985/91A patent/AU642465B2/en not_active Ceased
- 1991-03-02 KR KR1019910003498A patent/KR0171899B1/ko not_active Expired - Fee Related
- 1991-03-12 TW TW080101945A patent/TW201788B/zh active
-
1993
- 1993-06-30 LV LVP-93-981A patent/LV11198B/lv unknown
- 1993-12-07 LT LTIP1541A patent/LT3752B/lt not_active IP Right Cessation
-
1994
- 1994-07-11 MD MD94-0401A patent/MD940401A/ro unknown
-
1995
- 1995-09-28 GR GR950402682T patent/GR3017569T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB2241515B (en) | 1993-08-25 |
| DE69111263T2 (de) | 1995-12-21 |
| LT3752B (en) | 1996-03-25 |
| PL289263A1 (en) | 1991-12-02 |
| DE69111263D1 (de) | 1995-08-24 |
| KR0171899B1 (ko) | 1999-03-20 |
| EP0444647B1 (en) | 1995-07-19 |
| AU7198591A (en) | 1991-09-05 |
| LV11198A (lv) | 1996-04-20 |
| LV11198B (en) | 1996-08-20 |
| EP0444647A1 (en) | 1991-09-04 |
| AU642465B2 (en) | 1993-10-21 |
| PL166297B1 (pl) | 1995-05-31 |
| GR3017569T3 (en) | 1995-12-31 |
| MD940401A (ro) | 1996-02-29 |
| GB9104330D0 (en) | 1991-04-17 |
| GB2241515A (en) | 1991-09-04 |
| US5126387A (en) | 1992-06-30 |
| LTIP1541A (en) | 1995-06-26 |
| DK0444647T3 (da) | 1995-09-04 |
| JPH05279665A (ja) | 1993-10-26 |
| ES2077699T3 (es) | 1995-12-01 |
| KR910016904A (ko) | 1991-11-05 |
| ATE125317T1 (de) | 1995-08-15 |
| GB9004633D0 (en) | 1990-04-25 |
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