TWI646167B - Polarizing film with adhesive layer and image display device - Google Patents
Polarizing film with adhesive layer and image display device Download PDFInfo
- Publication number
- TWI646167B TWI646167B TW106130320A TW106130320A TWI646167B TW I646167 B TWI646167 B TW I646167B TW 106130320 A TW106130320 A TW 106130320A TW 106130320 A TW106130320 A TW 106130320A TW I646167 B TWI646167 B TW I646167B
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive layer
- polarizing film
- meth
- weight
- film
- Prior art date
Links
Landscapes
- Polarising Elements (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本發明之附黏著劑層之偏光薄膜係包含有偏光薄膜,及設於該偏光薄膜之黏著劑層者,前述偏光薄膜係僅於偏光子之單側具有透明保護薄膜,前述黏著劑層設於不具有前述透明保護薄膜側之偏光子,且前述黏著劑層係由包含(甲基)丙烯醯系聚合物(A)及鎓-含氟醯亞胺陰離子鹽(B)之黏著劑組成物所形成者;該附黏著劑層之偏光薄膜包含有具抗靜電功能,且滿足耐久性之黏著劑層,光學特性之劣化微小。 The polarizing film of the adhesive layer of the present invention comprises a polarizing film and an adhesive layer provided on the polarizing film, wherein the polarizing film has a transparent protective film on only one side of the polarizer, and the adhesive layer is disposed on the adhesive layer. The polarizer is not provided on the transparent protective film side, and the adhesive layer is composed of an adhesive composition containing a (meth) acrylonitrile-based polymer (A) and a ruthenium-fluorinated ruthenium anion salt (B). The polarizer film with the adhesive layer contains an adhesive layer having an antistatic function and satisfying durability, and the deterioration of optical characteristics is minute.
Description
本發明係有關於附黏著劑層之偏光薄膜,該附黏著劑層之偏光薄膜具有偏光薄膜及設於該偏光薄膜之黏著劑層。進而,本發明係有關於使用前述附黏著劑層之偏光薄膜之液晶顯示裝置、有機電致發光顯示裝置、PDP等之影像顯示裝置。 The present invention relates to a polarizing film with an adhesive layer having a polarizing film and an adhesive layer provided on the polarizing film. Further, the present invention relates to a liquid crystal display device using the above-described polarizing film with an adhesive layer, an organic electroluminescence display device, and an image display device such as a PDP.
液晶顯示裝置等,由於其影像形成方式,於液晶晶胞之兩側配置偏光元件係必要而不可或缺,一般是貼附有偏光薄膜。將液晶晶胞貼附於前述偏光薄膜時,一般係使用黏著劑。又,偏光薄膜與液晶晶胞之接著,通常為降低光損失,各個材料係使用黏著劑加以密著。於此場合,由於具有不需要用以讓偏光薄膜固著之乾燥程序等之優點,黏著劑一般係使用作為黏著劑層而預先設於偏光薄膜之單側之附黏著劑層之偏光薄膜。於附黏著劑層之偏光薄膜之黏著劑層,通常係貼附有離型薄膜。 In the liquid crystal display device or the like, it is necessary to arrange a polarizing element on both sides of the liquid crystal cell due to the image forming method, and a polarizing film is generally attached. When a liquid crystal cell is attached to the above polarizing film, an adhesive is generally used. Further, the polarizing film and the liquid crystal cell are usually followed by a reduction in light loss, and each material is adhered with an adhesive. In this case, since there is an advantage that a drying process for fixing the polarizing film is not required, the adhesive generally uses a polarizing film which is provided as an adhesive layer on the one side of the polarizing film. The adhesive layer of the polarizing film with the adhesive layer is usually attached with a release film.
液晶顯示裝置於製造時,將前述附黏著劑層之偏光薄膜貼附於液晶晶胞時,係由附黏著劑層之偏光薄膜之 黏著劑層將離型薄膜加以剝離,惟由於該離型薄膜之剝離,會產生靜電。如此產生之靜電會對液晶顯示裝置內部之液晶的配向產生影響,招致不良情況。又,於液晶顯示裝置使用時,會因靜電而產生顯示不均之情況。靜電之產生雖可藉由譬如於偏光薄膜之外部面形成抗靜電層而加以抑制,但有其效果不彰,無法根本的防止靜電產生之問題。因此,為根本的抑制靜電產生,係要求對於黏著劑層賦予抗靜電功效。作為對於黏著劑層給予抗靜電功效之方法,係提出有譬如於形成黏著劑層之黏著劑摻合離子化合物(專利文獻1至2)。專利文獻1中記載有包含咪唑陽離子及無機陰離子之離子固體,專利文獻2至4中記載有將包含四級氮原子之碳數6~50之陽離子、及包含氟原子之陰離子構成之鎓鹽等之常溫且液體之有機熔融鹽,摻合至使用於偏光薄膜之丙烯醯系黏著劑。又,提出有使用聚噻吩等之導電性聚合物之固著劑,於偏光薄膜與黏著劑層之間設置抗靜電層之方法等(專利文獻3)。再者,對於附黏著劑層之偏光薄膜,係要求於接著狀態中之耐久性。 In the manufacture of the liquid crystal display device, when the polarizing film with the adhesive layer is attached to the liquid crystal cell, it is a polarizing film with an adhesive layer. The adhesive layer peels off the release film, but static electricity is generated due to peeling of the release film. The static electricity generated in this way affects the alignment of the liquid crystal inside the liquid crystal display device, causing a problem. Further, when the liquid crystal display device is used, display unevenness may occur due to static electricity. The generation of static electricity can be suppressed by forming an antistatic layer on the outer surface of the polarizing film, but the effect is not obtained, and the problem of static electricity generation cannot be fundamentally prevented. Therefore, in order to fundamentally suppress the generation of static electricity, it is required to impart an antistatic effect to the adhesive layer. As a method of imparting an antistatic effect to an adhesive layer, an adhesive compound such as an adhesive for forming an adhesive layer is proposed (Patent Documents 1 to 2). Patent Document 1 describes an ionic solid containing an imidazole cation and an inorganic anion, and Patent Documents 2 to 4 include a cation including a cation having a carbon number of 6 to 50 including a quaternary nitrogen atom and an anion containing a fluorine atom. The organic molten salt at room temperature and liquid is blended into an acrylonitrile-based adhesive used for a polarizing film. Further, a method of using an anchor of a conductive polymer such as polythiophene or an antistatic layer between a polarizing film and an adhesive layer has been proposed (Patent Document 3). Further, the polarizing film with the adhesive layer is required to have durability in the next state.
專利文獻1 日本特開2009-251281號公報 Patent Document 1 Japanese Patent Laid-Open Publication No. 2009-251281
專利文獻2 國際公開2007/034533號公報 Patent Document 2 International Publication No. 2007/034533
專利文獻3 日本特開2003-246874號公報 Patent Document 3 Japanese Patent Laid-Open Publication No. 2003-246874
專利文獻1至2係藉由將以含有離子化合物之黏著劑組成物所形成之黏著劑層,應用於偏光薄膜而賦予抗靜電功效。專利文獻1至2中所適用之偏光薄膜,均係使用於偏光片之兩側具有透明保護薄膜等之保護基材者。 Patent Documents 1 to 2 impart antistatic effects by applying an adhesive layer formed of an adhesive composition containing an ionic compound to a polarizing film. The polarizing films to which the patent documents 1 to 2 are applied are used for a protective substrate having a transparent protective film or the like on both sides of the polarizing plate.
另一方面,作為附黏著劑層之偏光薄膜,有時亦使用僅於偏光片之單側設置透明保護薄膜,另一側不設置透明保護薄膜,且設有黏著劑層者。此種附黏著劑層之偏光薄膜,由於僅單側具有透明保護薄膜,相較於兩側均具有透明保護薄膜之態樣,係可削減透明保護薄膜一層份之成本,惟,讓黏著劑層含有離子化合物而賦予抗靜電功能時,該黏著劑層中之離子化合物將對於偏光片造成之影響重大,譬如,使用離子液體及離子固體作為離子化合物時,會讓偏光片劣化,而於潮濕試驗時具有光學特性大幅降低之問題。 On the other hand, as the polarizing film with an adhesive layer, a transparent protective film is provided on one side of the polarizer alone, and a transparent protective film is not provided on the other side, and an adhesive layer is provided. Since the polarizing film with the adhesive layer has a transparent protective film on only one side, compared with the transparent protective film on both sides, the cost of the transparent protective film can be reduced, but the adhesive layer is allowed. When an ionic compound is imparted to impart an antistatic function, the ionic compound in the adhesive layer may have a great influence on the polarizer. For example, when an ionic liquid or an ionic solid is used as the ionic compound, the polarizer is deteriorated, and the moisture test is performed. It has a problem that the optical characteristics are greatly reduced.
又,如專利文獻3,將含有聚噻吩等之導電聚合物之層設於偏光薄膜之態樣,偏光片亦劣化,光學特性降低。 Further, as disclosed in Patent Document 3, a layer containing a conductive polymer such as polythiophene is provided in a polarizing film, and the polarizer is also deteriorated, and optical characteristics are lowered.
本發明之目的係提供一種包含具抗靜電功效且滿足耐久性之黏著劑層,光學特性之劣化微小之附黏著劑層之偏光薄膜。 SUMMARY OF THE INVENTION An object of the present invention is to provide a polarizing film comprising an adhesive layer which has an antistatic effect and which satisfies durability, and which has a slight deterioration in optical characteristics.
又,本發明之目的係提供一種使用前述附黏著劑層之偏光薄膜之影像顯示裝置。 Further, it is an object of the present invention to provide an image display apparatus using the above-described polarizing film with an adhesive layer.
本案發明者群為解決前述課題而經銳意研究之 結果,找出下述附黏著劑層之偏光薄膜而完成本發明。 The inventors of this case have been keenly studying to solve the aforementioned problems. As a result, the polarizing film with the following adhesive layer was found to complete the present invention.
亦即,本發明係有關於一種附黏著劑層之偏光薄膜,其係具有偏光薄膜及設於該偏光薄膜之黏著劑層者,其特徵在於:前述偏光薄膜係僅於偏光子之單側具有透明保護薄膜,前述黏著劑層設於偏光子之不具有前述透明保護薄膜之側,且前述黏著劑層係由包含(甲基)丙烯醯系聚合物(A)及鎓-含氟醯亞胺陰離子鹽(B)之黏著劑組成物所形成者。 That is, the present invention relates to a polarizing film with an adhesive layer which has a polarizing film and an adhesive layer provided on the polarizing film, wherein the polarizing film has only one side of the polarizer. a transparent protective film, wherein the adhesive layer is provided on a side of the polarizer that does not have the transparent protective film, and the adhesive layer is composed of a (meth) acrylonitrile-based polymer (A) and a ruthenium-fluoride-containing fluorene The composition of the adhesive composition of the anionic salt (B).
前述附黏著劑層之偏光薄膜中,前述鎓-含氟醯亞胺陰離子鹽(B)中之鎓宜選自含氮鎓、含硫鎓及含磷鎓中之至少1種。 In the polarizing film with an adhesive layer, at least one of the cerium-fluorinated quinone anion salt (B) is at least one selected from the group consisting of nitrogen-containing cerium, cerium-containing cerium, and phosphorus-containing cerium.
又,前述附黏著劑層之偏光薄膜中,前述鎓-含氟醯亞胺陰離子鹽(B)中之鎓宜選自銨、吡咯烷鎓、哌啶及鋶中之至少1種。 Further, in the polarizing film with an adhesive layer, at least one of ammonium, pyrrolidinium, piperidine and anthracene is preferably selected from the above-mentioned barium-fluorinated quinone anion salt (B).
又,前述附黏著劑層之偏光薄膜中,前述鎓-含氟醯亞胺陰離子鹽(B)中之鎓宜不具有不飽和鍵。 Further, in the polarizing film with the adhesive layer, the cerium-fluorinated quinone anion salt (B) preferably does not have an unsaturated bond.
又,前述附黏著劑層之偏光薄膜中,前述鎓-含氟醯亞胺陰離子鹽(B)中之鎓係一具有碳數1~4之烷基之烷鎓。 Further, in the polarizing film with an adhesive layer, the fluorene in the fluorene-fluorene quinone anion salt (B) is an alkane having an alkyl group having 1 to 4 carbon atoms.
前述附黏著劑層之偏光薄膜中,相對於(甲基)丙烯醯系聚合物(A)100重量份,宜含有0.1~10重量份之前述鎓-含氟醯亞胺陰離子鹽(B)。 In the polarizing film with an adhesive layer, it is preferable to contain 0.1 to 10 parts by weight of the above-mentioned fluorene-fluorene sulfinium anion salt (B) per 100 parts by weight of the (meth) acrylonitrile-based polymer (A).
前述附黏著劑層之偏光薄膜中,偏光子宜使用厚 度10μm以下者。 In the polarizing film with the adhesive layer, the polarizer should be thick. Degrees below 10μm.
前述附黏著劑層之偏光薄膜中,(甲基)丙烯醯系聚合物(A)宜含有甲基丙醯酸烷酯及含羥基單體作為單體單元。 In the polarizing film with an adhesive layer, the (meth) acrylonitrile-based polymer (A) preferably contains a methyl propyl acrylate and a hydroxyl group-containing monomer as a monomer unit.
前述附黏著劑層之偏光薄膜中,(甲基)丙烯醯系聚合物(A)宜含有甲基丙醯酸烷酯及含羧基單體作為單體單元。 In the polarizing film with an adhesive layer, the (meth) acrylonitrile-based polymer (A) preferably contains a methyl propyl acrylate and a carboxyl group-containing monomer as a monomer unit.
前述附黏著劑層之偏光薄膜中,前述黏著劑組成物可進而含有交聯劑。該黏著劑組成物中,相對於(甲基)丙烯醯系聚合物(A)100重量份,宜含有0.01~20重量份之交聯劑(C)。作為交聯劑(C),宜選自異氰酸酯系化合物及過氧化物之至少1種。 In the polarizing film with an adhesive layer, the adhesive composition may further contain a crosslinking agent. The adhesive composition preferably contains 0.01 to 20 parts by weight of the crosslinking agent (C) based on 100 parts by weight of the (meth)acrylonitrile-based polymer (A). The crosslinking agent (C) is preferably at least one selected from the group consisting of an isocyanate compound and a peroxide.
前述附黏著劑層之偏光薄膜中,相對於(甲基)丙烯醯系聚合物(A)100重量份,可進一步含有矽烷偶合劑(D)0.001~5重量份。 The polarizing film with an adhesive layer may further contain 0.001 to 5 parts by weight of the decane coupling agent (D) based on 100 parts by weight of the (meth) acrylonitrile-based polymer (A).
前述附黏著劑層之偏光薄膜中,相對於(甲基)丙烯醯系聚合物(A)100重量份,可進一步含有聚醚改質矽氧烷化合物0.001~10重量份。 In the polarizing film with the adhesive layer, the polyether modified siloxane compound may further contain 0.001 to 10 parts by weight based on 100 parts by weight of the (meth) acrylonitrile-based polymer (A).
前述附黏著劑層之偏光薄膜中,(甲基)丙烯醯系聚合物(A)之重量平均分子量宜為50萬~300萬。 In the polarizing film with the adhesive layer, the weight average molecular weight of the (meth) acrylonitrile-based polymer (A) is preferably from 500,000 to 3,000,000.
前述附黏著劑層之偏光薄膜中,宜於偏光薄膜與黏著劑層之間具有易接著層。 In the polarizing film with the adhesive layer, it is preferred to have an easy adhesion layer between the polarizing film and the adhesive layer.
又,本發明係有關一種影像顯示裝置,其特徵在於:使用至少1個前述之附黏著劑層之偏光薄膜。 Further, the present invention relates to an image display device characterized in that at least one of the above-mentioned polarizing films with an adhesive layer is used.
在將丙烯醯系聚合物作為基底聚合物使用之黏著劑中,藉由在該黏著中記摻合離子性化合物,係可賦予抗靜電效能。此時,可考慮藉由讓離子性化合物由黏著劑層表面釋放,而可有效地展現抗靜電功效。另一方面,由於離子性化合物接觸到偏光子,而有偏光度等之光學特性低落之情況。 In the adhesive used as the base polymer of the acrylonitrile-based polymer, the antistatic property can be imparted by incorporating an ionic compound in the adhesive. At this time, it is considered that the antistatic effect can be effectively exhibited by allowing the ionic compound to be released from the surface of the adhesive layer. On the other hand, since the ionic compound is in contact with the polarizer, the optical characteristics such as the degree of polarization are lowered.
形成本發明之附黏著劑層之偏光薄膜其黏著劑層之黏著劑層組成物,除基底聚合物之(甲基)丙烯醯系聚合物(A),並含有作為離子性化合物且可賦予抗靜電功效之鎓-含氟醯亞胺陰離子鹽(B),藉由該黏著劑層組成物而形成之黏著劑層,抗靜電功效優異。又,可知本發明藉由使用前述鎓-含氟醯亞胺陰離子鹽(B),可不招致偏光子劣化,且可賦予抗靜電功效。 The adhesive layer composition of the adhesive layer forming the polarizing film of the adhesive layer of the present invention, in addition to the (meth) acrylonitrile-based polymer (A) of the base polymer, and containing as an ionic compound and imparting resistance The electrostatic effect 鎓-fluorinated quinone imine anion salt (B), the adhesive layer formed by the adhesive layer composition, has excellent antistatic effect. Further, it is understood that the present invention can impart an antistatic effect without causing degradation of a polarizer by using the above-described fluorene-fluorene sulfinium anion salt (B).
形成本發明之附黏著劑層之偏光薄膜的黏著劑層之黏著劑組成物,係含有(甲基)丙烯醯系聚合物(A)作為基底聚合物。一般上,(甲基)丙烯醯系聚合物(A)係含有(甲基)丙烯酸烷酯為主成分以作為單體單元。又,(甲基)丙烯酸酯意指丙烯酸酯及/或甲基丙烯酸酯,與本發明中之(甲基)同義。 The adhesive composition of the adhesive layer forming the polarizing film with the adhesive layer of the present invention contains a (meth)acryl fluorene-based polymer (A) as a base polymer. In general, the (meth)acrylonitrile-based polymer (A) contains an alkyl (meth)acrylate as a main component as a monomer unit. Further, (meth) acrylate means acrylate and/or methacrylate, and is synonymous with (meth) in the present invention.
構成(甲基)丙烯醯系聚合物(A)之主骨架之(甲基)丙烯酸烷酯,係可例示直鏈狀或支鏈狀之烷基之碳數1~18者。譬如作為前述之烷基,可例示甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、己基、環己基、庚基、2-乙基己基、異辛基、壬基、癸基、異癸基、十二基、異十四基、月桂基、十三基、十五基、十六基、十七基、十八基等。其等可單獨或組合使用。該等烷基之平均碳數宜為3~9。 The alkyl (meth)acrylate constituting the main skeleton of the (meth) acrylonitrile-based polymer (A) may, for example, be a linear or branched alkyl group having 1 to 18 carbon atoms. For example, as the alkyl group described above, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, and the like are exemplified. Sulfhydryl, fluorenyl, isodecyl, dodecyl, isotetradecyl, lauryl, thirteen, fifteen, heptyl, heptadecyl, and octadecyl. They can be used singly or in combination. The average carbon number of the alkyl groups is preferably from 3 to 9.
前述(甲基)丙烯醯系聚合物(A)中,以改善接著性及耐熱性為目的,係可藉由共聚合而導入1種類以上、具有(甲基)丙烯醯基或乙烯基等具不飽和雙鍵之聚合性官能基的共聚合單體。作為此種共聚合單體之具體例,係可例舉如:(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酸或(4-羥甲基環己基)-丙烯酸甲酯等之含羥基單體;(甲基)丙烯酸、羥乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、伊康酸、馬來酸、延胡索酸、巴豆酸等之含羧機單體;丙烯酸之己內酯加成物;苯乙烯磺酸或烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙烷磺酸、(甲基)丙烯醯胺丙烷磺酸、磺丙基(甲基)丙烯酸酯、(甲基)丙烯醯氧基萘磺酸等之含磺酸單體;2-羥乙基丙烯醯基燐酸酯等之含燐酸基單體等。 In the (meth) acrylonitrile-based polymer (A), for the purpose of improving the adhesion and the heat resistance, one type or more of the (meth) acrylonitrile group or the vinyl group can be introduced by copolymerization. A copolymerizable monomer of a polymerizable functional group of an unsaturated double bond. Specific examples of such a copolymerizable monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauric acid (meth)acrylate or (4-hydroxymethyl) a hydroxyl group-containing monomer such as cyclohexyl)-methyl acrylate; (meth)acrylic acid, hydroxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, Carboxylic acid monomer such as crotonic acid; caprolactone adduct of acrylic acid; styrenesulfonic acid or allylsulfonic acid, 2-(methyl)acrylamidoxime-2-methylpropanesulfonic acid, (A) a sulfonic acid-containing monomer such as acrylamide sulfonium sulfonic acid, sulfopropyl (meth) acrylate or (meth) propylene phthaloxy naphthalene sulfonic acid; 2-hydroxyethyl acryl decyl phthalate; The phthalic acid-containing monomer or the like.
又,改質目的之單體例亦可舉出:(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺或N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等 之(N-取代)醯胺系單體;(甲基)丙烯酸胺乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等之(甲基)丙烯酸烷基胺烷酯系單體;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等之(甲基)丙烯酸烷氧基烷酯系單體;N-(甲基)丙烯醯基亞甲基丁二醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基丁二醯亞胺、N-(甲基)丙烯醯基-8-氧基伸辛基丁二醯亞胺、N-丙烯醯基瑪福琳等之丁二醯亞胺系單體;N-環己基馬來醯亞胺或N-異丙基馬來西亞胺、N-月桂基馬來醯亞胺或N-苯基馬來醯亞胺等之醯亞胺系單體;N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等之伊康醯亞胺系單體等。 Further, examples of the monomer for the purpose of modification include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide or N. -Hydroxymethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc. (N-substituted) guanamine monomer; amine methyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, tert-butylamino (meth) acrylate An alkyl alkoxyalkyl (meth)acrylate such as an ester; an alkoxyalkyl (meth)acrylate such as methoxyethyl (meth)acrylate or ethoxyethyl (meth)acrylate; Monomer; N-(methyl)propenylmethylenebutylidene or N-(methyl)propenyl-6-oxyhexamethylenebutaneimine, N-(A) Base) butyl fluorenyl-8-oxy octyl succinimide, N-propylene decyl melamine, etc.; N-cyclohexylmaleimide or N-iso a quinone imine monomer such as propyl ketamine, N-lauryl maleimide or N-phenyl maleimide; N-methyl Ikonide, N-ethyl Itaconium Imine, N-butyl Ikonideimine, N-octylkonkineimine, N-2-ethylhexylkkonium imine, N-cyclohexylkkonium imine, N-lauryl An Ikonideimine monomer such as ikonium imine.
再者,作為改質單體,亦可使用醋酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基六氫吡、乙烯基吡、乙烯基吡咯、乙烯基咪唑、乙烯基噁唑、乙烯基瑪福琳、N-乙烯基羧醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等之乙烯基系單體;丙烯腈、甲基丙烯腈等之氰基丙烯酸酯系單體;(甲基)丙烯酸環氧丙基酯等之含環氧基丙烯酸系單體;(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯等之二醇系丙烯酸酯單體;(甲基)丙烯酸四氫呋喃甲酯、氟素(甲基)丙烯酸酯、聚矽氧烷(甲 基)丙烯酸酯、2-甲氧基乙基丙烯酸酯等之丙烯酸酯系單體。進而,可例舉如異戊二烯、丁二烯、異丁烯、乙烯基醚等。 Further, as the modifying monomer, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine may also be used. Vinyl hexahydropyridinium Vinylpyr Ethylene, vinylpyrrole, vinylimidazole, vinyl oxazole, vinyl marfoline, N-vinyl carbamide, styrene, α-methylstyrene, N-vinyl caprolactam, etc. a base monomer; a cyanoacrylate monomer such as acrylonitrile or methacrylonitrile; an epoxy group-containing acrylic monomer such as a glycidyl (meth)acrylate; and a (meth)acrylic poly(ethylene) a glycol-based acrylate monomer such as a glycol ester, a polypropylene glycol (meth)acrylate, a methoxyethylene glycol (meth)acrylate, or a methoxypolypropylene glycol (meth)acrylate; An acrylate-based monomer such as tetrahydrofuran methyl acrylate, fluoro (meth) acrylate, polydecane (meth) acrylate or 2-methoxyethyl acrylate. Further, for example, isoprene, butadiene, isobutylene, vinyl ether or the like can be mentioned.
進而,上述以外之可共聚合單體,可例舉含有矽原子之矽烷系單體等。作為矽烷系單體,可舉出譬如3-丙烯醯氧丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯氧癸基三甲氧基矽烷、10-丙烯醯氧基癸基三甲氧基矽烷、10-甲基丙烯醯氧癸基三乙氧基矽烷、10-丙烯醯氧癸基三乙氧基矽烷等。 Further, the copolymerizable monomer other than the above may, for example, be a decane-based monomer containing a ruthenium atom. Examples of the decane-based monomer include 3-propenylmethoxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 4-vinylbutyltrimethoxydecane, and 4 -vinylbutyltriethoxydecane, 8-vinyloctyltrimethoxydecane, 8-vinyloctyltriethoxydecane, 10-methylpropenyloxydecyltrimethoxydecane, 10- Propylene decyl decyl trimethoxy decane, 10-methyl propylene fluorenyl decyl triethoxy decane, 10- propylene fluorenyl decyl triethoxy decane, and the like.
又,共聚合單體亦可使用三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等之(甲基)丙烯酸與多價醇的酯化物等具有2個以上的(甲基)丙烯醯基、乙烯基等不飽和雙鍵的多官能性單體,抑或在聚酯、環氧化物、胺基甲酸酯等的骨架附加2個以上,作為與單體成分相同之官能基的(甲基)丙烯醯基、乙烯基等不飽和雙鍵而成之聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯等。 Further, as the copolymerizable monomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A may also be used. Epoxypropyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa a polyfunctional monomer having two or more unsaturated double bonds such as a (meth)acryl fluorenyl group or a vinyl group, such as an esterified product of (meth)acrylic acid or the like, such as a methyl acrylate, and a polyvalent alcohol, or A polyester obtained by adding two or more kinds of a skeleton such as an ester, an epoxide, or a urethane to an unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group which is a functional group similar to the monomer component ( Methyl) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like.
(甲基)丙烯醯系聚合物(A)於全部構成單體之重量比中,係以(甲基)丙烯酸烷酯為主成分,而(甲基)丙烯醯系聚合物(A)中之前述共聚合單體的比率並無特別限制,惟前述共聚合單體之比率於全部構成單體之重量比中,約0~20%、約0.1~15%,進而,0.1~10%為宜。 In the weight ratio of the (meth)acrylonitrile-based polymer (A) to all the constituent monomers, the (meth)acrylic acid alkyl ester is mainly composed, and the (meth)acrylonitrile-based polymer (A) is used. The ratio of the above-mentioned copolymerized monomer is not particularly limited, but the ratio of the above-mentioned copolymerized monomer is about 0 to 20%, about 0.1 to 15% by weight of the total constituent monomers, and further preferably 0.1 to 10%. .
其等共聚合單體之中,由接著性、耐久性之觀點,宜使用含羥基單體或含羧基單體。可併用含羥基單體及含羧基單體。其等共聚合單體於黏著劑組成物含有交聯劑時,會成為與交聯劑之反應點。含羥基單體、含羧基單體等,係富有與分子間交聯劑之反應性,故適合使用以提高所得之黏著劑層之凝集性及耐熱性提高。含羥基單體於再加工性之點是為理想,又,含羧基單體於兼顧耐久性與再加工性之點,是適宜的。 Among these copolymerized monomers, a hydroxyl group-containing monomer or a carboxyl group-containing monomer is preferably used from the viewpoint of adhesion and durability. A hydroxyl group-containing monomer and a carboxyl group-containing monomer may be used in combination. When the copolymerizable monomer contains a crosslinking agent in the adhesive composition, it becomes a reaction point with the crosslinking agent. Since a hydroxyl group-containing monomer or a carboxyl group-containing monomer is rich in reactivity with an intermolecular crosslinking agent, it is suitably used to improve the aggregation property and heat resistance of the obtained adhesive layer. The hydroxyl group-containing monomer is desirable in terms of reworkability, and the carboxyl group-containing monomer is suitable in terms of both durability and reworkability.
作為共聚合單體,具有含羥基單體時,其比率宜為0.01~15重量%,0.03~10重量%較佳,進而,0.05~7重量%更佳。作為共聚合單體,具有含羧基單體時,其比率宜為0.05~10重量%,0.1~8重量%較佳,進而,0.2~6重量%更佳。 When the hydroxyl group-containing monomer is used as the copolymerizable monomer, the ratio thereof is preferably 0.01 to 15% by weight, preferably 0.03 to 10% by weight, more preferably 0.05 to 7% by weight. When the carboxyl group-containing monomer is a copolymerizable monomer, the ratio thereof is preferably 0.05 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight.
本發明之(甲基)丙烯醯系聚合物(A),通常係使用重量平均分子量為50萬~300萬之範圍者。若考量到耐久性,特別是耐熱性,宜使用重量平均分子量為70萬~270萬者。進而,80萬~250萬為佳。若重量平均分子量小於50萬,於耐熱性之點並不理想。又,若重量平均分子量大於300萬,為調整成塗敷所用之黏度,需要大量的稀釋溶劑,會 提高成本,故不理想。又,重量平均分子量係指以GPC(Gel Permeation Chromatography膠透層析術)加以測量,並由聚苯乙烯換算而算出之值。 The (meth) acrylonitrile-based polymer (A) of the present invention is usually one having a weight average molecular weight of from 500,000 to 3,000,000. When considering durability, particularly heat resistance, it is preferred to use a weight average molecular weight of 700,000 to 2.7 million. Furthermore, 800,000 to 2.5 million is preferred. If the weight average molecular weight is less than 500,000, it is not preferable in terms of heat resistance. Moreover, if the weight average molecular weight is more than 3 million, in order to adjust the viscosity for coating, a large amount of diluent solvent is required, It is not ideal to increase costs. Further, the weight average molecular weight means a value measured by GPC (Gel Permeation Chromatography) and calculated from polystyrene.
此種(甲基)丙烯醯系聚合物(A)之製造,係可適宜地選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等習知的製造方法。又,所得之(甲基)丙烯醯系聚合物(A)可為無規共聚物、嵌段共聚物、接枝共聚物等之任一者。 In the production of such a (meth) acrylonitrile-based polymer (A), a conventional production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected. Further, the obtained (meth) acrylonitrile-based polymer (A) may be any of a random copolymer, a block copolymer, and a graft copolymer.
又,溶液聚合中,作為聚合溶劑,係可使用譬如醋酸乙酯、甲苯等。作為具體的溶液聚合例,反應係於氮等惰性氣體氣流下,加入聚合起始劑,且通常以約50~70℃、約5~30小時之反應條件進行。 Further, in the solution polymerization, as the polymerization solvent, for example, ethyl acetate, toluene or the like can be used. As a specific solution polymerization example, the reaction is carried out under a flow of an inert gas such as nitrogen, and a polymerization initiator is added, and it is usually carried out at a reaction temperature of about 50 to 70 ° C for about 5 to 30 hours.
自由基聚合所使用之聚合起始劑、鏈轉移劑、乳化劑等並無特別限定,可適宜地選擇使用。又,(甲基)丙烯醯系聚合物(A)之重量平均分子量,係可藉由聚合起始劑、鏈轉移劑之使用量、反應條件而加以控制,並因應其等之種類而適宜地調整其使用量。 The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. Further, the weight average molecular weight of the (meth) acrylonitrile-based polymer (A) can be controlled by the amount of the polymerization initiator, the chain transfer agent used, and the reaction conditions, and is appropriately selected depending on the type thereof. Adjust its usage.
聚合起始劑係可例舉如2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲腈基丙烷)二氯酸鹽、2,2’-偶氮雙[2-(5-甲基-2-咪唑啶-2-基)丙烷]二氯酸鹽、2,2’-偶氮雙(2-甲基丙腈)二硫酸鹽、2,2’-偶氮雙(N,N’-二亞甲基異丁腈)、2,2’-偶氮雙[N-(2-羧乙基)-2-甲基丙腈]水合物(和光純藥工業株式會社製VA-057)等之偶氮系起始劑;過硫酸鉀、過硫酸銨、過硫酸鹽等之過硫酸鹽;二(2-乙基己基)過氧化二碳酸酯、二(4-第三丁基環己基)過氧化二碳酸酯、二-第二丁基過氧化 二碳酸酯、第三丁基過氧化新癸酸酯、第三己基過氧化三甲基乙酸酯、第三丁基過氧化三甲基乙酸酯、二月桂醯過氧化物、二-正辛醯過氧化物、1,1,3,3-四甲基丁基過氧化-2-乙基己酸酯、二(4-甲基苯甲醯)過氧化物、二苯甲醯過氧化物、第三丁基過氧化異丁酸酯、1,1-二(第三己基過氧化)環己烷、第三丁基過氧化氫、過氧化氫等之過氧化物系起始劑;過硫酸鹽及亞硫酸鹽之組合、過氧化物及抗壞血酸鈉之組合等的過氧化物與還原劑而成之氧化還原起始劑等,但不限定於此。 The polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-carbonitrilepropane) dichlorate or 2,2'-azobis. [2-(5-Methyl-2-imidazolidin-2-yl)propane]dichlorate, 2,2'-azobis(2-methylpropionitrile) disulfate, 2,2'- Azobis(N,N'-dimethylmethyleneisobutyronitrile), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionitrile]hydrate (Wako Pure Chemicals) An azo initiator such as VA-057) manufactured by Industrial Co., Ltd.; a persulfate such as potassium persulfate, ammonium persulfate or persulphate; bis(2-ethylhexyl)peroxydicarbonate; 4-tert-butylcyclohexyl)peroxydicarbonate, di-secondary butyl peroxidation Dicarbonate, tert-butyl peroxy neodecanoate, third hexylperoxyperoxyacetate, tert-butylperoxytrimethylacetate, dilaurin peroxide, di-positive Octanol peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, bis(4-methylbenzhydrazide) peroxide, benzophenone peroxidation a peroxide-based initiator of tributyl butyl peroxybutyrate, 1,1-di(t-hexylperoxy)cyclohexane, tert-butyl hydroperoxide, hydrogen peroxide or the like; A redox initiator such as a peroxide and a reducing agent such as a combination of a persulfate and a sulfite, a combination of a peroxide and sodium ascorbate, and the like, but is not limited thereto.
前述聚合起始劑係可單獨使用,或亦可混合2種以上使用,惟全體之含量係相對於單體100重量份,宜約為0.005~1重量份,約0.02~0.5重量份更佳。 The polymerization initiator may be used singly or in combination of two or more kinds, and the total content is preferably about 0.005 to 1 part by weight, more preferably about 0.02 to 0.5 part by weight, per 100 parts by weight of the monomer.
又,作為聚合起始劑,譬如使用2,2’-偶氮雙異丁脒來製造前述重量平均分子量之(甲基)丙烯醯系聚合物(A)時,聚合起始劑之使用量係相對於單體成分總量100重量份,宜約為0.06~0.2重量份,進而以約0.08~0.175重量份為宜。 Further, when a (meth)acrylic fluorene-based polymer (A) having the above weight average molecular weight is produced by using 2,2'-azobisisobutyl hydrazine as a polymerization initiator, the amount of the polymerization initiator used is It is preferably about 0.06 to 0.2 parts by weight, and more preferably about 0.08 to 0.175 parts by weight, based on 100 parts by weight of the total of the monomer components.
作為鏈轉移劑,係可舉出如月桂基硫醇、環氧丙基硫醇、巰基醋酸、2-巰基乙醇、硫乙二醇酸、硫乙二醇酸2-乙基己酯、2,3-二巰基-1-丙醇等。鏈轉移劑係可單獨使用,或亦可混合2種以上使用,惟全體之含量相對於單體成分的總量100重量份,宜約為0.1重量份以下。 Examples of the chain transfer agent include lauryl mercaptan, epoxypropyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2, 3-dimercapto-1-propanol and the like. The chain transfer agent may be used singly or in combination of two or more kinds, and the total content is preferably about 0.1 part by weight or less based on 100 parts by weight of the total of the monomer components.
又,進行乳化聚合時所使用之乳化劑,係可例舉月桂基硫酸鈉、月桂基硫酸銨、十二基苯磺酸鈉、聚氧乙烯烷基醚硫酸銨、聚氧乙烯烷苯醚硫酸鈉等之硫酸鈉等之陰離 子系乳化劑;聚氧乙烯烷基醚、聚氧乙烯烷苯醚、聚氧乙烯脂肪酸酯、聚氧乙烯-聚氧丙烯嵌段聚合物等之非離子系乳化劑等。其等乳化劑可單獨使用,亦可併用2種類以上。 Further, the emulsifier used in the emulsion polymerization may, for example, be sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate or polyoxyethylene alkyl ether sulfate. Anion such as sodium sulfate A emulsifier; a nonionic emulsifier such as a polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether, a polyoxyethylene fatty acid ester, or a polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used singly or in combination of two or more.
進而,作為反應性乳化劑,如導入有丙烯基、烯丙基醚基等之自由基聚合性官能基之乳化劑,具體上係譬如有Aqualon()HS-10、HS-20、KH-10、BC-05、BC-10、BC-20(以上均為第一工業製藥公司製),ADEKA REASO SE10N(旭電化工公司製)等。由於反應性乳化劑於聚合後被取入聚合物鏈,因此耐水性變佳,是為合宜。乳化劑之使用量係相對於單體成分之總量100重量份,為0.3~5重量份,由聚合穩定性及機械性的穩定性,0.5~1重量份更佳。 Further, as the reactive emulsifier, for example, an emulsifier having a radical polymerizable functional group such as a propenyl group or an allyl ether group is introduced, and specifically, for example, Aqualon ( ) HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all of which are manufactured by First Industrial Pharmaceutical Co., Ltd.), ADEKA REASO SE10N (made by Asahi Chemical Co., Ltd.). Since the reactive emulsifier is taken into the polymer chain after the polymerization, the water resistance is improved, which is suitable. The amount of the emulsifier used is 0.3 to 5 parts by weight based on 100 parts by weight of the total of the monomer components, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.
本發明之黏著劑組成物,除前述(甲基)丙烯醯系聚合物(A),並含有前述鎓-含氟醯亞胺陰離子鹽(B)。前述鎓-含氟醯亞胺陰離子鹽(B)係「離子性化合物」,「離子性化合物」亦稱為離子性液體、離子性固體。前述鎓-含氟醯亞胺陰離子鹽(B)係由陽離子成分及陰離子成分構成之陽離子-陰離子鹽。於本發明,係使用該陽離子-陰離子鹽之中,陽離子為鎓,陰離子為含氟醯亞胺陰離子之鎓-含氟醯亞胺陰離子鹽。 The adhesive composition of the present invention contains the above-mentioned fluorene-fluorene quinone anion salt (B) in addition to the above (meth) acrylonitrile-based polymer (A). The fluorene-fluorene quinone anion salt (B) is an "ionic compound", and the "ionic compound" is also called an ionic liquid or an ionic solid. The hydrazine-fluorinated quinone anion salt (B) is a cation-anion salt composed of a cationic component and an anionic component. In the present invention, among the cation-anion salts, an anthracene-fluorinated quinone imine anion salt having a cation as a ruthenium and an anion as a fluorine-containing quinone imine anion is used.
<含氟醯亞胺陰離子> <Fluorinated quinone anion>
作為構成前述鎓-含氟醯亞胺陰離子鹽(B)中之陰離子部的含氟醯亞胺陰離子,係可例示如具有全氟烴基之亞胺陰離子。 The fluorine-containing quinone imine anion constituting the anion portion in the fluorene-fluorene quinone anion salt (B) may, for example, be an imine anion having a perfluorohydrocarbon group.
具體上,係可使用(CF3SO2)(CF3CO)N-、或下述一般式(1)~(3)所示者,即:(1):(CnF2n+1SO2)2N-(惟n為1~10之整數)、(2):CF2(CmF2mSO2)2N-(惟m為1~10之整數)、(3):(CpF2p+1SO2)N-(CqF2q+1SO2)(惟p、q為1~10之整數)。其等含氟醯亞胺陰離子由於可獲得離子解離性優異之離子性化合物,故可合宜地使用。又,前述含氟醯亞胺陰離子係具有碳數1~4之氟化烷基或氟化伸烷基者,在可減少表面電阻值且抑制靜電紊亂方面,是為理想。作為前述含氟醯亞胺陰離子,宜為以(CF3SO2)2N-、(C2F5SO2)2N-等之前述一般式(1)表示之(全氟過氧化烷基磺醯亞胺),特別是以(CF3SO2)2N-表示之(三氟甲烷磺醯亞胺)為宜。 Specifically, (CF 3 SO 2 )(CF 3 CO)N − or the following general formulas (1) to (3) can be used, namely: (1): (C n F 2n+1 SO 2 ) 2 N - (only n is an integer from 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N - (only m is an integer from 1 to 10), (3): (C p F 2p+1 SO 2 )N - (C q F 2q+1 SO 2 ) (only p and q are integers from 1 to 10). The fluorine-containing quinone imine anion can be suitably used because it can obtain an ionic compound excellent in ion dissociation property. Further, the fluorine-containing quinone imine anion has a fluorinated alkyl group or a fluorinated alkyl group having 1 to 4 carbon atoms, and is preferable in that it can reduce the surface resistance value and suppress static electricity. The fluorine-containing quinone imine anion is preferably represented by the above general formula (1) of (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - or the like (perfluoroperoxyalkyl group) Sulfoimine), particularly (CF 3 SO 2 ) 2 N - (trifluoromethanesulfonimide) is preferred.
<鎓> <鎓>
作為構成前述鎓-含氟醯亞胺陰離子鹽(B)中之陽離子部的鎓,係成為鎓離子之原子經質子化者。又,本發明之鎓由不會因雙鍵、三鍵等之不飽和鍵而形成鎓鹽者可抑制偏光子劣化之點,是為合宜。亦即,本發明之鎓宜為以有機基等之置換而形成鎓離子之有機鎓為佳。 The ruthenium constituting the cation portion in the ruthenium-fluorinated quinone anion salt (B) is a protonated atom of ruthenium ions. Further, in the present invention, it is preferable that the bismuth salt is not formed by an unsaturated bond such as a double bond or a triple bond, and the deterioration of the photon can be suppressed. That is, it is preferred that the present invention is an organic hydrazine which forms a cerium ion by substitution with an organic group or the like.
又,作為前述有機鎓中之有機基,係可例示烷基、烷氧基、烯基等。其等之中,由抑制偏光子劣化之點,係以不具有不飽和鍵者為佳。烷基之碳數係可譬如由1~12選擇,較佳為1~8,更佳者為1~4。作為有機鎓,所有的置換基宜為具有碳數1~4之烷基的烷鎓。烷基係可使用直鏈或分支鏈,惟直鏈較佳。再者,有機鎓具有環狀構造時,鎓 宜具有5環或6環,其他的置換基宜為碳數1~4之烷基。 Further, examples of the organic group in the organic oxime include an alkyl group, an alkoxy group, and an alkenyl group. Among them, it is preferable that the point at which the deterioration of the photon is suppressed is not to have an unsaturated bond. The carbon number of the alkyl group may be selected from 1 to 12, preferably from 1 to 8, more preferably from 1 to 4. As the organic hydrazine, all of the substituents are preferably an alkane having an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a straight chain or a branched chain, but a straight chain is preferred. Furthermore, when the organic enamel has a ring structure, 鎓 It is preferred to have 5 rings or 6 rings, and the other substituents are preferably alkyl groups having 1 to 4 carbon atoms.
作為前述鎓,並無特別限制,可例舉如含氮鎓、含硫鎓、含磷鎓等。其等之中以含氮鎓、含硫鎓為宜。 The hydrazine is not particularly limited, and examples thereof include a hydrazine-containing hydrazine, a hydrazine-containing hydrazine, and a phosphorus-containing hydrazine. Among them, nitrogen-containing ruthenium and bismuth-containing ruthenium are preferred.
作為含氮鎓,可例舉銨陽離子、哌啶陽離子、吡咯烷陽離子、吡陽離子、具吡咯啉骨架之陽離子、具吡咯骨架之陽離子、咪唑鹽陽離子、四氫嘧啶陽離子、二氫嘧啶陽離子、吡唑陽離子、二氫化吡唑等。其等之中由抑制偏光子劣化之點,宜為銨陽離子、哌啶陽離子、吡咯烷陽離子。特別是以四烷基銨陽離子、烷基哌啶陽離子、烷基吡咯烷陽離子為宜。 As the nitrogen-containing ruthenium, an ammonium cation, a piperidine cation, a pyrrolidine cation, and a pyridyl group are exemplified. a cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium salt cation, a tetrahydropyrimidine cation, a dihydropyrimidine cation, a pyrazole cation, a dihydropyrazole or the like. Among them, the point of suppressing deterioration of the polarizer is preferably an ammonium cation, a piperidine cation or a pyrrolidine cation. In particular, a tetraalkylammonium cation, an alkylpiperidine cation or an alkylpyrrolidine cation is preferred.
作為含硫翁,可例舉鋶陽離子等。又,作為含磷鎓,可例舉鏻陽離子。 As the sulfur-containing article, a phosphonium cation or the like can be exemplified. Further, as the phosphorus-containing ruthenium, a phosphonium cation is exemplified.
鎓-含氟醯亞胺陰離子鹽之具體例,係可適宜地選擇使用前述鎓成分與含氟醯亞胺陰離子成分之組合而成之化合物,且可合宜地使用選自含氮鎓鹽、含硫鎓鹽及含磷鎓鹽中之至少一者。進而,可適宜地使用選自銨鹽、吡咯烷鹽、哌啶鹽及鋶鹽中之至少一者。 Specific examples of the cerium-fluorinated quinone imine anion salt can be suitably selected from the group consisting of a combination of the above cerium component and a fluorinated quinone imine anion component, and can be suitably selected from a nitrogen-containing cerium salt, At least one of a sulfonium salt and a phosphorus-containing phosphonium salt. Further, at least one selected from the group consisting of an ammonium salt, a pyrrolidine salt, a piperidine salt, and a phosphonium salt can be suitably used.
可例舉如1-丁基-3-甲基吡雙(三氟甲基磺醯)醯亞胺、1-丁基-3-甲基吡雙(五氟乙烷磺醯)醯亞胺、1-乙基-3-甲基咪唑雙(三氟甲基磺醯)醯亞胺、1-乙基-3-甲基咪唑雙(五氟乙烷磺醯)醯亞胺、1-丁基-3-甲基咪唑雙(三氟甲基磺醯)醯亞胺、1,2-二甲基-3-丙基咪唑雙(三氟甲基磺醯)醯亞胺、四己基銨雙(三氟甲基磺醯)醯亞胺、二烯丙基二甲基銨雙(三氟甲基磺醯)醯亞胺二烯丙基二甲基銨雙(五 氟乙烷磺醯)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(三氟甲基磺醯)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(五氟乙烷磺醯)醯亞胺、縮水甘油基三甲基銨雙(三氟甲基磺醯)醯亞胺、縮水甘油基三甲基銨雙(五氟乙烷磺醯)醯亞胺、N,N-二甲基-N-乙基-N-丙基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-乙基-N-丁基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-乙基-N-戊基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-乙基-N-己基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-乙基-N-庚基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-乙基-N-壬基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N,N-雙丙基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-丙基-N-丁基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-丙基-N-戊基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-丙基-N-己基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-丙基-N-庚基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-丁基-N-己基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-丁基-N-庚基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N-戊基-N-己基銨雙(三氟甲基磺醯)醯亞胺、N,N-二甲基-N,N-十二烷銨雙(三氟甲基磺醯)醯亞胺、三甲基庚基銨雙(三氟甲基磺醯)醯亞胺、N,N-二乙基-N-甲基-N-丙基銨雙(三氟甲基磺醯)醯亞胺、N,N-二乙基-N-甲基-N-戊基銨雙(三氟甲基磺醯)醯亞胺、N,N-二乙基-N-甲基-N-庚基銨雙(三氟甲基磺醯)醯亞胺、N,N-二乙基-N-丙基-N-戊基銨雙(三氟甲基磺醯)醯亞胺、三乙基丙基銨雙(三氟 甲基磺醯)醯亞胺、三乙基戊基銨雙(三氟甲基磺醯)醯亞胺、三乙基庚基銨雙(三氟甲基磺醯)醯亞胺、N,N-雙丙基-N-甲基-N-乙基銨雙(三氟甲基磺醯)醯亞胺、N,N-雙丙基-N-甲基-N-戊基銨雙(三氟甲基磺醯)醯亞胺、N,N-雙丙基-N-丁基-N-己基銨雙(三氟甲基磺醯)醯亞胺、N,N-雙丙基-N,N-十二烷銨雙(三氟甲基磺醯)醯亞胺、N,N-二丁基-N-甲基-N-戊基銨雙(三氟甲基磺醯)醯亞胺、N,N-二丁基-N-甲基-N-己基銨雙(三氟甲基磺醯)醯亞胺、三辛基甲基銨雙(三氟甲基磺醯)醯亞胺、N-甲基-N-乙基-N-丙基-N-戊基銨雙(三氟甲基磺醯)醯亞胺等。其等之市售品係可使用譬如「CIL-314」(Japan Carlit Co.,Ltd.製)、「ILA2-1」(KOEI CHEMICAL COMPANY,LIMITED製)等。 1-butyl-3-methylpyridyl Bis(trifluoromethylsulfonyl) quinone imine, 1-butyl-3-methylpyridyl Bis(pentafluoroethanesulfonate) quinone imine, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-3-methylimidazolium bis(pentafluoro Ethyl sulfonium) quinone imine, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) quinone imine, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethyl) Sulfhydrazinium sulfonium imide, tetrahexylammonium bis(trifluoromethylsulfonyl) quinone imine, diallyldimethylammonium bis(trifluoromethylsulfonate) quinone imine diallyl Alkyl ammonium bis(pentafluoroethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonate) hydrazine Imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonate) quinone imine, glycidyl trimethylammonium bis ( Trifluoromethanesulfonyl) fluorene imine, glycidyl trimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-propyl ammonium double (trifluoromethylsulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl -N-ethyl-N-amyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-hexylammonium bis(trifluoromethylsulfonate) Yttrium, N, N-Dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-decyl ammonium double (three Fluoromethylsulfonyl) quinone imine, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl-N-propyl --N-butylammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethylsulfonate) quinone imine , N,N-Dimethyl-N-propyl-N-hexyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-heptyl ammonium double (trifluoromethylsulfonium) quinone imine, N,N-dimethyl-N-butyl-N-hexyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl- N-butyl-N-heptyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethylsulfonate) hydrazine Imine, N,N-dimethyl-N,N-dodecylammonium bis(trifluoromethylsulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethylsulfonate) quinone imine ,N,N-Diethyl-N-methyl-N-propylammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-diethyl-N-methyl-N-amyl ammonium Bis(trifluoromethylsulfonyl) quinone imine, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethylsulfonate) hydrazine Imine, N,N-diethyl-N-propyl-N-pentyl ammonium bis(trifluoromethylsulfonyl) quinone imine, triethyl propyl ammonium bis(trifluoromethylsulfonate) hydrazine Imine, triethylammonium bis(trifluoromethylsulfonyl) quinone imine, triethylheptyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dipropyl-N -Methyl-N-ethylammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-bispropyl-N-methyl-N-pentyl ammonium bis(trifluoromethylsulfonate) hydrazine Imine, N,N-dipropyl-N-butyl-N-hexyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dipropyl-N,N-dodecane ammonium double (Trifluoromethanesulfonyl) quinone imine, N,N-dibutyl-N-methyl-N-pentyl ammonium bis(trifluoromethylsulfonyl) quinone imine, N,N-dibutyl -N-methyl-N-hexyl ammonium bis(trifluoromethylsulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethylsulfonate) quinone imine, N-methyl-N-B Base-N-propyl-N-pentyl ammonium bis(trifluoromethylsulfonate) quinone imine or the like. For the commercial products, such as "CIL-314" (manufactured by Japan Carlit Co., Ltd.), "ILA2-1" (manufactured by KOEI CHEMICAL COMPANY, LIMITED), or the like can be used.
又,譬如可例舉四甲基銨雙(三氟甲基磺醯)醯亞胺、三甲基乙基銨雙(三氟甲基磺醯)醯亞胺、三甲基丁基銨雙(三氟甲基磺醯)醯亞胺、三甲基戊基銨雙(三氟甲基磺醯)醯亞胺、三甲基庚基銨雙(三氟甲基磺醯)醯亞胺、三甲基辛基銨雙(三氟甲基磺醯)醯亞胺、四乙基銨雙(三氟甲基磺醯)醯亞胺、三乙基丁基銨雙(三氟甲基磺醯)醯亞胺、四丁基銨雙(三氟甲基磺醯)醯亞胺、四己基銨雙(三氟甲基磺醯)醯亞胺等。 Further, for example, tetramethylammonium bis(trifluoromethylsulfonate) quinone imine, trimethylethylammonium bis(trifluoromethylsulfonate) quinone imine, and trimethylbutylammonium bis ( Trifluoromethylsulfonium) quinone imine, trimethylammonium bis(trifluoromethylsulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethylsulfonate) quinone imine, three Methyloctyl ammonium bis(trifluoromethylsulfonyl) quinone imine, tetraethylammonium bis(trifluoromethylsulfonyl) quinone imine, triethyl butyl ammonium bis(trifluoromethylsulfonate) Yttrium imine, tetrabutylammonium bis(trifluoromethylsulfonyl) quinone imine, tetrahexylammonium bis(trifluoromethylsulfonyl) quinone imine, and the like.
再者,可例舉如1-二甲基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1- 戊基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-戊基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1,1-雙丙基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-丙基-1-丁基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1,1-二丁基吡咯烷鎓雙(三氟甲基磺醯)醯亞胺、1-丙基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-戊基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1,1-二甲基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-乙基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-丙基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-丁基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-戊基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-己基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-甲基-1-庚基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-丙基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-丁基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-戊基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-己基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-乙基-1-庚基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1,1-雙丙基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1-丙基-1-丁基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1,1-二丁基哌啶鎓雙(三氟甲基磺醯)醯亞胺、1,1-二甲基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙 (五氟乙烷磺醯)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-戊基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-戊基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1,1-雙丙基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-丙基-1-丁基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1,1-二丁基吡咯烷鎓雙(五氟乙烷磺醯)醯亞胺、1-丙基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-戊基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1,1-二甲基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-乙基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-丙基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-丁基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-戊基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-己基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-甲基-1-庚基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-丙基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-庚基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-戊基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-己基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-乙基-1-庚基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1-丙基-1-丁基哌啶鎓雙(五氟乙烷磺醯)醯亞胺、1,1-雙丙基哌啶鎓雙(五氟乙烷磺醯) 醯亞胺、1,1-二丁基哌啶鎓雙(五氟乙烷磺醯)醯亞胺等。 Further, for example, 1-dimethylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethylsulfonate) hydrazine can be exemplified. Imine, 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethylsulfonate) hydrazine Imine, 1-methyl-1- Amylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-glycol Pyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-butene Pyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-hexyl Pyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1,1-dipropylpyrrolidine Bis(trifluoromethylsulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethylsulfonyl) quinone imine, 1,1-dibutylpyrrolidinium double (trifluoromethylsulfonyl) quinone imine, 1-propylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-pentylpiperidinium bis(trifluoromethylsulfonate) Amine, 1,1-dimethylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis ( Fluoromethylsulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis (trifluoro Methylsulfonium) quinone imine, 1-methyl-1-heptylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis (trifluoro Methylsulfonium) quinone imine, 1-ethyl-1-butylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis (trifluoro Methylsulfonium sulfonium imide, 1-ethyl-1-hexylpiperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis (trifluoromethyl) Sulfonamide, quinone imine, 1,1-dipropyl piperidinium bis(trifluoromethylsulfonyl) quinone imine, 1-propyl-1-butylpiperidinium bis(trifluoromethylsulfonate醯) quinone imine, 1,1-dibutyl piperidinium bis(trifluoromethylsulfonyl) quinone imine, 1,1-dimethylpyrrolidinium bis(pentafluoroethane sulfonate) Amine, 1-methyl-1-ethylpyrrolidinium double (pentafluoroethanesulfonate) quinone imine, 1-methyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonate) quinone imine, 1-methyl-1-butylpyrrolidinium double (pentafluoroethane sulfonium) quinone imine, 1-methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis ( Pentafluoroethane sulfonate) quinone imine, 1-methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis ( Pentafluoroethane sulfonate) quinone imine, 1-ethyl-1-butylpyrrolidinium bis(pentafluoroethane sulfonate) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis ( Pentafluoroethane sulfonate) quinone imine, 1-ethyl-1-hexyl pyrrolidinium bis(pentafluoroethane sulfonate) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis (five Fluoroethane sulfonate) quinone imine, 1,1-bispropylpyrrolidinium bis(pentafluoroethane sulfonate) quinone imine, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethylene) Alkylsulfonium sulfonium imide, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonate) quinone imine, 1-propylpiperidinium bis(pentafluoroethanesulfonate) quinone imine , 1-pentylpiperidinium bis(pentafluoroethanesulfonate) quinone imine, 1,1-dimethylpiperidinium bis(pentafluoroethane醯)imine, 1-methyl-1-ethylpiperidinium bis(pentafluoroethanesulfonate) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethane sulfonate醯) quinone imine, 1-methyl-1-butylpiperidinium bis(pentafluoroethane sulfonate) quinone imine, 1-methyl-1-pentylpiperidinium bis(pentafluoroethane sulfonate醯)imine, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonate)醯imino, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethane sulfonate)醯imino, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(pentafluoroethane sulfonate) Yttrium, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonate) Yttrium imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonate) Yttrium imine, 1,1-dibutyl piperidinium bis(pentafluoroethanesulfonate) quinone imine, and the like.
又,取代前述化合物之鎓成分,係可例舉使用三甲基硫鎓陽離子、三乙基硫鎓陽離子、三丁基硫鎓陽離子、三己基硫鎓陽離子、二乙基甲基硫鎓陽離子、二丁基乙基硫鎓陽離子、二甲基癸基硫鎓陽離子、四甲基鏻陽離子、四乙基鏻陽離子、四丁基鏻陽離子、四己基鏻陽離子等之化合物等。 Further, in place of the ruthenium component of the above compound, a trimethylsulfonium cation, a triethylsulfonium cation, a tributylsulfonium cation, a trihexylsulfonium cation, a diethylmethylsulfonium cation, or a diethylmethylsulfonium cation may be used. A compound such as dibutylethylsulfonium cation, dimethylmercaptosulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation or tetrahexylphosphonium cation.
又,取代前述之雙(三氟甲基磺醯)醯亞胺,係可例舉使用雙(五氟乙烷磺醯)醯亞胺、雙(七氟丙基磺醯)醯亞胺、雙(九氟丁基磺醯)醯亞胺、三氟甲磺醯九氟丁基磺醯醯亞胺、七氟丙基磺醯三氟甲磺醯醯亞胺、五氟乙基磺醯九氟丁基磺醯醯亞胺、環六氟丙基-1,3-雙(磺醯)醯亞胺陰離子等之化合物等。 Further, in place of the above-mentioned bis(trifluoromethylsulfonyl) quinone imine, bis(pentafluoroethanesulfonyl) quinone imine, bis(heptafluoropropylsulfonyl) quinone imine, and double may be used. (nonafluorobutylsulfonium) quinone imine, trifluoromethanesulfonate, nonafluorobutylsulfonimide, heptafluoropropylsulfonium trifluoromethanesulfonimide, pentafluoroethylsulfonate A compound such as butyl sulfoximine, cyclohexafluoropropyl-1,3-bis(sulfonate) quinone imine or the like.
本發明之黏著劑組成物中之鎓-含氟醯亞胺陰離子鹽(B)之比例,係相對於(甲基)丙烯醯系聚合物(A)100重量份,宜為0.1~10重量份。前述鎓-含氟醯亞胺陰離子鹽(B)不滿0.1重量份,會有抗靜電功能提高效果不足之情況。前述鎓-含氟醯亞胺陰離子鹽(B)宜為0.2重量份以上,進而0.5重量份以上為佳。另一方面,前述鎓-含氟醯亞胺陰離子鹽(B)若超過10重量份,會有耐久性變得不充分之情況。前述鎓-含氟醯亞胺陰離子鹽(B)宜為5重量份以下,3重量份以下較佳,進而2重量份以下為佳。前述鎓-含氟醯亞胺陰離子鹽(B)之比例,係可採用前述上限值或下限值而設定合宜之範圍。 The ratio of the cerium-fluorinated quinone anion salt (B) in the adhesive composition of the present invention is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylonitrile-based polymer (A). . When the cerium-fluorinated quinone imine anion salt (B) is less than 0.1 part by weight, the effect of improving the antistatic function may be insufficient. The cerium-fluorinated quinone imine anion salt (B) is preferably 0.2 parts by weight or more, more preferably 0.5 parts by weight or more. On the other hand, when the cerium-fluorinated quinone imine anion salt (B) exceeds 10 parts by weight, the durability may be insufficient. The cerium-fluorinated quinone imine anion salt (B) is preferably 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less. The ratio of the above-mentioned fluorene-fluorene quinone anion salt (B) can be set to a suitable range by using the above upper limit value or lower limit value.
進而,本發明之黏著劑組成物可含有交聯劑(C)。交聯劑(C)可使用有機系交聯劑或多官能性金屬螯合物。有機系交聯劑可舉例如異氰酸系交聯劑、過氧化物系交聯劑、環氧系交聯劑、亞胺系交聯劑等。多官能性金屬螯合物係多價金屬與有機化合物共價鍵結或配位鍵結者。多價金屬原子可例舉Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。共價鍵結或配位鍵結之有機化合物中之原子,係可舉出氧原子等,有機化合物可舉出烷基酯、醇化合物、羧氧化合物、醚化合物、銅化合物等。 Further, the adhesive composition of the present invention may contain a crosslinking agent (C). As the crosslinking agent (C), an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imide crosslinking agent. Polyfunctional metal chelates are those in which a polyvalent metal is covalently bonded or coordinated to an organic compound. The polyvalent metal atom may, for example, be Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn or Ti. The atom in the organic compound of the covalent bond or the coordinate bond may be an oxygen atom or the like, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxyl compound, an ether compound, and a copper compound.
交聯劑(C)宜為異氰酸系交聯劑及/或過氧化物系交聯劑。異氰酸系交聯劑之化合物係可例舉如二異氰酸甲苯酯、氯伸苯基二異氰酸酯、四亞甲基二異氰酸酯、伸苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯等之異氰酸酯單體,以及將該等異氰酸酯單體與三羥甲基丙烷等行加成反應而成之化合物或異氰尿酸酯化物、滴定管型化合物,進而,添加聚醚多元醇或聚酯多元醇、丙烯酸多元醇、聚丁二烯、聚異戊二烯多元醇等並加以反應之聚氨酯預聚物型之異氰酸酯等。特別理想者係聚異氰酸酯化合物,且選自由六亞甲基二異氰酸酯、氫化伸苯二甲基二異氰酸酯及異佛酮二異氰酸酯組成之群中之一者或由其而來之聚異氰酸酯化合物。此處,選自由六亞甲基二異氰酸酯、氫化伸苯二甲基二異氰酸酯及異佛酮二異氰酸酯組成之群中之一者或由其而來之聚異氰 酸酯化合物中,係含有六亞甲基二異氰酸酯、氫化伸苯二甲基二異氰酸酯、異佛酮二異氰酸酯、多元醇改質六亞甲基二異氰酸酯、多元醇改質氫化伸苯二甲基二異氰酸酯、三聚物型氫化伸苯二甲基二異氰酸酯及多元醇改質異佛酮二異氰酸酯等。所例示之聚異氰酸酯化合物,由於其與羥基之反應速度,特別是如將聚合物所含之酸、鹽作為觸媒般,而可迅速地進行,故,對於交聯之速度進行特別有幫助,而為理想者。 The crosslinking agent (C) is preferably an isocyanate crosslinking agent and/or a peroxide crosslinking agent. Examples of the isocyanate crosslinking agent compound include toluene diisocyanate, chlorophenyl diisocyanate, tetramethylene diisocyanate, benzoyl diisocyanate, and diphenylmethane diisocyanate. An isocyanate monomer such as hydrogenated diphenylmethane diisocyanate, or a compound obtained by addition reaction of the isocyanate monomer and trimethylolpropane, or an isocyanurate compound or a burette type compound, and further added A polyurethane prepolymer type isocyanate or the like which is reacted with a polyether polyol or a polyester polyol, an acrylic polyol, a polybutadiene, a polyisoprene polyol, or the like. Particularly preferred is a polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated terephthalic diisocyanate, and isophorone diisocyanate or a polyisocyanate compound derived therefrom. Here, one selected from the group consisting of hexamethylene diisocyanate, hydrogenated terephthalic diisocyanate, and isophorone diisocyanate or polyisocyanate therefrom The ester compound contains hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol modified hexamethylene diisocyanate, polyol modified hydrogenated benzene dimethyl Diisocyanate, terpolymer type hydrogenated xylylene diisocyanate, and polyol modified isophorone diisocyanate. The polyisocyanate compound exemplified is particularly effective in the rate of crosslinking because of its reaction rate with a hydroxyl group, particularly, such as by using an acid or a salt contained in the polymer as a catalyst. And ideal.
作為過氧化物,只要是可藉由加熱或光照射而產生自由基活性種,讓黏著劑組成物之基底聚合物之交聯進行者,即可適宜地加以使用,惟考量作業性及穩定性,宜使用1分鐘半衰期溫度為80℃~160℃之過氧化物,使用90℃~140℃之過氧化物更佳。 As the peroxide, if a radical active species can be generated by heating or light irradiation, and the base polymer of the adhesive composition is crosslinked, it can be suitably used, but the workability and stability are considered. It is preferred to use a peroxide having a half-life temperature of 80 ° C to 160 ° C for 1 minute, and a peroxide of 90 ° C to 140 ° C is preferred.
可使用之過氧化物,譬如可舉出二(2-乙基己酯)過氧化二碳酸酯(1分鐘半衰期溫度:90.6℃)、二(4-t-丁基環己基)過氧化二碳酸酯(1分鐘半衰期溫度:92.1℃)、二-sec-丁基過氧化二碳酸酯(1分鐘半衰期溫度:92.4℃)、t-丁基過氧化新癸酸酯(1分鐘半衰期溫度:103.5℃)、t-己基過氧化新戊酸酯(1分鐘半衰期溫度:109.1℃)、t-丁基過氧化新戊酸酯(1分鐘半衰期溫度:110.3℃)、二月桂醯過氧化物(1分鐘半衰期溫度:116.4℃)、二-n-辛醯過氧化物(1分鐘半衰期溫度:117.4℃)、1,1,3,3-四甲基丁基過氧化物-2-乙酸乙酯酯(1分鐘半衰期溫度:124.3℃)、二(4-甲基苯甲醯)過氧化物(1分鐘半衰期溫度:128.2℃)、二苯甲醯過氧化物 (1分鐘半衰期溫度:130.0℃)、t-丁基過氧化異丁酸酯(1分鐘半衰期溫度:136.1℃)、1,1-二(t-己基過氧化)環己烷(1分鐘半衰期溫度:149.2℃)等。其中,特別是由交聯反應效率優異之點,宜使用二(4-t-丁基環己基)過氧化二碳酸酯(1分鐘半衰期溫度:92.1℃)、二月桂醯過氧化物(1分鐘半衰期溫度:116.4℃)、二苯甲醯過氧化物(1分鐘半衰期溫度130.0℃)等。 A peroxide which can be used, for example, bis(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), bis(4-t-butylcyclohexyl)peroxydicarbonate Ester (1 minute half-life temperature: 92.1 ° C), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C), t-butyl peroxy neodecanoate (1 minute half-life temperature: 103.5 ° C ), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C), dilaurin peroxide (1 minute) Half-life temperature: 116.4 ° C), di-n-octyl peroxide (1 minute half-life temperature: 117.4 ° C), 1,1,3,3-tetramethylbutyl peroxide-2-ethyl acetate ( 1 minute half-life temperature: 124.3 ° C), bis(4-methylbenzhydrazide) peroxide (1 minute half-life temperature: 128.2 ° C), benzotrifluoride peroxide (1 minute half-life temperature: 130.0 ° C), t-butyl peroxyisobutyrate (1 minute half-life temperature: 136.1 ° C), 1,1-di (t-hexyl peroxy) cyclohexane (1 minute half-life temperature) : 149.2 ° C) and so on. Among them, in particular, it is preferable to use bis(4-t-butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1 ° C) and dilaurin peroxide (1 minute) from the viewpoint of excellent crosslinking reaction efficiency. Half-life temperature: 116.4 ° C), benzotrione peroxide (1 minute half-life temperature 130.0 ° C) and the like.
又,過氧化物之半衰期,係表示過氧化物之分解速度的指標,意指迄至過氧化物之殘存量低至一半之時間。有關於為在任意時間下達到半衰期之分解溫度,或在任意溫度下之半衰期時間,係記載於廠商型錄等,譬如記載於日本油脂株式會社(NOF CORPORATION.)之「有機過氧化物型錄第9版(2003年5月)」等。 Further, the half-life of the peroxide is an index indicating the decomposition rate of the peroxide, and means the time until the residual amount of the peroxide is as low as half. The decomposition temperature for achieving the half-life at any time, or the half-life time at any temperature, is described in the manufacturer's catalogue, etc., for example, in the "Organic peroxide catalogue" reported by NOF CORPORATION. The 9th edition (May 2003) and so on.
交聯劑(C)之使用量,相對於(甲基)丙烯醯系聚合物(A)100重量份,宜為0.01~20重量份,進而,0.03~10重量份為佳。又,若交聯劑(C)低於0.01重量份,會有黏著劑之凝集力不足的傾向,加熱時恐有發泡產生之虞,另一方面,超過20重量份時,耐溼性並不充分,於可靠度試驗等易產生剝離情況。 The amount of the crosslinking agent (C) to be used is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, per 100 parts by weight of the (meth)acrylonitrile-based polymer (A). In addition, when the crosslinking agent (C) is less than 0.01 part by weight, the cohesive force of the adhesive tends to be insufficient, and there is a fear that foaming occurs during heating. On the other hand, when it exceeds 20 parts by weight, the moisture resistance is high. Insufficient, it is easy to cause peeling in reliability test.
前述異氰酸酯系交聯劑係可單獨1種使用,亦可混合2種以上使用,惟全體之含量,相對於前述(甲基)丙烯醯係聚合物(A)100重量份,含有前述聚異氰酸酯化合物交聯劑0.01~2重量份而成者為佳,含有0.02~2重量份而成者更佳,含有0.05~1.5重量份而成者尤佳。亦可考量預防凝集 力、耐久性試驗之剝離情況而適宜地含有。 The isocyanate-based crosslinking agent may be used alone or in combination of two or more kinds thereof, and the polyisocyanate compound may be contained in an amount of 100 parts by weight based on 100 parts by weight of the (meth)acryl fluorene-based polymer (A). The crosslinking agent is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and more preferably 0.05 to 1.5 parts by weight. Can also consider prevention of agglutination It is suitably contained in the peeling of the force and durability test.
前述過氧化物可單獨1種使用,亦可混合2種以上使用,惟全體之含量,相對於前述(甲基)丙烯醯係聚合物(A)100重量份,前述過氧化物為0.01~2重量份,含有0.04~1.5重量份而成者為宜,含有0.05~1重量份而成者更佳。為調整加工性、重工性、交聯穩定性、剝離性等,可於此範圍內適宜地選擇。 The peroxide may be used singly or in combination of two or more kinds, and the total amount of the peroxide is 0.01 to 2 based on 100 parts by weight of the (meth) acrylonitrile-based polymer (A). The weight fraction is preferably from 0.04 to 1.5 parts by weight, more preferably from 0.05 to 1 part by weight. In order to adjust workability, reworkability, crosslinking stability, peelability, and the like, it can be suitably selected within this range.
又,作為反應處理後殘存之過氧化物分解量之測量方法,係譬如可藉由HPLC(高速液體層析法)加以測量。 Further, the method for measuring the amount of decomposition of the peroxide remaining after the reaction treatment can be measured by, for example, HPLC (High Speed Liquid Chromatography).
更具體地,譬如可將反應處理後之黏著劑組成物以每份約0.2g取出,浸漬於醋酸乙酯10ml,並以振盪機於25℃下以120rpm振盪3小時後,取出於室溫靜置三天。其次,加入10ml乙腈,於25℃下以120rpm振盪30分鐘,以膜過濾機(0.45μm)過濾,將所得之取出液10μl注入HPLC進行分析,作為反應處理後之過氧化物量。 More specifically, for example, the adhesive composition after the reaction treatment may be taken out in an amount of about 0.2 g per part, immersed in 10 ml of ethyl acetate, and shaken at 120 ° C for 3 hours at 25 ° C with an oscillating machine, and then taken out at room temperature. Set for three days. Next, 10 ml of acetonitrile was added, and the mixture was shaken at 120 rpm for 30 minutes at 25 ° C, filtered through a membrane filter (0.45 μm), and 10 μl of the obtained extract was poured into HPLC for analysis as the amount of peroxide after the reaction treatment.
再者,本發明之黏著劑組成物中可含有矽烷偶合劑(D)。藉由使用矽烷偶合劑(D),可提高耐久性。矽烷偶合劑具體上係可舉出譬如3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油醚丙基三乙氧基矽烷、3-縮水甘油醚氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己烷基)乙基三甲氧基矽烷等之含環氧基矽烷偶合劑;3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基亞丁基)丙基胺、N-苯基-γ-胺基丙基三甲氧基矽烷等之含胺基矽烷偶合劑;3-丙烯醯氧丙 基三甲氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等之含(甲基)丙烯醯基矽烷偶合劑;3-異氰酸酯丙基三乙氧基矽烷等之含異氰酸酯基之矽烷偶合劑等。 Further, the adhesive composition of the present invention may contain a decane coupling agent (D). Durability can be improved by using a decane coupling agent (D). The decane coupling agent may specifically be exemplified by, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidyloxypropyltriethoxydecane, 3-glycidyloxypropylmethyldiethoxylate. Epoxy-containing decane coupling agent such as decane, 2-(3,4-epoxycyclohexane)ethyltrimethoxydecane; 3-aminopropyltrimethoxydecane, N-2-(amine Benzyl)-3-aminopropylmethyldimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl- An amine-containing decane coupling agent such as γ-aminopropyltrimethoxydecane; 3-propene oxime (meth)acrylonitrile-based decane coupling agent such as trimethoxy decane, 3-methyl propylene oxypropyl triethoxy decane, etc.; isocyanate group-containing according to 3-isocyanate propyl triethoxy decane A decane coupling agent or the like.
前述矽烷偶合劑(D)係可單獨使用,亦可混合2種類以上使用,惟全體之含量相對於前述(甲基)丙烯醯系聚合物(A)100重量份,前述矽烷偶合劑宜為0.001~5重量份,0.01~1重量份較佳,進而0.02~1重量份更佳,而0.05~0.6重量份尤佳。其係可提高耐久性,適度的保持對於液晶晶胞等光學構件之接著力量。 The decane coupling agent (D) may be used singly or in combination of two or more kinds, and the total amount of the decane coupling agent is preferably 0.001 based on 100 parts by weight of the (meth) acrylonitrile-based polymer (A). ~5 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.02 to 1 part by weight, more preferably 0.05 to 0.6 part by weight. It can improve durability and moderately maintain the bonding force to optical members such as liquid crystal cells.
進而,可於本發明之黏著劑組成物摻雜聚醚改質矽氧烷化合物。聚醚改質矽氧烷化合物係可使用譬如日本特開2010-275522號公報所揭示者。 Further, the polyether modified siloxane compound can be doped with the adhesive composition of the present invention. The polyether modified siloxane compound can be used, for example, as disclosed in JP-A-2010-275522.
聚醚改質矽氧烷化合物係具有聚醚骨架,且至少於一個末端具有以下述一般式(1):-SiRaM3-a The polyether modified siloxane compound has a polyether skeleton and has at least one terminal having the following general formula (1): -SiR a M 3-a
(式中,R為可具有取代基之碳數1~20之1價有機基,M為羥基或水解性基,a為0~2之整數。惟R為複數存在時,複數個R可為彼此相同或相異,M為複數存在時,複數個M可為相彼此同或相異)表示之反應性矽烷基。 (wherein R is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2. When R is a plural, a plurality of R may be Reactive decyl groups which are the same or different from each other, and M is a plural number, and a plurality of M may be the same or different from each other.
前述聚醚改質矽氧烷化合物係可舉出以一般式(2):RaM3-aSi-X-Y-(AO)n-Z The polyether modified siloxane compound is exemplified by the general formula (2): R a M 3-a Si-XY-(AO) n -Z
(式中,R為可具有取代基之碳數1~20之1價有機基,M為羥基或水解性基,a為0~2之整數。惟R為複數存在時,複數個R可為彼此相同或相異,M為複數存在時,複數個M可為彼此相同或相異。AO為表示直鏈或分支鏈之碳數1~10之 氧基伸烷基,n為1~1700,表示氧基伸烷基之平均添加莫耳數。X為表示碳數1~20之直鏈或分支鏈之伸烷基。Y為表示醚鍵、酯鍵、胺基甲酸酯鍵或碳酸酯鍵。) (wherein R is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2. When R is a plural, a plurality of R may be When they are the same or different from each other, when M is a complex number, the plurality of Ms may be the same or different from each other. AO is a carbon number of 1 to 10 representing a straight chain or a branched chain. The alkyloxy group, n is from 1 to 1700, and represents the average number of moles added to the alkyloxy group. X is an alkyl group which represents a linear or branched chain having 1 to 20 carbon atoms. Y represents an ether bond, an ester bond, a urethane bond or a carbonate bond. )
Z為氫原子、1價之碳數1~10之烴基;一般式(2A):-Y1-X-SiRaM3-a Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms; general formula (2A): -Y 1 -X-SiR a M 3-a
(式中,R、M、X係與前述相同。Y1為表示單鍵結、-CO-鍵、-CONH-鍵或-COO-鍵),或一般式(2B):-Q{-(OA)n-Y-X-SiRaM3-a}m (wherein R, M, and X are the same as described above. Y 1 represents a single bond, -CO- bond, -CONH- bond or -COO- bond), or general formula (2B): -Q{-( OA) n -YX-SiR a M 3-a } m
(式中,R、M、X、Y係與前述相同。OA與前述之AO相同,n與前述相同。Q為2價以上之碳數1~10之烴基,m與該烴基之價數相同)所表示之基)所示之化合物。 (In the formula, R, M, X, and Y are the same as described above. OA is the same as AO described above, and n is the same as above. Q is a hydrocarbon group having a carbon number of 1 to 10 or more, and m is the same as the number of the hydrocarbon group. The compound shown by the base).
聚醚改質矽氧烷化合物之具體例係可例舉如日本社(KANEKA CORPORATION)製之MS聚合物S203、S303、S810;SILYL EST250、EST280;SAT10、SAT200、SAT220、SAT350、SAT400,日本旭硝子社(ASASHI GLASS CO.,LTD.)製之EXCESTAR S2410、S2420或S3430等。 Specific examples of the polyether modified siloxane compound can be exemplified by Japan. MS polymer S203, S303, S810, SILYL EST250, EST280, SAT10, SAT200, SAT220, SAT350, SAT400, manufactured by KANEKA CORPORATION, EXCESTAR S2410, S2420, manufactured by ASASHI GLASS CO., LTD. S3430 and so on.
進而,本發明之黏著劑組成物中亦可含有其他已知之添加劑,譬如可依使用聚丙烯乙二醇等之聚烯烴乙二醇的聚醚化合物、著色劑、顏料等之粉體、染料、界面活性劑、可塑劑、黏著性賦予劑、表面潤滑劑、流平劑、軟化劑、抗氧化劑、抗老化劑、光安定劑、紫外線吸收劑、聚合禁止劑、無機或有機之充填劑、金屬粉、粒子狀、箔狀物等之用途而適宜地添加。又,亦於可抑制之範圍內, 採用添加還原劑之氧化還原系者。 Further, the adhesive composition of the present invention may contain other known additives, such as a polyether compound of a polyolefin glycol such as polypropylene glycol, a powder, a dye, or the like, a dye, or the like. Surfactant, plasticizer, adhesion imparting agent, surface lubricant, leveling agent, softener, antioxidant, anti-aging agent, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic or organic filler, metal It is suitably added for the use of a powder, a particulate form, a foil, etc. Also, within the range that can be suppressed, A redox system using a reducing agent is used.
藉由前述黏著劑組成物而形成黏著劑層,但黏著劑層形成時,宜調整交聯劑整體之添加量,並且充分考量交聯處理溫度及交聯處理時間之影響。 The adhesive layer is formed by the above-mentioned adhesive composition. However, when the adhesive layer is formed, it is preferable to adjust the addition amount of the entire crosslinking agent, and to sufficiently consider the influence of the crosslinking treatment temperature and the crosslinking treatment time.
藉由使用之交聯劑,交聯處理溫度及交聯處理時間係可加以調整。交聯處理溫度宜為170℃以下。 The crosslinking treatment temperature and the crosslinking treatment time can be adjusted by using the crosslinking agent. The crosslinking treatment temperature is preferably 170 ° C or less.
又,此種交聯處理係可以黏著劑層乾燥程序時之溫度進行,亦可於乾燥程序後另外進行交聯處理程序。 Further, such a crosslinking treatment may be carried out at a temperature at which the adhesive layer is dried, or may be additionally subjected to a crosslinking treatment procedure after the drying procedure.
又,有關交聯處理時間,係可考慮生產性及作業性而加以設定,惟通常約0.2~20分鐘,約0.5~10分鐘為宜。 Further, the cross-linking treatment time can be set in consideration of productivity and workability, but it is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.
本發明之附黏著劑層之偏光薄膜,係僅於偏光子之單側是這透明保護薄膜,另一側並不設置透明保護薄膜,藉由前述黏著劑組成物而將黏著劑層形成於偏光子。 The polarizing film with an adhesive layer of the present invention is a transparent protective film on only one side of the polarizer, and no transparent protective film is provided on the other side, and the adhesive layer is formed on the polarized light by the adhesive composition. child.
形成黏著劑層之方法,係譬如可藉由以下之方法加以製作,即,將前述黏著劑組成物塗布於經剝離處理之離型材等,乾燥去除聚合溶劑等而形成黏著劑層後轉移至偏光薄膜之方法,或在偏光薄膜塗布前述黏著劑組成物,乾燥去除聚合溶劑等而於偏光薄膜性成黏著劑層之方法等。又,進行黏著劑塗布時,亦可適宜地重新加入聚合溶劑以外之一種以上之溶劑。 The method of forming the adhesive layer can be carried out, for example, by applying the above-mentioned adhesive composition to a release-treated release material or the like, drying and removing a polymerization solvent or the like to form an adhesive layer, and then transferring to a polarized light. The method of the film, or the method of applying the above-mentioned adhesive composition to a polarizing film, drying and removing a polymerization solvent or the like, and forming a pressure-sensitive adhesive layer on a polarizing film. Further, when the adhesive is applied, one or more solvents other than the polymerization solvent may be appropriately added.
作為經剝離處理之離型材,宜使用聚矽氧烷離型襯材。於此種襯材上塗布本發明之接著劑組成物並使其乾燥而形成黏著劑層之程序中,作為使黏著劑層乾燥之方法,係可依目的而適宜地採用適切之方法。理想者,可採 用加熱乾燥前述塗布膜之方法。加熱乾燥溫度宜為40℃~200℃,進而50℃~180℃為佳,70℃~170℃尤佳。藉由使加熱溫度為前述範圍,可獲得具有優異黏著特性之黏著劑。 As the release-treated release profile, a polyoxyalkylene release liner is preferably used. In the procedure of applying the adhesive composition of the present invention to the lining material and drying it to form an adhesive layer, as a method of drying the adhesive layer, a suitable method can be suitably employed depending on the purpose. Ideal The method of drying the aforementioned coating film by heating. The heating and drying temperature is preferably 40 ° C ~ 200 ° C, and further preferably 50 ° C ~ 180 ° C, 70 ° C ~ 170 ° C is particularly good. By setting the heating temperature to the above range, an adhesive having excellent adhesive properties can be obtained.
乾燥時間係可適宜地採用適切之方法。前述乾燥時間宜為5秒~20分鐘,5秒~10分鐘為佳,10秒~5分鐘尤佳。 The drying time can be suitably carried out by a suitable method. The drying time is preferably 5 seconds to 20 minutes, preferably 5 seconds to 10 minutes, and preferably 10 seconds to 5 minutes.
又,亦可於偏光薄膜之表面形成錨定層,於施行電暈處理、電漿處理等各種易接著處理後而形成黏著劑層。再者,亦可於黏著劑層之表面進行易接著處理。 Further, an anchor layer may be formed on the surface of the polarizing film, and an adhesive layer may be formed by performing various subsequent treatments such as corona treatment and plasma treatment. Furthermore, it is also possible to carry out an easy subsequent treatment on the surface of the adhesive layer.
黏著劑層之形成方法係可使用各種方法。具體上,係可例舉如輥塗法、接觸上膠輥塗佈法、凹板塗佈法、逆輥塗佈法、滾動刷塗法、噴塗法、浸漬輥塗佈法、棒塗佈法、刮刀塗佈法、氣動刮刀塗佈法、簾塗佈法、模嘴塗佈法、鑄模塗佈法等之押出成形法等。 Various methods can be used to form the adhesive layer. Specifically, for example, a roll coating method, a contact top coat coating method, a gravure coating method, a reverse roll coating method, a roll brushing method, a spray coating method, a dip roll coating method, and a bar coating method. An extrusion molding method such as a knife coating method, a pneumatic blade coating method, a curtain coating method, a die coating method, and a mold coating method.
黏著劑層之厚度並無特別限制,譬如約1~100μm。宜為2~50μm,較佳為2~40μm,5~35μm尤佳。 The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm. It is preferably 2 to 50 μm, preferably 2 to 40 μm, and particularly preferably 5 to 35 μm.
前述黏著劑層露出時,迄至供予實際使用,亦可以經剝離處理之片材(離型材)來保護黏著劑層。 When the adhesive layer is exposed, it may be used for practical use, and the adhesive layer may be protected by a release-treated sheet (release material).
作為離型材之構成材料,係可例舉如聚乙烯、聚丙烯、聚對苯二甲乙二酯、聚酯薄膜等之塑料薄膜;紙、布、不織布等之多孔質材料;網狀物、發泡片材、金屬箔及其等之積層體等的適宜的薄葉體等,惟由表面平化性優異之點,塑料薄膜係適宜使用。 The constituent material of the release material may, for example, be a plastic film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film; a porous material such as paper, cloth or non-woven fabric; A suitable thin leaf body such as a foam sheet, a metal foil, or the like, and the like, is excellent in surface flatness, and a plastic film is suitably used.
作為該塑料薄膜,只要是可保護前述黏著劑層之 薄膜,即無特別限定,譬如可例舉聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯化乙烯薄膜、氯化乙烯酯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚胺基甲酸酯薄膜、乙烯-醋酸乙烯酯共聚物薄膜。 As the plastic film, as long as it is capable of protecting the aforementioned adhesive layer The film is not particularly limited, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride copolymer film. , polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film.
前述離型材之厚度通常為5~200μm,宜約為5~100μm。於前述離型材,亦可依需求,進行經由聚矽氧烷系、氟素系、長鏈烷基系或脂肪酸胺系之離型劑、氧化矽粉末等之離型及防污處理,或塗佈型、揉合型、蒸鍍型等之抗靜電處理。特別係可適宜地對前述離型材之表面進行聚矽氧烷處理、長鏈烷基處理、氟素處理等之剝離處理,而更提高自前述黏著劑層剝離性。 The thickness of the above-mentioned release profile is usually 5 to 200 μm, preferably about 5 to 100 μm. In the above-mentioned release profile, a release agent and an antifouling treatment, such as a release agent of a polyoxyalkylene system, a fluorine-based, a long-chain alkyl group or a fatty acid amine, or a cerium oxide powder, or a coating may be carried out as needed. Antistatic treatment of cloth type, twist type, vapor deposition type, etc. In particular, the surface of the release material can be suitably subjected to a release treatment such as polyoxyalkylene treatment, long-chain alkyl treatment, or fluorine treatment to further improve the peelability from the adhesive layer.
又,製作前述附黏著劑層之偏光薄膜時使用的經剝離處理之片材,係可直接作為附黏著劑層之偏光薄膜之離型材使用,於程序面可加以簡化。 Further, the release-treated sheet used in the production of the polarizing film with the adhesive layer described above can be directly used as a release sheet of a polarizing film with an adhesive layer, which can be simplified on the program surface.
偏光薄膜係使用僅於偏光子之單側具有透明保護薄膜者。 The polarizing film is a film having a transparent protective film on only one side of the polarizer.
偏光子並無特別限定,可使用各種偏光子。作為偏光子,係可例舉如聚乙烯醇系薄膜、部分縮甲醛化之聚乙烯醇系薄膜、於乙烯-醋酸乙烯酯共聚合物系部分皂化薄膜等之親水性高分子薄膜,吸附碘或二色性染料之二色性物質並作單軸延伸者;聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等之聚烯系配向薄膜等。其等之中,係以由聚乙烯醇系薄膜與碘等二色性物質構成之偏光子為宜。 其等偏光子之厚度並無特別限制,惟通常約80μm以下。 The polarizer is not particularly limited, and various polarizers can be used. The polarizing film may, for example, be a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or a hydrophilic polymer film such as an ethylene-vinyl acetate copolymer-based partially saponified film, which adsorbs iodine or A dichroic dye of a dichroic dye is used as a uniaxially stretched product; a dehydrated material of polyvinyl alcohol or a polyolefin-based alignment film such as a dechlorination treatment of polyvinyl chloride. Among them, a polarizer composed of a polyvinyl alcohol-based film and a dichroic material such as iodine is preferred. The thickness of the equal-polarizer is not particularly limited, but is usually about 80 μm or less.
將聚乙烯醇系薄膜以碘染色並單軸延伸之偏光子,係譬如可藉由將聚乙烯醇系薄膜浸漬於碘之水溶液而加以染色,延伸為原來長度的3~7倍而製成。可依需要浸漬於其中亦可含有硼酸、硫酸鋅、氯化鋅等之碘化鉀等的水溶液中。進而,亦可依需求於染色前將聚乙烯醇系薄膜浸漬於水中加以水洗。藉由將聚乙烯醇系薄膜加以水洗,除可洗淨聚乙烯醇系薄膜表面之污垢及結塊,且亦有可藉由讓聚乙烯醇系薄膜變得膨脹濕潤而防止染色不均等不均一的效果。延伸可於碘染色後進行,亦可邊進行染色邊進行延伸,又,亦可延伸後再以碘染色。亦可於硼酸及碘化鉀等之水溶液或水浴中進行延伸。 The polarizer in which the polyvinyl alcohol-based film is iodine-dyed and uniaxially stretched can be obtained by, for example, immersing a polyvinyl alcohol-based film in an aqueous solution of iodine and dyeing it, and extending it to 3 to 7 times the original length. It may be immersed in an aqueous solution such as potassium iodide such as boric acid, zinc sulfate or zinc chloride. Further, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing as needed. By washing the polyvinyl alcohol-based film with water, it is possible to remove the dirt and agglomeration on the surface of the polyvinyl alcohol-based film, and it is also possible to prevent unevenness in dyeing unevenness by allowing the polyvinyl alcohol-based film to expand and wet. Effect. The extension can be carried out after iodine dyeing, or it can be extended while dyeing, or it can be extended and then dyed with iodine. It can also be extended in an aqueous solution or a water bath such as boric acid or potassium iodide.
又,作為偏光子,可使用厚度為10μm以下之薄型偏光子。若由薄型化之觀點言之,該厚度宜為1~7μm。此種薄型偏光子係厚度不均少,視辨性優,且尺寸變化少,故耐久性優異,進而,作為偏光薄膜之厚度亦可追求薄型化,因而為宜。另一方面,薄型偏光子係易偏光劣化。本發明之附黏著劑層之偏光薄膜,係黏著劑層含有鎓-含氟醯亞胺陰離子鹽(B),因此不會招致光學特性劣化,且可賦予抗靜電功效。本發明之附黏著劑層之偏光薄膜係縱或使用薄型偏光子時,亦可抑制偏光特性低落。 Further, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. The thickness is preferably 1 to 7 μm from the viewpoint of thinning. Such a thin polarizer has a small thickness unevenness, is excellent in visibility, and has small dimensional change, so that it is excellent in durability, and further, it is preferable to reduce the thickness of the polarizing film. On the other hand, the thin polarizer is susceptible to polarization degradation. The polarizing film with an adhesive layer of the present invention contains an antimony-fluorinated quinone anion salt (B), so that the optical properties are not deteriorated and an antistatic effect can be imparted. When the polarizing film of the adhesive layer of the present invention is used vertically or when a thin polarizer is used, the polarization characteristics can be suppressed from being lowered.
作為薄型偏光子,代表性地係可例舉記載於日本特開昭51-069644號公報與特開2000-338329號公報、以及WO2010/100917號說明書、PCT/JP2010/001460之說明書, 或特願2010-269002號說明書及特願2010-263692號說明書中之薄型偏光層。其等薄型偏光層係可經由包含將聚乙烯醇系樹脂(以下亦稱PVA系樹脂)層及延伸用樹脂基材,以積層體之狀態延伸之程序與染色程序之製法而獲得。若為此製法,即使PVA系樹脂層很薄,亦可以延伸用樹脂基材加以支撐,而無因延伸而破裂斷開等之不理想情況地加以延伸。 The thin-type polarizer is exemplified by the descriptions of JP-A-51-069644, JP-A-2000-338329, and WO2010/100917, and PCT/JP2010/001460. Or a thin polarizing layer in the specification of 2010-269002 and the specification of Japanese Patent Application No. 2010-263692. The thin polarizing layer can be obtained by a method including a method of extending a polyvinyl alcohol-based resin (hereinafter also referred to as PVA resin) layer and a resin substrate for stretching in a state of a laminate, and a dyeing procedure. According to this method, even if the PVA-based resin layer is thin, it can be stretched and supported by a resin substrate, and it is not stretched without being undesirably broken due to elongation.
前述薄型偏光層,即使於包含以積層體之狀態而延伸之程序及染色程序之製法中,由可高倍率地延伸而提高偏光性能之點,係宜為如WO2010/100917號說明書、PCT/JP2010/001460之說明書,或特願2010-269002號說明書及特願2010-263692號說明書中所記載之包含於硼酸水溶液中延伸之程序的製法而獲得者,特別宜為藉由願2010-269002號說明書及特願2010-263692號說明書中所記載之包含於硼酸水溶液中延伸前,補助性地空中延伸之程序的製法而獲得者。 The thin polarizing layer is preferably a method capable of extending at a high magnification and improving the polarizing performance even in a method including a process of extending the laminated body and a dyeing process, as described in WO2010/100917, PCT/JP2010. The method of the method of the method of extending the aqueous solution of boric acid described in the specification of the Japanese Patent No. 2010-269002 or the specification of the Japanese Patent Application No. 2010-263692, especially the specification of the Japanese Patent Application No. 2010-269002 And the method described in the specification of the Japanese Patent Application No. 2010-263692, which is incorporated in the aqueous solution of boric acid, and is obtained by a process of assisting the air extension.
前述PCT/JP2010/001460之說明書所記載之薄型高機能偏光層,係由在樹脂基材一體地製膜,讓二色性物質配向之PVA系樹脂構成之厚度為7μm以下之薄型高機能偏光層,具有單體穿透率為42.0%以上以及偏光度為99.95%以上之光學特性。 The thin high-performance polarizing layer described in the specification of the above-mentioned PCT/JP2010/001460 is a thin high-performance polarizing layer having a thickness of 7 μm or less, which is formed of a PVA-based resin which is integrally formed on a resin substrate and has a dichroic substance aligned. It has an optical property of a monomer transmittance of 42.0% or more and a degree of polarization of 99.95% or more.
前述薄型高機能偏光層係可於具有至少20μm厚度之樹脂基材,藉由PVA系樹脂之塗佈及乾燥而生成PVA系樹脂層,將所生成之PVA系樹脂層浸漬於二色性物質之染色液中,讓二色性物質吸附於PVA系樹脂層,並將吸附 有二色性物質之PVA系樹脂層,於硼酸水溶液中,與樹脂基材一體地使總延伸倍率為原來長度5倍以上地加以延伸,而加以製造。 The thin high-performance polarizing layer can form a PVA-based resin layer by coating and drying a PVA-based resin on a resin substrate having a thickness of at least 20 μm, and immersing the produced PVA-based resin layer in a dichroic substance. In the dyeing solution, the dichroic substance is adsorbed to the PVA-based resin layer and adsorbed The PVA-based resin layer having a dichroic material is produced by extending the total stretch ratio to the original length of the resin substrate in an aqueous solution of boric acid by a factor of 5 or more.
又,製作包含配向有二色性物質之薄型高機能偏光層之積層體薄膜的方法,係包含有:生成積層體薄膜之程序,該積層體薄膜係包含具有至少20μm厚度之樹脂基材,及於樹脂基材之單面塗佈含有PVA系樹脂之水溶液並使其乾燥而形成之PVA系樹脂層之程序;吸附二色性物質之程序,其係藉由將包含樹脂基材及形成於樹脂基材單面之PVA系樹脂層之前述積層體薄膜,浸漬於含有二色性物質之染色液中,而使二色性物質吸附於積體層薄膜所含之PVA系樹脂層;延伸程序,係將包含吸附有二色性物質之PVA系樹脂層之前述積層體薄膜,於硼酸水溶液中,使總延伸倍率為原來長度5倍以上地加以延伸;及製作形成有薄型高機能偏光層之積層體薄膜程序,係藉由讓吸附有二色性物質之PVA系樹脂層與樹脂基材一體地延伸,而在樹脂基材之單面,製得由配向有二色性物質之PVA系樹脂層構成,厚度7μm以下、具有單體穿透率42.0%以上且偏光度99.95%以上之光學特性的薄型高積層偏光層;且藉由上述程序而製造前述薄型高積層偏光層。 Further, a method of producing a laminate film comprising a thin high-performance polarizing layer having a dichroic material includes a method of forming a laminate film comprising a resin substrate having a thickness of at least 20 μm, and a procedure for applying a PVA-based resin layer formed by drying an aqueous solution containing a PVA-based resin on one surface of a resin substrate; and a method of adsorbing a dichroic substance by including a resin substrate and forming a resin The laminated film of the PVA-based resin layer on one side of the substrate is immersed in a dyeing liquid containing a dichroic substance, and the dichroic substance is adsorbed to the PVA-based resin layer contained in the integrated layer film; The laminate film comprising the PVA-based resin layer to which the dichroic substance is adsorbed is stretched in a boric acid aqueous solution to have a total stretching ratio of 5 times or more of the original length; and a laminate having a thin high-performance polarizing layer is formed. In the film process, a PVA-based resin layer having a dichroic substance adsorbed thereon is integrally extended with a resin substrate, and a PVA having a dichroic substance is prepared on one side of the resin substrate. The resin constituting the layer, the thickness of 7μm or less, a thin laminate having a high polarizing layer more monomers transmittance and a polarization degree of 42.0% 99.95% or more of the optical characteristics of; and be manufactured by the procedure described above the laminated thin high polarizing layer.
本發明中,如前述,於前述附黏著劑層之偏光薄膜,作為厚度10μm以下之偏光子係由配向有二色性物質之PVA系樹脂所構成之連續卷狀偏光層,其可使用包含成膜於熱可塑性樹脂基材之聚乙烯醇系樹脂上的積層體,以包 含空中補助延伸及硼酸水中延伸構成之2段延伸程序來加以延伸而獲致者。前述熱可塑性樹脂基材,宜為非晶形酯系熱可塑性樹脂基材或結晶形酯系熱可塑性樹脂基材。 In the present invention, as described above, the polarizing film having the thickness of 10 μm or less is a continuous roll-shaped polarizing layer composed of a PVA-based resin having a dichroic material, and can be used as a polarizing film having a thickness of 10 μm or less. a laminate of a film on a polyvinyl alcohol-based resin of a thermoplastic resin substrate, in a package The two extensions consisting of an extension of the air support and an extension of the boric acid water are used to extend it. The thermoplastic resin substrate is preferably an amorphous ester-based thermoplastic resin substrate or a crystalline ester-based thermoplastic resin substrate.
前述特願2010-269002號說明書籍特願2010-263692號說明書之薄型偏光層,係由配向有二色性物質之PVA系樹脂所構成之連續卷狀偏光層,且包含形成於非晶形酯系熱可塑性樹脂基材上之PVA系樹脂層的積層體,藉由以包含空中補助延伸及硼酸水中延伸構成之2段延伸程序來加以延伸,而做成10μm以下之厚度。此種薄型偏光層係令單體穿透率為T、偏光度為P時,宜具有滿足P>-(100.929T-42.4-1)×100(惟T<42.3)以及P≧99.9(惟T≧42.3)之條件的光學特性者。 The thin polarizing layer described in the specification of Japanese Patent Application No. 2010-263692 is a continuous roll-shaped polarizing layer composed of a PVA resin having a dichroic substance, and is formed in an amorphous ester system. The laminate of the PVA-based resin layer on the thermoplastic resin substrate is stretched by a two-stage extension process including an air-assisted extension and a boric acid water extension to have a thickness of 10 μm or less. Such a thin polarizing layer is such that when the monomer transmittance is T and the degree of polarization is P, it is preferable to satisfy P>-(10 0.929T-42.4 -1)×100 (but T<42.3) and P≧99.9 (only The optical characteristics of the conditions of T≧42.3).
具體上,前述薄型偏光層係可藉由包含有下述程序之薄型偏光層之製造方法來製造,即:生成延伸中間生成物程序,係藉由對於形成於連續卷狀非晶形酯系熱可塑性樹脂基材上之PVA系樹脂層進行空中高溫延伸,而生成由經配向之PVA系樹脂層所構成之延伸中間生成物;生成著色中間生成物程序,係藉由對延伸中間生成物進行二色性物質之吸附,而生成由經配向二色性物質(宜為碘、或碘與有機染料之混合物)之PVA系樹脂層構成之著色中間生成物;及生成偏光層程序,係藉由對著色中間生成物進行硼酸水中延伸,而生成由經配向二色性物質之PVA系樹脂層構成之厚度10μm以下之偏光層。 Specifically, the thin polarizing layer can be produced by a manufacturing method of a thin polarizing layer comprising the following procedure, that is, a process of forming an extended intermediate product by thermal plasticity formed in a continuous roll-shaped amorphous ester system The PVA-based resin layer on the resin substrate is extended in the air at a high temperature to form an extended intermediate product composed of the aligned PVA-based resin layer, and a colored intermediate product is produced by performing two-color processing on the extended intermediate product. Adsorption of a substance to form a colored intermediate product composed of a PVA-based resin layer which is a dichroic substance (preferably iodine or a mixture of iodine and an organic dye); and a method of producing a polarizing layer by coloring The intermediate product is extended in boric acid water to form a polarizing layer having a thickness of 10 μm or less, which is composed of a PVA-based resin layer having a dichroic material.
於此製造方法中,形成於以空中高溫延伸及硼酸 水中延伸而得之非晶形酯系熱可塑性樹脂基材上的PVA系樹脂層之總延伸倍率,宜為5倍以上。用以於硼酸水中延伸之硼酸水溶液的液溫,可為60℃以上。於硼酸水溶液中延伸著色中間生成物前,對於著色中間生成物宜施行不溶解化處理,此時,宜藉由將前述著色中間生成物浸漬於液溫不超過40℃之硼酸水溶液中而進行。前述非晶形酯系熱可塑性樹脂基材,可為包含共聚合間苯二甲酸之共聚合聚對苯二甲酸乙二酯共聚物、共聚合環己烷二甲醇之共聚合聚對苯二甲酸乙二酯共聚物、或其他共聚合聚對苯二甲酸乙二酯共聚物之非晶形聚對苯二甲酸乙二酯,且宜為由透明樹脂構成者,其厚度可為經製膜之PVA系樹脂層之厚度的7倍以上。又,空中高溫延伸之延伸倍率宜為3.5倍以下,空中高溫延伸之延伸溫度宜高於PVA系樹脂之玻璃轉化溫度,具體上,宜為95℃~150℃之範圍。空中高溫延伸係以自由端單軸延伸進行時,經成膜於非晶形酯系熱可塑性樹脂基材之PVA系樹脂層之總延伸倍率,宜為5倍以上、7.5倍以下。又,空中高溫延伸以固定端單軸延伸進行時,經成膜於非晶形酯系熱可塑性樹脂基材之PVA系樹脂層之總延伸倍率,宜為5倍以上、8.5倍以下。 In this manufacturing method, it is formed in a high temperature extension in the air and boric acid The total stretching ratio of the PVA-based resin layer on the amorphous ester-based thermoplastic resin substrate obtained by stretching in water is preferably 5 times or more. The liquid temperature of the aqueous boric acid solution used for extending in boric acid water may be 60 ° C or higher. Before the coloring intermediate product is extended in the aqueous boric acid solution, the coloring intermediate product is preferably subjected to an insolubilization treatment. In this case, it is preferred to carry out the immersion intermediate product in a boric acid aqueous solution having a liquid temperature of not more than 40 °C. The amorphous ester-based thermoplastic resin substrate may be a copolymerized polyethylene terephthalate copolymer containing copolymerized isophthalic acid or a copolymerized cyclohexanedimethanol copolymerized polyethylene terephthalate. An ester copolymer or other copolymerized polyethylene terephthalate copolymer amorphous polyethylene terephthalate, and preferably composed of a transparent resin, the thickness of which may be a film-formed PVA resin The thickness of the layer is more than 7 times. Moreover, the stretching ratio of the high temperature extension in the air is preferably 3.5 times or less, and the extension temperature of the high temperature extension in the air is preferably higher than the glass transition temperature of the PVA resin, and specifically, it is preferably in the range of 95 ° C to 150 ° C. When the airborne high-temperature extension is carried out by uniaxial stretching at the free end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 7.5 times or less. In addition, when the high-temperature extension in the air is performed by the uniaxial extension of the fixed end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 8.5 times or less.
進一步,更具體上,係可藉由以下之方法來製造薄型偏光層。 Further, more specifically, the thin polarizing layer can be produced by the following method.
製作共聚合有6mol%間苯二甲酸之間苯二甲酸-聚對苯二甲酸乙二酯共聚合(非晶形PET)之連續卷狀基材。非晶形PET之玻璃轉化溫度為75℃。以下述方法來製作 由連續卷狀之非晶形PET基材及聚乙烯醇(PVA層)構成之積層體。順帶一提,PVA之玻璃轉化溫度為80℃。 A continuous roll substrate having a copolymerization of 6 mol% of isophthalic acid-polyethylene terephthalate copolymer (amorphous PET) was produced. The glass transition temperature of amorphous PET was 75 °C. Made in the following way A laminate comprising a continuous roll of amorphous PET substrate and polyvinyl alcohol (PVA layer). Incidentally, the glass transition temperature of PVA is 80 °C.
準備將200μm厚之非晶形PET基材,及聚合度1000以上、皂化度99%以上之PVA粉末溶解於水之4~5%濃度的PVA水溶液。其次,將PVA水溶液塗佈於200μm厚之非晶形PET基材,以50~60℃之溫度乾燥,獲得於非晶形PET基材成膜有7μm厚之PVA層的積層體。 An amorphous PET substrate having a thickness of 200 μm and a PVA powder having a polymerization degree of 1,000 or more and a saponification degree of 99% or more were prepared and dissolved in a PVA aqueous solution having a concentration of 4 to 5% in water. Next, the PVA aqueous solution was applied onto an amorphous PET substrate having a thickness of 200 μm, and dried at a temperature of 50 to 60 ° C to obtain a laminate in which a PVA layer having a thickness of 7 μm was formed on an amorphous PET substrate.
讓包含7μm厚之PVA層的積層體,經由包含空中補助延伸及硼酸水中延伸之2段延伸程序的以下程序,而製造3μm厚之薄型高機能偏光層。藉由第1段之空中補助延伸程序,讓包含7μm厚之PVA層的積層體與非晶形PET基材一體地延伸,生成包含5μm厚之PVA層的延伸積體層。具體上,該延伸積體層係將7μm厚之PVA層,置於配備有設定為130℃之延伸溫度環境之烘箱的延伸裝置,並以延伸倍率為1.8倍方式作自由端單軸延伸而成者。經此延伸處理,係可令包含於延伸積層體之PVA層轉變為PVA分子經配向之5μm厚的PVA層。 A laminate having a PVA layer having a thickness of 7 μm was subjected to the following procedure including a two-stage extension procedure in which the air-assisted extension and the boric acid water were extended to produce a thin, high-performance polarizing layer having a thickness of 3 μm. The layered body including the PVA layer having a thickness of 7 μm was integrally extended with the amorphous PET substrate by the air-assisted extension program of the first stage to form an extended body layer including a PVA layer having a thickness of 5 μm. Specifically, the extended integrated layer is a 7 μm thick PVA layer placed in an extension device equipped with an oven set to an extended temperature of 130 ° C, and is a free end uniaxial extension with a stretching ratio of 1.8 times. . Through this stretching treatment, the PVA layer contained in the extended laminated body can be converted into a 5 μm thick PVA layer in which the PVA molecules are aligned.
其次,藉由染色程序,生成讓PVA分子經配向之5μm厚的PVA層吸附有碘之著色積層體。具體上,該著色積層體係藉由將延伸積層體,以使構成最後產生之高機能偏光層之PVA層的單體穿透率為40~44%,於任意時間,浸漬於液溫30℃之包含碘及碘化鉀之染色液中,俾使延伸積層體所包含之PVA層吸附碘而成者。於本程序,染色液係以水作為溶劑,令碘濃度為0.12~0.30重量%之範圍內,碘化 鉀濃度為0.7~2.1重量%之範圍內。碘及碘化鉀之濃度比為1比7。順帶一提,將碘溶解於水係需要碘化鉀。更詳而言之,藉由將延伸積層體浸漬於碘濃度0.30重量%、碘化鉀濃度2.1重量%之染色液60秒鐘,而於PVA分子經配向之5μm厚的PVA層生成吸附有碘之著色積層體。 Next, a coloring layer body in which iodine is adsorbed by a PVA layer having a 5 μm thick orientation by PVA molecules is formed by a dyeing procedure. Specifically, the coloring layer system is formed by extending the laminated body so that the PVA layer constituting the finally produced high-performance polarizing layer has a monomer transmittance of 40 to 44%, and is immersed in a liquid temperature of 30 ° C at any time. In the dyeing solution containing iodine and potassium iodide, yttrium is used to adsorb iodine in the PVA layer contained in the extended laminate. In the present procedure, the dyeing solution uses water as a solvent to make the iodine concentration in the range of 0.12 to 0.30% by weight, iodide. The potassium concentration is in the range of 0.7 to 2.1% by weight. The concentration ratio of iodine to potassium iodide is 1 to 7. Incidentally, potassium iodide is required to dissolve iodine in the water system. More specifically, by immersing the extended layered body in a dyeing liquid having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, a PVA layer having a 5 μm thick PVA layer is formed to have an iodine-adsorbing color. Laminated body.
再者,藉由第2段硼酸水中延伸程序,將著色積層體與非晶形PET基材一體地更佳延伸,生成包含構成3μm厚高機能偏光層之PVA層的光學薄膜積層體。具體上,該光學薄膜積層體係將著色積層體,置於配備有處理裝置之延伸裝置,以延伸倍率為3.3倍方式作自由端單軸延伸而成者,前述處理裝置設有包含硼酸及碘化鉀之液溫範圍60~85℃之硼酸水溶液。更詳而言之,硼酸水溶液之液溫為65℃。又,令硼酸含量相對水100重量份為4重量份,令碘化鉀含量相對於水100重量份為5重量份。本程序中,係先將調整過碘吸附量之著色積層體,浸漬於硼酸水溶液中5~10秒。之後,讓該著色積層體直接通過配備有處理裝置之延伸裝置之周速相異的多數組輥筒間,經30~90秒以令延伸倍率為3.3倍方式作自由端單軸延伸。藉此延伸,可使著色積層體所含有之PVA層轉變為所吸附之碘為多碘離子錯合體,且經單一方向高度配向之3μm厚PVA層。該PVA層係構成光學薄膜積層體之高機能偏光層。 Further, the colored layered product and the amorphous PET substrate were integrally extended more integrally by the second-stage boric acid water extending procedure to form an optical film layered body including a PVA layer constituting a 3 μm-thick high-performance polarizing layer. Specifically, the optical film layering system places the colored layered body in an extension device equipped with a processing device, and has a stretching ratio of 3.3 times as a free end uniaxial extension, and the processing device is provided with boric acid and potassium iodide. A boric acid aqueous solution having a liquid temperature range of 60 to 85 °C. More specifically, the liquid temperature of the aqueous boric acid solution was 65 °C. Further, the boric acid content was 4 parts by weight based on 100 parts by weight of water, and the potassium iodide content was 5 parts by weight based on 100 parts by weight of water. In the present procedure, the colored layer body having the adjusted iodine adsorption amount is first immersed in a boric acid aqueous solution for 5 to 10 seconds. Thereafter, the colored layered body is directly uniaxially stretched between the multi-array rolls having different peripheral speeds of the stretching device equipped with the processing means for 30 to 90 seconds at a stretching ratio of 3.3 times. By this extension, the PVA layer contained in the colored layered body can be converted into a 3 μm thick PVA layer in which the adsorbed iodine is a polyiodide ion-coupled body and highly aligned in a single direction. The PVA layer constitutes a high-performance polarizing layer of an optical film laminate.
雖非為光學薄膜積層體之製造中所必要的程序,但宜藉由洗淨程序,將光學薄膜積層體由硼酸水溶液取出,將附著在經成膜於非晶形PET基材上之3μm厚PVA層 表面的硼酸,以碘化鉀水溶液洗淨。之後,將業已洗淨之光學薄膜積層體,藉由60℃溫風之乾燥程序予以乾燥。又,洗淨程序係用以消除硼酸析出等之外觀不良的程序。 Although it is not a procedure necessary for the manufacture of the optical film laminate, it is preferable to remove the optical film laminate from the aqueous boric acid solution by a cleaning procedure, and adhere to a 3 μm thick PVA which is formed on the amorphous PET substrate. Floor The boric acid on the surface was washed with an aqueous solution of potassium iodide. Thereafter, the cleaned optical film laminate was dried by a drying process at 60 ° C. Further, the cleaning procedure is a procedure for eliminating appearance defects such as precipitation of boric acid.
同樣地,雖非為光學薄膜積層體之製造中所必要的程序,但亦可藉由貼合及/或轉移程序,將接著劑塗佈在成膜於非晶形PET基材上之3μm厚PVA層表面,同時貼合80μm厚之三醋酸纖維素薄膜後,將非晶形PET基材剝離,使3μm厚之PVA層轉移至80μm厚之三醋酸纖維素薄膜。 Similarly, although it is not a procedure necessary for the manufacture of an optical film laminate, the adhesive may be applied to a 3 μm thick PVA formed on an amorphous PET substrate by a bonding and/or transfer procedure. After the 80 μm thick triacetylcellulose film was bonded to the surface of the layer, the amorphous PET substrate was peeled off, and the 3 μm thick PVA layer was transferred to a 80 μm thick triacetate film.
[其他程序] [other programs]
前述薄型偏光層之製造方法除前述程序,並可包含其他程序。其他程序係可例舉不溶解化程序、交聯程序、乾燥(水分率調節)程序等。其他程序係可以在任意的適當時間點進行。 The method for producing the aforementioned thin polarizing layer may include other programs in addition to the aforementioned procedures. Other programs may, for example, be an insolubilization program, a crosslinking program, a drying (moisture rate adjustment) program, or the like. Other programs can be performed at any appropriate point in time.
前述不溶解化程序,代表性地係藉由將PVA系樹脂層浸漬於硼酸水溶液而進行。藉由進行不溶解化處理,可給予PVA系樹脂層耐水性。該硼酸水溶液之濃度係相對於水100重量份,宜為1重量份~4重量份。不溶解化浴(硼酸水溶液)之液溫,宜為20℃~50℃。較佳者為不溶解化程序係於積層體製作後、染色程序或水中延伸程序之前進行。 The insolubilization procedure is typically carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. The water resistance of the PVA-based resin layer can be imparted by performing the insolubilization treatment. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight per 100 parts by weight of water. The liquid temperature of the insoluble bath (aqueous boric acid solution) is preferably from 20 ° C to 50 ° C. Preferably, the insolubilization procedure is performed after the production of the laminate, prior to the dyeing procedure or the water extension procedure.
前述交聯程序,代表性地係藉由將PVA系樹脂層浸漬於硼酸水溶液而進行。藉由進行交聯處理,可給予PVA系樹脂層耐水性。該硼酸水容亦濃度係相對於水100重量份,宜為1重量份~4重量份。又,於進行前述染色程序後進行交聯程序時,宜進一步混合碘化物。藉由混合碘化物,係可抑 制吸附於PVA系樹脂層之碘溶出。碘化物之混合量係相對於水100重量份,宜為1重量份~5重量份。碘化物之具體例係如前述。交聯浴(硼酸水溶液)之液溫,宜為20℃~50℃。較佳者,交聯程序係於前述第2硼酸水中延伸程序之前進行。較佳實施形態中,係以染色程序、交聯程序及第2硼酸水中延伸程序之順序進行。 The crosslinking procedure is typically carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. The PVA-based resin layer can be imparted with water resistance by performing a crosslinking treatment. The boric acid water content is also preferably from 1 part by weight to 4 parts by weight based on 100 parts by weight of the water. Further, when the crosslinking procedure is carried out after performing the above dyeing procedure, it is preferred to further mix the iodide. By mixing iodide, it is possible to suppress The iodine adsorbed on the PVA-based resin layer is eluted. The compounding amount of the iodide is preferably from 1 part by weight to 5 parts by weight per 100 parts by weight of the water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably from 20 ° C to 50 ° C. Preferably, the crosslinking procedure is carried out prior to the second boric acid water extension procedure. In a preferred embodiment, the dyeing procedure, the crosslinking procedure, and the second boric acid water extension procedure are performed.
作為構成透明保護薄膜之材料,係可使用譬如機械性強度、熱穩定性、水分阻絕性、等向性等優異之熱可塑性樹脂。此種熱可塑性樹脂之具體例,係可例舉如三醋酸纖維素等之纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚烯亞胺樹脂、聚烯烴樹脂(降莰烯系樹脂)、(甲基)丙烯酸樹脂、環狀聚烯烴樹脂(降莰烯系樹脂)、聚芳族酯樹脂、聚苯乙烯樹脂、聚乙烯醇數至及其等之混合物。透明保護薄膜中,亦可包含1種類以上任意的適當添加劑。作為添加劑,係可舉出如紫外線吸收劑、抗氧化劑、滑劑、可塑劑、離型劑、抗著色劑、難燃劑、成核劑、抗靜電劑、顏料、著色劑等。透明保護薄膜中之前述熱可塑性樹脂之含量,宜為50~100重量%,較佳為50~99重量%,進而,60~98重量%為佳,70~97重量%尤佳。透明保護薄膜中之前述熱可塑性樹脂之含量為50重量%以下時,恐有熱可塑性樹脂本身具有之高透明性等無法充分展現之疑慮。 As the material constituting the transparent protective film, a thermoplastic resin excellent in mechanical strength, thermal stability, moisture resistance, and isotropic properties can be used. Specific examples of such a thermoplastic resin include cellulose resins such as cellulose triacetate, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyenes. Amine resin, polyolefin resin (northene-based resin), (meth)acrylic resin, cyclic polyolefin resin (northene-based resin), polyarylate resin, polystyrene resin, polyvinyl alcohol to a mixture of them and the like. The transparent protective film may contain any suitable additive of one type or more. Examples of the additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, release agents, anti-colorants, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, preferably from 50 to 99% by weight, more preferably from 60 to 98% by weight, particularly preferably from 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, there is a fear that the high transparency of the thermoplastic resin itself cannot be sufficiently exhibited.
又,透明保護薄膜係藉由接著劑層而貼合於偏光子之單側。偏光子與透明保護薄膜之接著處理係使用接著 劑。接著劑係可例示異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯基系乳膠系、水系聚酯等。前述接著劑通常係作為由水溶液構成之接著劑使用,一般含有0.5~60重量%之固形份。除前述,作為偏光子及透明保護薄膜之接著劑,係可例舉紫外線硬化型接著劑、電子束硬化型接著劑等。電子束硬化型偏光薄膜用接著劑,對於前述各種透明保護薄膜係顯示合宜之接著性。又,本發明所使用之接著劑,亦可含有金屬化合物填料。 Further, the transparent protective film is bonded to one side of the polarizer by the adhesive layer. The subsequent processing of the polarizer and the transparent protective film is followed by Agent. Examples of the subsequent agent include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, and an aqueous polyester. The above-mentioned adhesive is usually used as an adhesive composed of an aqueous solution, and generally contains 0.5 to 60% by weight of a solid portion. In addition to the above, examples of the binder of the polarizer and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for an electron beam curing type polarizing film exhibits an appropriate adhesion to the above various transparent protective film systems. Further, the adhesive used in the present invention may further contain a metal compound filler.
又,前述偏光薄膜係可與其他的光學薄膜積層。其他的光學薄膜係可例舉如反射板或反穿透板、相位差薄膜(包含1/2或1/4等之波長板)、視覺補償薄膜、增亮膜等,作為形成液晶顯示裝置等所使用之光學層。其等係可在實際使用時,使用1層或2層以上,積層於前述偏光薄膜。 Further, the polarizing film can be laminated with another optical film. The other optical film system may, for example, be a reflection plate or a reverse transmission plate, a retardation film (including a wavelength plate of 1/2 or 1/4 or the like), a visual compensation film, a brightness enhancement film, or the like, as a liquid crystal display device or the like. The optical layer used. These may be used in one or two or more layers in actual use, and laminated on the polarizing film.
於偏光薄膜積層有前述光學層之光學薄膜,在液晶顯示裝置等之製造過程,亦可以依次個別地積層之方式形成,惟預先積層而成為光學薄膜者對於品質穩定性及組裝作業等方面較佳,具有可提升液晶顯示裝置等之製造程序的優點。積層時,可使用黏著層等適合的接著方法。前述偏光薄膜與其他光學層接著時,其等光學軸係可依作為目標之相位差特性等而施予適宜的配置角度。 The optical film in which the optical layer is laminated on the polarizing film may be formed by sequentially laminating in a process of manufacturing a liquid crystal display device or the like. However, it is preferable to laminate the film to form an optical film for quality stability and assembly work. There is an advantage that the manufacturing process of the liquid crystal display device or the like can be improved. When laminating, a suitable joining method such as an adhesive layer can be used. When the polarizing film is bonded to another optical layer, the optical axis system can be applied at an appropriate arrangement angle depending on the target phase difference characteristics or the like.
本發明之附黏著劑層之偏光薄膜,係可合宜地使用於液晶顯示裝置等各種影像顯示裝置之形成等。液晶顯示裝置之形成,可依習知進行。亦即,液晶顯示裝置一般係藉由適宜地組裝液晶晶胞等顯示面板與附黏著劑層之偏 光薄膜,以及視需求之照明系統等的構成構件,並安裝驅動電路等而形成,於本發明中,除使用本發明之附黏著劑層之偏光薄膜之點,並無特別限定,可依習知進行。有關液晶晶胞,可使用譬如TN型或STN型、π型、VA型、IPS型等任意種類之任意形式。 The polarizing film with an adhesive layer of the present invention can be suitably used for formation of various image display devices such as liquid crystal display devices. The formation of the liquid crystal display device can be carried out by conventional knowledge. That is, the liquid crystal display device is generally biased by a display panel such as a liquid crystal cell and an adhesive layer. The optical film and the constituent members of the illumination system and the like are formed by mounting a driving circuit or the like. In the present invention, the point of using the polarizing film with the adhesive layer of the present invention is not particularly limited, and can be used. Know to carry out. As the liquid crystal cell, any form such as TN type, STN type, π type, VA type, or IPS type can be used.
可形成於液晶晶胞等之顯示面板的單側或雙側,配置有附黏著劑層之偏光薄膜之液晶顯示裝置,或於照明系統使用背光或反射板者等之適宜的液晶顯示裝置。此時,本發明之附黏著劑層之偏光薄膜,係可設置於液晶晶胞等顯示面板之單側或雙側。於兩側設置光學薄膜時,其等可為相同者,亦可為不同者。進而,形成液晶顯示裝置時,可將譬如擴散層、抗眩層、抗反射膜、保護板、稜鏡陣列、透鏡陣列片、光擴散板、背光等適宜的構件,1層或2層以上配置於適合之位置。 A liquid crystal display device in which a polarizing film with an adhesive layer is disposed on one side or both sides of a display panel such as a liquid crystal cell, or a liquid crystal display device such as a backlight or a reflector for an illumination system can be used. In this case, the polarizing film of the adhesive layer of the present invention may be provided on one side or both sides of a display panel such as a liquid crystal cell. When an optical film is provided on both sides, the same may be the same or different. Further, when a liquid crystal display device is formed, an appropriate member such as a diffusion layer, an antiglare layer, an antireflection film, a protective plate, a tantalum array, a lens array sheet, a light diffusing plate, or a backlight can be disposed in one layer or two layers or more. In a suitable location.
以下,依實施例具體說明本發明,但本發明並不受其等實施例所限制。又,各例中之「份」及「%」均以重量為基準。以下並無特別規定之室溫放置條件係全為23℃ 65%RH。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. In addition, the "parts" and "%" in each case are based on weight. The room temperature conditions which are not specifically defined below are all 23 ° C 65% RH.
<(甲基)丙烯醯系聚合物(A)之重量平均分子量之測定> <Measurement of weight average molecular weight of (meth) propylene fluorene-based polymer (A)>
(甲基)丙烯醯系聚合物(A)之重量平均分子量係以GPC(膠透層析術)測量。 The weight average molecular weight of the (meth)acrylonitrile-based polymer (A) is measured by GPC (gel permeation chromatography).
‧分析裝置:東社(TOSOH CORPORATION)製、 HLC-8120GPC ‧ Analysis device: East TOSOH CORPORATION, HLC-8120GPC
‧管柱:東社(TOSOH CORPORATION)製、G7000HXL+GMHXL+GMHXL ‧Tube: East TOSOH CORPORATION, G7000H XL +GMH XL +GMH XL
‧管柱尺寸:各7.8mmψ×30cm計90cm ‧Tube size: 7.8mm each ψ×30cm 90cm
‧管柱溫度:40℃ ‧column temperature: 40 ° C
‧流量:0.8ml/min ‧Flow: 0.8ml/min
‧注入量:100μl ‧Injection amount: 100μl
‧溶離液:四氫呋喃 ‧Dissolved solution: tetrahydrofuran
‧檢出器:微差折射計(RI) ‧Detector: differential refractometer (RI)
‧標準樣品:聚苯乙烯 ‧Standard sample: polystyrene
<偏光薄膜(1)之製作> <Production of polarizing film (1)>
為製作薄型偏光層,首先,藉由延伸溫度130℃之空中補助延伸,讓於非晶形PET基材成膜有9μm厚之PVA層的積層體生成延生積層體,其次,藉由讓延伸積層體染色而生成著色積層體,進而使著色積層體於延伸溫度65度之硼酸水中延伸,生成包含以總延伸倍率為5.94倍方式而與非晶形PET基材一體地延伸之4μm厚PVA層之光學薄膜積層體。藉由此種2段延伸,可生成包含厚度4μm之PVA層之光學薄膜積層體,其係構成經成膜於非晶形PET基材之PVA層的PVA分子呈高度配向,且以染色而吸附之碘係以多碘離子錯合體單一方向地高度配向之高機能偏光層。進而,將聚乙烯醇系接著劑塗佈於該光學薄膜積層體之偏光層表面,同時貼合經皂化之40μm厚三醋酸纖維素薄膜後,剝離 非晶形PET基材,製作使用薄型偏光層之偏光薄膜。以下,將其稱為薄型偏光薄膜(1)。 In order to produce a thin polarizing layer, first, a laminate of a PVA layer having a thickness of 9 μm is formed on an amorphous PET substrate by an extension of a temperature of 130 ° C to form an extended laminated body, and secondly, by extending the laminated body The coloring layer is formed by dyeing, and the colored layered body is further extended in boric acid water having an extension temperature of 65 degrees to form an optical film comprising a 4 μm thick PVA layer extending integrally with the amorphous PET substrate at a total stretching ratio of 5.94 times. Laminated body. By such two-stage extension, an optical thin film laminate comprising a PVA layer having a thickness of 4 μm can be formed, which constitutes a PVA molecule which is formed into a PVA layer of an amorphous PET substrate, which is highly aligned and adsorbed by dyeing. Iodine is a highly functional polarizing layer that is highly aligned in a single direction with a polyiodide ion complex. Further, a polyvinyl alcohol-based adhesive is applied onto the surface of the polarizing layer of the optical film laminate, and the saponified 40 μm-thick cellulose triacetate film is bonded thereto and then peeled off. An amorphous PET substrate was used to produce a polarizing film using a thin polarizing layer. Hereinafter, this is referred to as a thin polarizing film (1).
<偏光薄膜(2)之製作> <Production of polarizing film (2)>
將厚度80μm聚乙烯醇薄膜置於速度比相異之輥筒間,於30℃且0.3%濃度之碘溶液中染色1分鐘,同時延伸至3倍。之後,於包含60℃且4%濃度之硼酸、10%濃度之碘化鉀的水溶液中,浸漬0.5分鐘,同時總延伸倍率延伸至6倍。其次,藉由於包含30℃且1.5%濃度之碘化鉀之水溶液中浸漬10秒而加以洗淨,之後,以50℃進行乾燥4分鐘,製得厚度20μm之偏光子。於該偏光子之單面,藉由聚乙烯醇系接著劑貼合經皂化之厚度40μm之三醋酸纖維素薄膜,製作偏光薄膜。以下,將其稱為TAC係偏光薄膜(2)。 A polyethylene film having a thickness of 80 μm was placed between rolls of different speed ratios, and dyed in a 0.3% iodine solution at 30 ° C for 1 minute while extending to 3 times. Thereafter, it was immersed in an aqueous solution containing boric acid at a concentration of 4% and a 10% strength of potassium iodide at 60 ° C for 0.5 minutes while the total stretching ratio was extended to 6 times. Next, it was washed by immersing in an aqueous solution containing potassium iodide at a concentration of 1.5% and a concentration of 1.5% at 30 ° C for 10 seconds, and then dried at 50 ° C for 4 minutes to obtain a polarizer having a thickness of 20 μm. On one side of the polarizer, a saponified triacetate film having a thickness of 40 μm was bonded to a single side of the polarizer to prepare a polarizing film. Hereinafter, this is called a TAC-based polarizing film (2).
製造例1 Manufacturing example 1
<丙烯醯系聚合物(A-1)之製作> <Production of propylene-based polymer (A-1)>
配備有攪拌器具、溫度計、氮氣導入管、冷卻器之4個反應容器中,加入含有丙烯酸丁酯99份、丙烯酸4-羥丁基1份之單體混合物。進而,將作為起始劑且相對於前述單體混合物(固形份)100份,2,2’-偶氮雙異丁腈0.1份與醋酸乙酯一起加入,邊緩慢攪拌,邊導入氮,進行氮置換後,將反應容器內之液溫保持於60℃附近,進行7小時聚合反應。之後,於所得之反應液加入醋酸乙酯,調整為固形濃度30%,調製重量平均分子量140萬之丙烯醯系聚合物(A-1)之溶液。 A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was placed in four reaction vessels equipped with a stirring device, a thermometer, a nitrogen gas introduction tube, and a cooler. Further, as a starter, 100 parts of 2,2'-azobisisobutyronitrile, and 0.1 part of 2,2'-azobisisobutyronitrile were added together with ethyl acetate as a starter, and nitrogen was introduced while slowly stirring. After the nitrogen substitution, the liquid temperature in the reaction vessel was maintained at around 60 ° C, and polymerization reaction was carried out for 7 hours. Thereafter, ethyl acetate was added to the obtained reaction solution to adjust the solid concentration to 30%, and a solution of the propylene-based polymer (A-1) having a weight average molecular weight of 1.4 million was prepared.
製造例2 Manufacturing Example 2
<丙烯醯系聚合物(A-2)之製作> <Production of propylene-based polymer (A-2)>
配備有攪拌器具、溫度計、氮氣導入管、冷卻器之4個反應容器中,加入含有丙烯酸丁酯99份、丙烯酸2-羥丁基0.5份及丙烯酸0.5份之單體混合物。進而,將作為起始劑且相對於前述單體混合物(固形份)100份,2,2’-偶氮雙異丁腈0.1份與醋酸乙酯一起加入,邊緩慢攪拌,邊導入氮,進行氮置換後,將反應容器內之液溫保持於60℃附近,進行7小時聚合反應。之後,於所得之反應液加入醋酸乙酯,調整為固形濃度30%,調製重量平均分子量140萬之丙烯醯系聚合物(A-2)之溶液。 A monomer mixture containing 99 parts of butyl acrylate, 0.5 part of 2-hydroxybutyl acrylate, and 0.5 part of acrylic acid was placed in four reaction vessels equipped with a stirring device, a thermometer, a nitrogen gas introduction tube, and a cooler. Further, as a starter, 100 parts of 2,2'-azobisisobutyronitrile, and 0.1 part of 2,2'-azobisisobutyronitrile were added together with ethyl acetate as a starter, and nitrogen was introduced while slowly stirring. After the nitrogen substitution, the liquid temperature in the reaction vessel was maintained at around 60 ° C, and polymerization reaction was carried out for 7 hours. Thereafter, ethyl acetate was added to the obtained reaction solution to adjust the solid concentration to 30%, and a solution of the propylene-based polymer (A-2) having a weight average molecular weight of 1.4 million was prepared.
實施例1 Example 1
(黏著劑組成物之製作) (Production of adhesive composition)
相對於製造例1所製得之丙烯醯系聚合物(A-1)溶液之固形份100份,摻合三甲基丙基胺雙(三氟甲烷磺醯)醯亞胺(東京化成工業)0.2份,進而,摻合三羥丙烷二甲基苯二異氰酸二甲基苯酯(三井化學製: D110N(TAKENATETM))0.1份,及過氧化二苯甲醯基0.3份、γ-環氧丙氧基丙基甲氧基矽烷(信越化學工業製:KBM-403)0.075份,調製丙烯醯系黏著劑溶液。 100 parts of the solid portion of the acrylonitrile-based polymer (A-1) solution prepared in Production Example 1 was blended with trimethylpropylamine bis(trifluoromethanesulfonate) quinone imine (Tokyo Chemical Industry Co., Ltd.) 0.2 parts, further blended with dimethyl phenyl trimethylol dimethyl phenyl diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.: 0.1 parts of D110N (TAKENATE TM )), 0.3 parts of benzoyl peroxide, γ-glycidoxypropyl methoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403), 0.075 parts, and prepared propylene oxime system Adhesive solution.
(附黏著劑層之偏光薄膜之製作) (Production of polarizing film with adhesive layer)
其次,藉由噴注式刮刀塗佈機將前述丙烯醯係黏著劑溶液,均一地塗於以矽氧烷系剝離劑處理過後之聚對苯二甲酸乙二酯(隔離膜)表面,並以155℃之空氣循環式恆溫爐乾燥2分鐘,於隔離膜表面形成厚度20μm之黏著劑層。再者,於以前述做成之薄型偏光薄膜(1)之偏光子其偏光層側,轉移 形成於隔離膜上之黏著劑層,製作附黏著劑層之偏光薄膜。 Next, the acryl-based adhesive solution is uniformly applied to the surface of the polyethylene terephthalate (separator) treated with a decane-based release agent by a jet knife coater, and The film was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the separator. Further, the polarizer of the thin polarizing film (1) formed as described above is transferred to the polarizing layer side. The adhesive layer formed on the separator is used to form a polarizing film with an adhesive layer.
實施例2~20、比較例1~4 Examples 2 to 20 and Comparative Examples 1 to 4
除於實施例1中調製黏著劑組成物時,讓各成分之種類或使用量如表1所示般加以變化,以及製作附黏著劑層之偏光薄膜時,讓偏光薄膜之種類如表1所示般加以變化,其餘係與實施例1同樣地製作附黏著劑層之偏光薄膜。 When the adhesive composition was prepared in Example 1, the type or amount of each component was changed as shown in Table 1, and when a polarizing film with an adhesive layer was prepared, the type of the polarizing film was as shown in Table 1. In the same manner as in Example 1, a polarizing film with an adhesive layer was prepared in the same manner as in the above.
對於前述實施例及比較例所得之附黏著劑層之偏光薄膜,進行以下之評價。將評價結果顯示於表1。 The polarizing films with the adhesive layers obtained in the above Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Table 1.
<表面電阻值:初期> <surface resistance value: initial stage>
剝離附黏著劑層之偏光薄膜之隔離膜後,使用三菱化学社(MITSUBISHI CHEMICAL ANALYTECH CO.,LTD.)製MCP-HT450來測量黏著劑表面之表面電阻值(Ω/□)。 After peeling off the separator of the polarizing film with the adhesive layer, use Mitsubishi Chemical MCP-HT450 was manufactured by MITSUBISHI CHEMICAL ANALYTECH CO., LTD. to measure the surface resistance value (Ω/□) of the surface of the adhesive.
<抗靜電評價> <Antistatic evaluation>
將所製得之附黏著劑層之偏光薄膜切斷成100mm×100mm之大小,貼附于液晶面板。將該面板置於具有10000cd之亮度的背光上,使用靜電產生裝置之ESD(SANKI社製、ESD-8012A),產生5kv之靜電,藉此引起液晶之配向紊亂。使用瞬間多點測光分析儀(大塚電子社製、MCPD-3000),測量該配向不良產生之顯示不良的回復時間(秒),並以下述基準加以評價。 The polarizing film of the obtained adhesive layer was cut into a size of 100 mm × 100 mm, and attached to a liquid crystal panel. The panel was placed on a backlight having a brightness of 10,000 cd, and ESD (manufactured by SANKI Corporation, ESD-8012A) using an electrostatic generating device was used to generate static electricity of 5 kV, thereby causing alignment disorder of the liquid crystal. The recovery time (seconds) of the display failure due to the alignment failure was measured using an instantaneous multi-point photometric analyzer (manufactured by Otsuka Electronics Co., Ltd., MCPD-3000), and evaluated based on the following criteria.
◎:顯示不良不到1秒即消失。 ◎: The display disappeared in less than 1 second.
○:顯示不良在1秒以上、未達10秒即消失。 ○: The display failure disappeared after 1 second or more and less than 10 seconds.
×:顯示不良10秒以上才消失。 ×: The display disappears for 10 seconds or more before disappearing.
<耐久性> <Durability>
將附黏著劑層之偏光薄膜之隔離膜剝離,使用積層裝置將之貼附於厚度0.7mm之無鹼玻璃(社(CORNING INCORPORATED)製、1737)。其次,以50℃、5atm,進行15分鐘之高壓釜處理,讓前述附黏著劑層之偏光薄膜完全密著於無鹼玻璃。接著,將之分別投入80℃之加熱爐(加熱)及60℃/90%RH之恆溫恆濕機(加濕)之條件下,以下述基準評價500小時後之偏光薄膜有無剝離。 The separator of the polarizing film with the adhesive layer was peeled off, and attached to an alkali-free glass having a thickness of 0.7 mm using a laminating device ( CORNING INCORPORATED, 1737). Next, the autoclave treatment was carried out at 50 ° C and 5 atm for 15 minutes to completely adhere the polarizing film of the adhesive layer to the alkali-free glass. Subsequently, the mixture was placed in a heating oven (heating) at 80 ° C and a constant temperature and humidity machine (humidification) at 60 ° C / 90% RH, and the polarizing film was peeled off after 500 hours.
◎:確認完全無剝離。 ◎: It was confirmed that there was no peeling at all.
○:確認目視下無法確認程度之剝離。 ○: It was confirmed that the degree of peeling could not be confirmed under visual observation.
△:確認目視下可確認之微小剝離。 △: A small peeling which can be confirmed by visual observation was confirmed.
×:確認明顯剝離。 ×: Obvious peeling was confirmed.
<偏光度之測量> <Measurement of the degree of polarization>
將附黏著劑層之偏光薄膜之隔離膜剝離,使用積層裝置將之貼附於厚度0.7mm之無鹼玻璃(社(CORNING INCORPORATED)製、1737)。其次,以50℃、0.5MPa,進行15分鐘之高壓釜處理,讓前述附黏著劑層之偏光薄膜完全密著於無鹼玻璃。接著,將之投入60℃/90%RH之恆溫恆濕機500小時。使用日本分光(股份有限公司)製之V7100測量投入前及投入後之偏光薄膜之偏光度,求得變化量△P=(投入前之偏光度)-(投入後之偏光後)。 The separator of the polarizing film with the adhesive layer was peeled off, and attached to an alkali-free glass having a thickness of 0.7 mm using a laminating device ( CORNING INCORPORATED, 1737). Next, the autoclave treatment was carried out for 15 minutes at 50 ° C and 0.5 MPa, and the polarizing film of the adhesive layer was completely adhered to the alkali-free glass. Next, it was put into a constant temperature and humidity machine of 60 ° C / 90% RH for 500 hours. The V7100 manufactured by JASCO Corporation (Comp.) was used to measure the polarization of the polarizing film before and after the input, and the amount of change ΔP = (the degree of polarization before the input) - (after the polarization after the input).
Claims (17)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW106130320A TWI646167B (en) | 2013-08-26 | 2013-08-26 | Polarizing film with adhesive layer and image display device |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW106130320A TWI646167B (en) | 2013-08-26 | 2013-08-26 | Polarizing film with adhesive layer and image display device |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201809185A TW201809185A (en) | 2018-03-16 |
TWI646167B true TWI646167B (en) | 2019-01-01 |
Family
ID=62189754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW106130320A TWI646167B (en) | 2013-08-26 | 2013-08-26 | Polarizing film with adhesive layer and image display device |
Country Status (1)
Country | Link |
---|---|
TW (1) | TWI646167B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201235434A (en) * | 2010-12-13 | 2012-09-01 | Nitto Denko Corp | Adhesive composition for optical films, adhesive layer for optical films, adhesive optical film and image display device |
TW201331319A (en) * | 2011-10-19 | 2013-08-01 | Nitto Denko Corp | Water-dispersible acrylic adhesive composition, adhesive layer, and adhesive sheet |
-
2013
- 2013-08-26 TW TW106130320A patent/TWI646167B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201235434A (en) * | 2010-12-13 | 2012-09-01 | Nitto Denko Corp | Adhesive composition for optical films, adhesive layer for optical films, adhesive optical film and image display device |
TW201331319A (en) * | 2011-10-19 | 2013-08-01 | Nitto Denko Corp | Water-dispersible acrylic adhesive composition, adhesive layer, and adhesive sheet |
Also Published As
Publication number | Publication date |
---|---|
TW201809185A (en) | 2018-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101912968B1 (en) | Polarizing film with adhesive layer and image display apparatus | |
TWI630426B (en) | Polarizing film with adhesive layer and image display device | |
TWI627253B (en) | Polarizing film with adhesive layer and image display device | |
TWI606105B (en) | Adhesive composition for optical film, adhesive layer for optical film, optical film with adhesive layer, and image display device | |
TWI579356B (en) | Adhesive composition, adhesive layer, polarizing film with adhesive layer, and image forming device (2) | |
JP5860673B2 (en) | Adhesive composition, adhesive layer, polarizing plate with adhesive layer, and image forming apparatus | |
TWI441884B (en) | An adhesive composition, an adhesive layer, a polarizing film having an adhesive layer, and an image forming apparatus | |
TW201329182A (en) | Adhesive composition, adhesive layer, polarizing film having adhesive layer, and image forming device | |
JP5607691B2 (en) | Polarizing film with adhesive layer and image display device | |
JP6373299B2 (en) | Polarizing film with adhesive layer and image display device | |
TWI602896B (en) | Polarizing film with adhesive layer and image display device | |
JP6876544B2 (en) | Adhesive polarizing plate and image display device | |
JP2016028289A (en) | Pressure-sensitive adhesive polarizing plate and image display | |
JP2016028288A (en) | Adhesive polarizing plate and image display device | |
TWI646167B (en) | Polarizing film with adhesive layer and image display device | |
JP5921641B2 (en) | Polarizing film with adhesive layer and image display device | |
JP6920502B2 (en) | Adhesive polarizing plate and image display device | |
JP6931339B2 (en) | Polarizing film with adhesive layer and image display device | |
JP6724065B2 (en) | Polarizing film with adhesive layer and image display device | |
JP2016028287A (en) | Pressure-sensitive adhesive polarizing plate and image display | |
JP5947341B2 (en) | Polarizing film with adhesive layer and image display device | |
WO2015025421A1 (en) | Polarizing film with adhesive layer, and image display device | |
KR20190086428A (en) | Polarizing film with adhesive layer and image display device |