TWI667314B - Reagent, polarizing film, liquid crystal panel, optical film and image display device - Google Patents
Reagent, polarizing film, liquid crystal panel, optical film and image display device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/007—Polyrotaxanes; Polycatenanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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Abstract
本發明提供一種耐水性得到提高之活性能量線硬化型之接著劑。該接著劑包含活性能量線硬化性成分及聚輪烷,且該聚輪烷具有活性能量線聚合性基。於一個實施形態中,上述聚輪烷具有環狀分子、貫通該環狀分子之開口部之直鏈狀分子、及以該環狀分子不自該直鏈狀分子脫離之方式配置於該直鏈狀分子之兩端之封端基,且該環狀分子具有上述活性能量線聚合性基。 The present invention provides an active energy ray-curing type adhesive which is improved in water resistance. The adhesive includes an active energy ray-curable component and a polyrotaxane, and the polyrotaxane has an active energy ray polymerizable group. In one embodiment, the polyrotaxane has a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and is disposed in the linear chain so that the cyclic molecule is not detached from the linear molecule. A terminal group at both ends of the molecule, and the cyclic molecule has the above active energy ray polymerizable group.
Description
本發明係關於一種接著劑。該接著劑例如可用於偏光膜、各種光學膜及液晶單元之積層。又,本發明係關於一種包含該偏光膜、該各種光學膜、或該液晶單元之圖像顯示裝置。 The present invention is directed to an adhesive. The adhesive can be used, for example, for a laminate of a polarizing film, various optical films, and liquid crystal cells. Further, the present invention relates to an image display device comprising the polarizing film, the various optical films, or the liquid crystal cell.
於作為代表性之圖像顯示裝置之液晶顯示裝置中,起因於其圖像形成方式而於液晶單元之兩側配置有偏光元件。偏光元件通常係以至少於單面貼合有保護膜之偏光膜之形態使用。 In a liquid crystal display device which is a representative image display device, a polarizing element is disposed on both sides of a liquid crystal cell due to an image forming method. The polarizing element is usually used in the form of a polarizing film in which a protective film is bonded to at least one side.
作為用以將保護膜貼合於偏光元件之接著劑,提出有將聚乙烯醇系材料溶解於水而獲得之水系接著劑(例如,專利文獻1)或活性能量線硬化型接著劑(例如,專利文獻2)。根據活性能量線硬化型接著劑,與水系接著劑相比有如下優點:於偏光元件與保護膜之貼合時無需乾燥步驟;即便對於水分率較低之偏光元件亦獲得良好之接著性等。 As a binder for bonding a protective film to a polarizing element, a water-based adhesive obtained by dissolving a polyvinyl alcohol-based material in water (for example, Patent Document 1) or an active energy ray-curable adhesive (for example, Patent Document 2). According to the active energy ray-curable adhesive, compared with the water-based adhesive, there is an advantage that a drying step is not required when the polarizing element is bonded to the protective film, and good adhesion or the like is obtained even for a polarizing element having a low moisture content.
然而,關於先前之活性能量線硬化型接著劑(例如,專利文獻2),亦有於加水環境下等嚴酷環境下接著變得不充分之情形,有要求進而高等級之耐水性之情形。 However, the conventional active energy ray-curable adhesive (for example, Patent Document 2) may be insufficiently formed in a severe environment such as a water-added environment, and there is a demand for a high-grade water resistance.
另一方面,提出有一種包含(甲基)丙烯酸酯聚合物、交聯劑及聚輪烷,且適於光學構件之黏著劑組合物(例如,專利文獻3)。然而,認為該黏著劑組合物未表現出與耐水性相關之課題,且就該組成或用途之方面而言亦不易產生耐水性課題。 On the other hand, an adhesive composition containing a (meth) acrylate polymer, a crosslinking agent, and a polyrotaxane and being suitable for an optical member has been proposed (for example, Patent Document 3). However, it is considered that the adhesive composition does not exhibit a problem related to water resistance, and it is difficult to cause a water resistance problem in terms of the composition or use.
[專利文獻1]日本專利特開2005-338343號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-338343
[專利文獻2]日本專利特開2010-78700號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-78700
[專利文獻3]日本專利特開2013-56963號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-56963
本發明提供一種耐水性得到提高之活性能量線硬化型之接著劑。 The present invention provides an active energy ray-curing type adhesive which is improved in water resistance.
根據本發明,提供一種包含活性能量線硬化性成分及聚輪烷,且該聚輪烷具有活性能量線聚合性基之接著劑。 According to the present invention, there is provided an adhesive comprising an active energy ray-curable component and a polyrotaxane, and the polyrotaxane has an active energy ray polymerizable group.
於一個實施形態中,上述聚輪烷具有環狀分子、貫通該環狀分子之開口部之直鏈狀分子、及以該環狀分子不自該直鏈狀分子脫離之方式配置於該直鏈狀分子之兩端之封端基,且該環狀分子具有上述活性能量線聚合性基。 In one embodiment, the polyrotaxane has a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and is disposed in the linear chain so that the cyclic molecule is not detached from the linear molecule. A terminal group at both ends of the molecule, and the cyclic molecule has the above active energy ray polymerizable group.
於一個實施形態中,上述活性能量線硬化性成分之重量平均分子量為20~99,000。 In one embodiment, the active energy ray-curable component has a weight average molecular weight of 20 to 99,000.
於一個實施形態中,上述環狀分子進而具有疏水性修飾基。 In one embodiment, the cyclic molecule further has a hydrophobic modifying group.
於一個實施形態中,上述接著劑包括含羥基之單體作為上述活性能量線硬化性成分。 In one embodiment, the adhesive includes a hydroxyl group-containing monomer as the active energy ray-curable component.
於一個實施形態中,上述聚輪烷之調配量相對於活性能量線硬化性成分與聚輪烷之合計100重量份為2重量份~50重量份。 In one embodiment, the amount of the polyrotaxane is from 2 parts by weight to 50 parts by weight based on 100 parts by weight of the total of the active energy ray-curable component and the polyrotaxane.
於一個實施形態中,上述聚輪烷於1分子中所具有之活性能量線聚合性基之個數為2個~1280個。 In one embodiment, the number of active energy ray polymerizable groups of the polyrotaxane in one molecule is from 2 to 1,280.
於一個實施形態中,上述接著劑進而包含光聚合起始劑。 In one embodiment, the adhesive further includes a photopolymerization initiator.
於一個實施形態中,上述活性能量線硬化性成分為自由基聚合性單體。 In one embodiment, the active energy ray-curable component is a radical polymerizable monomer.
於一個實施形態中,上述活性能量線聚合性基為自由基聚合性基。 In one embodiment, the active energy ray polymerizable group is a radical polymerizable group.
根據本發明之另一態樣,提供一種偏光膜。該偏光膜包含偏光元件、及經由接著劑層而設置於該偏光元件之至少單面之保護膜。該接著劑層係藉由上述接著劑而形成。 According to another aspect of the present invention, a polarizing film is provided. The polarizing film includes a polarizing element and a protective film provided on at least one side of the polarizing element via an adhesive layer. The adhesive layer is formed by the above-mentioned adhesive.
根據本發明之另一態樣,提供一種液晶面板。該液晶面板包含液晶單元、及經由接著劑層而設置於該液晶單元之至少單面之偏光元件。該接著劑層係藉由上述接著劑而形成。 According to another aspect of the present invention, a liquid crystal panel is provided. The liquid crystal panel includes a liquid crystal cell and a polarizing element provided on at least one side of the liquid crystal cell via an adhesive layer. The adhesive layer is formed by the above-mentioned adhesive.
根據本發明之另一態樣,提供一種光學膜。該光學膜具有藉由上述接著劑而形成之接著劑層。 According to another aspect of the present invention, an optical film is provided. The optical film has an adhesive layer formed by the above-mentioned adhesive.
根據本發明之另一態樣,提供一種圖像顯示裝置。該圖像顯示裝置包含上述偏光膜或上述液晶面板。 According to another aspect of the present invention, an image display device is provided. The image display device includes the above polarizing film or the liquid crystal panel.
根據本發明,藉由調配活性能量線硬化性成分及具有活性能量線聚合性基之聚輪烷,可獲得耐水性得到提高之活性能量線硬化型之接著劑。 According to the present invention, an active energy ray-curable adhesive having improved water resistance can be obtained by blending an active energy ray-curable component and a polyrotaxane having an active energy ray-polymerizable group.
本發明之接著劑包含活性能量線硬化性成分、及具有活性能量線聚合性基之聚輪烷。本發明之接著劑為活性能量線硬化型,例如能以紫外線硬化型、電子束硬化型、可見光硬化型之態樣使用,較佳為以紫外線硬化型之態樣使用。雖然於以電子束硬化型使用之情形時並 不特別需要進而包含光聚合起始劑,但於以紫外線硬化型、可見光硬化型使用之情形時,本發明之接著劑可進而包含光聚合起始劑。 The adhesive of the present invention contains an active energy ray-curable component and a polyrotaxane having an active energy ray polymerizable group. The adhesive of the present invention is an active energy ray-curable type, and can be used, for example, in an ultraviolet curing type, an electron beam curing type, or a visible light curing type, and is preferably used in an ultraviolet curing type. Although used in the case of electron beam hardening type It is not particularly necessary to further contain a photopolymerization initiator, but in the case of use in an ultraviolet curing type or a visible light curing type, the adhesive of the present invention may further contain a photopolymerization initiator.
作為上述活性能量線硬化性成分,可使用具有活性能量線聚合性基之任意適當之硬化性化合物。硬化方式並無限定,可為自由基聚合方式,亦可為陽離子聚合方式。就與聚輪烷之相溶性及材料選擇之多樣性等觀點而言,可較佳地使用具有自由基聚合性基之自由基聚合性單體。作為自由基聚合性基,例如可列舉(甲基)丙烯醯基、(甲基)丙烯醯氧基等。再者,於本說明書中,所謂(甲基)丙烯醯基意指甲基丙烯醯基及/或丙烯醯基。 As the active energy ray-curable component, any suitable curable compound having an active energy ray-polymerizable group can be used. The curing method is not limited, and may be a radical polymerization method or a cationic polymerization method. From the viewpoints of compatibility with polyrotaxane and diversity of material selection, a radical polymerizable monomer having a radical polymerizable group can be preferably used. Examples of the radical polymerizable group include a (meth)acrylonitrile group and a (meth)acryloxy group. Further, in the present specification, the (meth)acryl fluorenyl group means a methacryl fluorenyl group and/or an acryl fluorenyl group.
作為上述活性能量線硬化性成分之重量平均分子量,可採用任意適當之值。上述重量平均分子量例如以GPC(Gel Permeation Chromatography,凝膠滲透層析法)換算值計為20~99,000,較佳為40~10000,更佳為60~1000,最佳為100~600。 Any suitable value can be employed as the weight average molecular weight of the active energy ray-curable component. The weight average molecular weight is, for example, 20 to 99,000, preferably 40 to 10,000, more preferably 60 to 1,000, and most preferably 100 to 600, in terms of GPC (Gel Permeation Chromatography).
作為上述活性能量線硬化性成分,可較佳地使用含羥基之單體。藉由使用含羥基之單體,可獲得對被接著體之良好之接著性及與聚輪烷之良好之相溶性。作為含羥基之單體之具體例,可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、丙烯酸2-羥基-3苯氧基酯、1,4-環己烷甲醇單丙烯酸酯等(甲基)丙烯酸羥基烷基酯;N-羥基乙基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺等N-羥基烷基(甲基)丙烯醯胺;(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-羥基-3-第三丁基苯氧基丙酯、2-羥基-3-苯基聚乙二醇(甲基)丙烯酸丙酯等含有芳香環及羥基之(甲基)丙烯酸酯;N-(2,2-二甲氧基-1-羥基乙基)-(甲基)丙烯醯胺、對羥基苯基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺等。其中,較佳為(甲基)丙烯酸4-羥基丁酯及N-羥基乙基(甲 基)丙烯醯胺。該等單體可單獨使用1種,或者組合2種以上而使用。 As the active energy ray-curable component, a hydroxyl group-containing monomer can be preferably used. By using a hydroxyl group-containing monomer, good adhesion to the adherend and good compatibility with the polyrotaxane can be obtained. Specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl acrylate. a hydroxyalkyl (meth) acrylate such as -3 phenoxy ester or 1,4-cyclohexane methanol monoacrylate; N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl (methyl) N-hydroxyalkyl (meth) acrylamide such as acrylamide; 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-t-butyl (meth) acrylate (meth) acrylate containing an aromatic ring and a hydroxyl group, such as phenoxypropyl ester, 2-hydroxy-3-phenyl polyethylene glycol (meth) propyl acrylate; N-(2,2-dimethoxy group) 1-hydroxyethyl)-(meth)acrylamide, p-hydroxyphenyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl-N-propane (Methyl) acrylamide and the like. Among them, 4-hydroxybutyl (meth)acrylate and N-hydroxyethyl (A) are preferred. Base) acrylamide. These monomers may be used alone or in combination of two or more.
作為其他較佳之活性能量線硬化性成分,可列舉不含羥基之N-取代醯胺系單官能性單體。藉由使用該N-取代醯胺系單體,可獲得對保護膜之良好之接著性及與聚輪烷之良好之相溶性。該N-取代醯胺系單體係由下述通式(1)所表示。 As another preferable active energy ray-curable component, an N-substituted guanamine-based monofunctional monomer which does not contain a hydroxyl group is mentioned. By using the N-substituted amide-based monomer, good adhesion to the protective film and good compatibility with the polyrotaxane can be obtained. The N-substituted guanamine system is represented by the following formula (1).
CH2=C(R1)-CONR2(R3) (1) CH 2 =C(R 1 )-CONR 2 (R 3 ) (1)
(R1表示氫原子或甲基,R2表示氫原子或可具有巰基、胺基或四級銨基之碳數1~4之直鏈或支鏈之烷基,R3表示氫原子或碳數1~4之直鏈或支鏈之烷基;然而,R2、R3同時為氫原子之情形除外;或者R2、R3鍵結而形成亦可包含氧原子之五員環或六員環)。 (R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms which may have a mercapto group, an amine group or a quaternary ammonium group, and R 3 represents a hydrogen atom or carbon a straight or branched alkyl group of 1 to 4; however, R 2 and R 3 are bonded to each other at the same time; or R 2 and R 3 are bonded to form a five-membered ring or a six-membered ring. Member ring).
作為上述通式(1)中之R2或R3中之碳數1~4之直鏈或支鏈之烷基,例如可列舉:甲基、乙基、異丙基、第三丁基等,作為具有胺基之烷基,可列舉胺甲基、胺乙基等。又,R2、R3於鍵結而形成亦可包含氧原子之五員環或六員環之情形時,可為具有氮之雜環。作為該雜環,可列舉:嗎啉環、哌啶環、吡咯啶環、哌環等。 Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R 2 or R 3 in the above formula (1) include a methyl group, an ethyl group, an isopropyl group, and a third butyl group. Examples of the alkyl group having an amine group include an amine methyl group and an amine ethyl group. Further, when R 2 and R 3 are bonded to form a five-membered ring or a six-membered ring which may contain an oxygen atom, it may be a heterocyclic ring having nitrogen. Examples of the heterocyclic ring include a morpholine ring, a piperidine ring, a pyrrolidine ring, and a piperidine. Ring and so on.
作為上述不含羥基之N-取代醯胺系單體之具體例,例如可列舉:N-甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、胺甲基(甲基)丙烯醯胺、胺乙基(甲基)丙烯醯胺、巰甲基(甲基)丙烯醯胺、巰乙基(甲基)丙烯醯胺等。又,作為具有雜環之含雜環單體,例如可列舉:N-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯啶、N-乙烯基吡咯啶酮(NVP)等。該等單體可單獨使用1種,或者組合2種以上而使用。 Specific examples of the N-substituted amide-based monomer having no hydroxyl group include N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N. , N-diethyl (meth) acrylamide, N-isopropyl acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, amine methyl ( Methyl) acrylamide, amine ethyl (meth) acrylamide, hydrazine methyl (meth) acrylamide, decyl ethyl (meth) acrylamide, and the like. Further, examples of the heterocyclic ring-containing monomer having a hetero ring include N-propenylmorphomorpholine, N-propenylhydrazine piperidine, N-methylpropenylpiperidine, and N-propenylpyridylpyridinium. , N-vinylpyrrolidone (NVP) and the like. These monomers may be used alone or in combination of two or more.
作為進而其他較佳之活性能量線硬化性成分,可列舉多官能性單體例如烴系或烴醚系之多官能性單體。烴系或烴醚系之多官能性單體係將以碳數4~100之烴基或烴醚基作為主骨架之多元醇之羥基加以 (甲基)丙烯酸酯化而成之化合物,就交聯所決定之接著性之方面而言較佳。作為上述多元醇之烴基,可列舉直鏈或支鏈之脂肪族烴基、芳香族烴基、脂環族烴基、及將該等烴基組合而成之烴基,作為上述烴醚基,可列舉將該等烴基加以醚化而成者。又,作為以烴醚基作為主骨架之多元醇,可列舉對上述多元醇加成碳數2~4之環氧烷而成之化合物(加成數1~30)、由碳數2~4之環氧烷所獲得之聚伸烷基二醇(加成數1~30)等。該等單體可單獨使用1種,或者組合2種以上而使用。 Further, other preferred active energy ray-curable components include polyfunctional monomers such as hydrocarbon-based or hydrocarbon-ether-based polyfunctional monomers. A hydrocarbon- or hydrocarbon ether-based polyfunctional single system will be a hydroxyl group of a polyol having a hydrocarbon group of 4 to 100 carbon atoms or a hydrocarbon ether group as a main skeleton. The (meth) acrylated compound is preferred in terms of the adhesion determined by crosslinking. The hydrocarbon group of the above-mentioned polyol may, for example, be a linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a hydrocarbon group in which the hydrocarbon groups are combined, and examples of the hydrocarbon ether group include The hydrocarbon group is etherified. Further, examples of the polyol having a hydrocarbon ether group as a main skeleton include a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to the above polyol (addition number: 1 to 30), and a carbon number of 2 to 4 A polyalkylene glycol obtained by alkylene oxide (addition number: 1 to 30) or the like. These monomers may be used alone or in combination of two or more.
作為上述烴系之二官能性單體之具體例,例如可列舉:1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,9-壬二醇(甲基)丙烯酸酯等伸烷基二醇之二(甲基)丙烯酸酯;環己烷二甲醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯等具有脂環族烴基之二醇化合物之二(甲基)丙烯酸酯;雙酚A二(甲基)丙烯酸酯等具有芳香族烴基之二醇化合物之二(甲基)丙烯酸酯等。 Specific examples of the hydrocarbon-based difunctional monomer include, for example, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1, a di(meth) acrylate such as 6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate or 1,9-nonanediol (meth)acrylate a bis(meth) acrylate of a diol compound having an alicyclic hydrocarbon group such as cyclohexane dimethanol di(meth) acrylate or tricyclodecane dimethanol di(meth) acrylate; bisphenol A di(meth)acrylate or the like of a diol compound having an aromatic hydrocarbon group such as A di(meth)acrylate.
作為上述烴醚系之二官能性單體之具體例,例如可列舉:烷氧基化己二醇二(甲基)丙烯酸酯、烷氧基化環己烷二甲醇二(甲基)丙烯酸酯、烷氧基化二(甲基)丙烯酸酯、烷氧基化新戊二醇二(甲基)丙烯酸酯、烷氧基化雙酚A二(甲基)丙烯酸酯等對上述烴系之二官能性單體中記載之伸烷基二醇或二醇化合物加成環氧烷而成之化合物之二(甲基)丙烯酸酯等。又,作為烴醚系之二官能性單體之具體例,可列舉:二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯等聚伸烷基二醇之二(甲基)丙烯酸酯、或二二醇二(甲基)丙烯酸酯等。 Specific examples of the above-mentioned hydrocarbon ether-based difunctional monomer include alkoxylated hexanediol di(meth)acrylate and alkoxylated cyclohexanedimethanol di(meth)acrylate. Alkoxylated di(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, alkoxylated bisphenol A di(meth)acrylate, etc. A di(meth)acrylate or the like of a compound obtained by adding an alkylene glycol or a diol compound to an alkylene oxide as described in the functional monomer. Further, specific examples of the hydrocarbon ether-based difunctional monomer include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(a). Di(meth)acrylic acid of a polyalkylene glycol such as acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate or dipropylene glycol di(meth)acrylate Ester, or two Glycol di(meth)acrylate or the like.
又,作為烴系或烴醚系之三官能性單體及四官能性單體之具體例,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲 基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、三羥甲基丙烷四(甲基)丙烯酸酯等三醇或四醇化合物之三(甲基)丙烯酸酯或四(甲基)丙烯酸酯、或對上述三醇或四醇化合物加成環氧烷而成之化合物之三(甲基)丙烯酸酯或四(甲基)丙烯酸酯等。 Further, specific examples of the hydrocarbon-based or hydrocarbon-ether-functional trifunctional monomer and the tetrafunctional monomer include trimethylolpropane tri(meth)acrylate and pentaerythritol tris(III). Tri(meth) acrylate of triol or tetraol compound such as acrylate, tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tetra(meth)acrylate Or a tetra(meth)acrylate or a tetra(meth)acrylate which is a compound obtained by adding an alkylene oxide to the above triol or a tetraol compound.
作為進而其他較佳之活性能量線硬化性成分,可列舉含羧基之單體。含羧基之單體就接著性方面而言亦較佳。作為含羧基之單體,例如可列舉:(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯等。其中較佳為丙烯酸。該等單體可單獨使用1種,或者組合2種以上而使用。 Further, other preferred active energy ray-curable components include a carboxyl group-containing monomer. The carboxyl group-containing monomer is also preferred in terms of adhesion. Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate. Among them, acrylic acid is preferred. These monomers may be used alone or in combination of two or more.
作為除上述成分以外可使用之活性能量線硬化性成分之具體例,可列舉:具有二環戊基、二環戊烯基、金剛烷基、三環戊基、三環戊烯基等橋接環結構之脂環式烴基之(甲基)丙烯酸酯;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸月桂酯等碳數1~12之(甲基)丙烯酸烷基酯;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體;順丁烯二酸酐、依康酸酐等含酸酐基之單體;丙烯酸之己內酯加成物;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體;2-羥基乙基丙烯醯基磷酸酯等含磷酸基之單體等。又,可列舉:(甲基)丙烯醯胺;順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺等;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸胺基丙酯、(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、(甲基)丙烯酸3-(3-吡啶基)丙酯等(甲基)丙烯酸烷基胺基烷基酯系單體;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基- 8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體等含氮之單體。 Specific examples of the active energy ray-curable component which can be used in addition to the above components include bridged rings having a dicyclopentyl group, a dicyclopentenyl group, an adamantyl group, a tricyclopentyl group, and a tricyclopentenyl group. Structure of alicyclic hydrocarbon group (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , (meth)acrylic acid alkyl ester having 1 to 12 carbon atoms such as isooctyl (meth)acrylate, isodecyl (meth)acrylate or lauryl (meth)acrylate; methoxy (meth)acrylate An alkoxyalkyl (meth) acrylate monomer such as ethyl ester or ethoxyethyl (meth) acrylate; an acid anhydride group-containing monomer such as maleic anhydride or isaconic anhydride; Ester adduct; styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) propylene decylamine-2-methylpropane sulfonic acid, (meth) acrylamide propyl sulfonic acid, (meth) acrylic acid a sulfonic acid group-containing monomer such as sulfopropyl ester or (meth) propylene decyl naphthalenesulfonic acid; a phosphate group-containing monomer such as 2-hydroxyethyl acryl phosphate. Further, (meth) acrylamide; maleimide, N-cyclohexylmethyleneimine, N-phenyl maleimide, etc.; (methyl) Aminoethyl acrylate, aminopropyl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, (methyl) An alkylaminoalkyl (meth) acrylate monomer such as 3-(3-pyridyl)propyl acrylate; N-(methyl) propylene oxymethylene succinimide or N-( Methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene fluorenyl- A nitrogen-containing monomer such as an amber quinone imine monomer such as 8-oxy octamethyl succinimide.
於較佳之實施形態中,將含羥基之單體與不含羥基之N-取代醯胺系單體及/或多官能性單體組合而使用。 In a preferred embodiment, a hydroxyl group-containing monomer is used in combination with a hydroxyl group-free N-substituted amide group monomer and/or a polyfunctional monomer.
接著劑所包含之含羥基之單體相對於全部活性能量線硬化性成分之比率例如為5重量%~70重量%,較佳為30重量%~70重量%,更佳為35重量%~60重量%。 The ratio of the hydroxyl group-containing monomer contained in the subsequent agent to the total active energy ray-curable component is, for example, 5% by weight to 70% by weight, preferably 30% by weight to 70% by weight, more preferably 35% by weight to 60% by weight. weight%.
接著劑所包含之不含羥基之N-取代醯胺系單體相對於全部活性能量線硬化性成分之比率例如為0重量%~70重量%,較佳為30重量%~70重量%,更佳為35重量%~60重量%。 The ratio of the N-substituted amide-based monomer containing no hydroxyl group to the total active energy ray-curable component in the subsequent agent is, for example, 0% by weight to 70% by weight, preferably 30% by weight to 70% by weight, more preferably It is preferably from 35 wt% to 60 wt%.
接著劑所包含之多官能單體相對於全部活性能量線硬化性成分之比率例如為0重量%~70重量%,較佳為30重量%~70重量%,更佳為35重量%~60重量%。 The ratio of the polyfunctional monomer contained in the subsequent agent to the total active energy ray-curable component is, for example, 0% by weight to 70% by weight, preferably 30% by weight to 70% by weight, more preferably 35% by weight to 60% by weight. %.
上述聚輪烷具有環狀分子、貫通該環狀分子之開口部之直鏈狀分子、及以該環狀分子不自該直鏈狀分子脫離之方式配置於該直鏈狀分子之兩端之封端基。 The polyrotaxane has a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and is disposed at both ends of the linear molecule so that the cyclic molecule is not detached from the linear molecule. End cap.
作為環狀分子,只要為將直鏈狀分子呈扡串狀地包藏於其開口部,可於直鏈狀分子上移動之分子,且為具有活性能量線聚合性基者則並無特別限定。再者,於本說明書中,「環狀分子」之「環狀」意指實質上為「環狀」。即,只要可於直鏈狀分子上移動,則環狀分子亦可不完全閉環。 The cyclic molecule is not particularly limited as long as it is a molecule which can be linearly entangled in the opening of the linear molecule and can be moved on the linear molecule, and has an active energy ray polymerizable base. In the present specification, the "ring" of the "cyclic molecule" means substantially "ring". That is, as long as it can move on a linear molecule, the cyclic molecule may not be completely closed.
作為環狀分子之具體例,可較佳地列舉:環狀聚醚、環狀聚酯、環狀聚醚胺、環狀聚胺等環狀聚合物,及α-環糊精、β-環糊精、γ-環糊精等環糊精。其中,就相對容易獲取且可大量選擇封端基之種類之方面而言,較佳為α-環糊精、β-環糊精、γ-環糊精等環糊精。環狀分子亦可於聚輪烷中或接著劑中混合存在2種以上。 Specific examples of the cyclic molecule include a cyclic polymer such as a cyclic polyether, a cyclic polyester, a cyclic polyether amine, and a cyclic polyamine, and an α-cyclodextrin and a β-ring. Cyclodextrin such as dextrin and γ-cyclodextrin. Among them, a cyclodextrin such as α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin is preferred in terms of being relatively easy to obtain and a large selection of the types of the terminal groups. The cyclic molecule may be mixed in two or more kinds in the polyrotaxane or in the adhesive.
於本發明所使用之聚輪烷中,上述環狀分子具有活性能量線聚合性基。藉此,即便於聚輪烷與活性能量線硬化性成分進行反應而硬化後,亦可獲得交聯點可動之接著劑,因此接著劑之耐水性提高。環狀分子所具有之活性能量線聚合性基只要為可與上述活性能量線硬化性化合物聚合之基即可,例如可列舉自由基聚合性基、及陽離子聚合性官能基。作為自由基聚合性基,例如可列舉(甲基)丙烯醯氧基、及(甲基)丙烯醯基,較佳為(甲基)丙烯醯氧基,更佳為丙烯醯氧基。藉由採用上述化學基作為自由基聚合性基,可達成較快之硬化速度,其結果,不僅可獲得較高之生產性,而且可賦予更高之耐水性。作為陽離子聚合性官能基,例如可列舉環氧基、及乙烯醚基。 In the polyrotaxane used in the present invention, the cyclic molecule has an active energy ray polymerizable group. Thereby, even if the polyrotaxane is reacted with the active energy ray-curable component and cured, a crosslinking agent capable of moving the crosslinking point can be obtained, so that the water resistance of the adhesive is improved. The active energy ray-polymerizable group of the cyclic molecule may be a group which can be polymerized with the active energy ray-curable compound, and examples thereof include a radical polymerizable group and a cationic polymerizable functional group. Examples of the radical polymerizable group include a (meth)acryloxy group and a (meth)acrylonitrile group, preferably a (meth)acryloxy group, more preferably an acryloxy group. By using the above chemical group as the radical polymerizable group, a faster curing rate can be achieved, and as a result, not only high productivity but also higher water resistance can be imparted. Examples of the cationically polymerizable functional group include an epoxy group and a vinyl ether group.
於使用環糊精作為環狀分子之情形時,活性能量線聚合性基較佳為經由任意適當之連接子(例如,下述式(I)或式(II)所表示之結構)而導入至環糊精之羥基。聚輪烷於1分子中所具有之活性能量線聚合性基之個數較佳為2個~1280個,更佳為100個~1100個,進而較佳為500個~1000個。藉由聚輪烷於1分子中所具有之活性能量線聚合性基之個數為特定個數以上,可確保硬化後之交聯點更多,因此賦予耐水性之效果提高。 In the case where cyclodextrin is used as the cyclic molecule, the active energy ray polymerizable group is preferably introduced to the appropriate one via a suitable linker (for example, a structure represented by the following formula (I) or formula (II)) The hydroxyl group of the cyclodextrin. The number of active energy ray polymerizable groups of the polyrotaxane in one molecule is preferably from 2 to 1,280, more preferably from 100 to 1,100, and still more preferably from 500 to 1,000. When the number of active energy ray-polymerizable groups in one molecule of the polyrotaxane is a specific number or more, the number of crosslinking points after curing can be ensured, and the effect of imparting water resistance is improved.
較佳為將疏水性修飾基導入至環狀分子。藉由疏水性修飾基之導入,可提高與活性能量線硬化性成分之相溶性。又,由於賦予了疏水性,故而於用作接著劑之情形時,可防止水滲入至接著劑層與被接著體之界面從而更進一步提高耐水性。作為疏水性修飾基,可列舉聚酯鏈、聚醯胺鏈、烷基鏈、氧伸烷基鏈、醚鏈等。作為具體例,可列舉WO2009/145073之[0027]~[0042]中記載之基。較佳之疏水性修飾基例如可具有以下之式(I)或式(II)所表示之結構。 It is preferred to introduce a hydrophobic modifying group into the cyclic molecule. The compatibility with the active energy ray-curable component can be improved by introduction of the hydrophobic modifying group. Further, since hydrophobicity is imparted, when it is used as an adhesive, water can be prevented from infiltrating into the interface between the adhesive layer and the adherend, thereby further improving water resistance. Examples of the hydrophobic modifying group include a polyester chain, a polyamine chain, an alkyl chain, an oxygen alkyl chain, and an ether chain. Specific examples include the groups described in [0027] to [0042] of WO2009/145073. A preferred hydrophobic modifying group may have, for example, a structure represented by the following formula (I) or formula (II).
[化1]
於式(I)或式(II)所表示之結構中,各重複單元中之Q可相同亦可不同。於Q不同之情形(即,該結構為共聚物狀之情形)時,其形態可為無規共聚物、嵌段共聚物、交替共聚物等任意形態。 In the structure represented by the formula (I) or the formula (II), Q in each repeating unit may be the same or different. When Q is different (that is, when the structure is in the form of a copolymer), the form may be any form such as a random copolymer, a block copolymer, or an alternating copolymer.
式中,Q為碳數1~8之直鏈狀伸烷基或伸烯基、碳數3~20之支鏈狀伸烷基或伸烯基、該伸烷基或伸烯基之一部分經-O-鍵或-NH-鍵取代而成之伸烷基、或者該伸烷基之氫之一部分經選自由羥基、羧基、醯基、苯基、鹵素原子及烯烴基所組成之群中之至少1種取代而成之伸烷基,較佳為碳數3~8之直鏈狀伸烷基、碳數5~10之支鏈狀伸烷基,更佳為碳數4~6之直鏈狀伸烷基。 In the formula, Q is a linear alkyl or alkenyl group having 1 to 8 carbon atoms, a branched alkyl group or an alkenyl group having 3 to 20 carbon atoms, and a part of the alkyl group or the alkenyl group. An alkyl group substituted with an -O- bond or a -NH- bond, or a portion of the hydrogen of the alkylene group is selected from the group consisting of a hydroxyl group, a carboxyl group, a thiol group, a phenyl group, a halogen atom, and an olefin group. At least one substituted alkylene group, preferably a linear alkyl group having 3 to 8 carbon atoms, a branched alkyl group having 5 to 10 carbon atoms, more preferably a carbon number of 4 to 6 Chain alkyl group.
n1及n2分別獨立為1~200,較佳為2~100,更佳為3~50。 N1 and n2 are independently 1 to 200, preferably 2 to 100, and more preferably 3 to 50.
上述式(I)所表示之結構及式(II)所表示之結構就較佳為來自內酯單體及/或內醯胺單體之開環聚合。作為內酯單體,例如可列舉:β-丙內酯、β-甲基丙內酯、L-絲胺酸-β-內酯衍生物等四員環內酯;γ-丁 內酯、γ-己內酯、γ-庚內酯、γ-辛內酯、γ-癸內酯、γ-十二烷內酯、α-己基-γ-丁內酯、α-庚基-γ-丁內酯、α-羥基-γ-丁內酯、γ-甲基-γ-癸內酯、α-亞甲基-γ-丁內酯、α,α-二甲基-γ-丁內酯、D-赤酮酸內酯、α-甲基-γ-丁內酯、γ-壬內酯、DL-泛解酸內酯、γ-苯基γ-丁內酯、γ-十一烷內酯、γ-戊內酯、2,2-五亞甲基-1,3-二氧雜環戊烷-4-酮、α-溴-γ-丁內酯、γ-巴豆醯內酯、α-亞甲基-γ-丁內酯、α-甲基丙烯醯氧基-γ-丁內酯、β-甲基丙烯醯氧基-γ-丁內酯等五員環內酯;δ-戊內酯、δ-己內酯、δ-辛內酯、δ-壬內酯、δ-癸內酯、δ-十一烷內酯、δ-十二烷內酯、δ-十三烷內酯、δ-十四烷內酯、DL-甲基二羥戊酸內酯、4-羥基-1-環己烷羧酸δ-內酯等六員環內酯;ε-己內酯等七員環內酯;乳酸交酯、1,5-二氧雜環庚烷-2-酮。其中,較佳為ε-己內酯、γ-丁內酯、α-甲基-γ-丁內酯、δ-戊內酯、乳酸交酯,更佳為ε-己內酯。 The structure represented by the above formula (I) and the structure represented by the formula (II) are preferably ring-opening polymerization from a lactone monomer and/or an indoleamine monomer. Examples of the lactone monomer include a four-membered ring lactone such as β-propiolactone, β-methylpropiolactone, and L-serine-β-lactone derivative; γ-butyl Lactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, γ-decalactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl- Γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decalactone, α-methylene-γ-butyrolactone, α,α-dimethyl-γ-butyl Lactone, D-erythronolactone, α-methyl-γ-butyrolactone, γ-decalactone, DL-pantolactone, γ-phenylγ-butyrolactone, γ-eleven Alkanolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolane-4-one, α-bromo-γ-butyrolactone, γ-crotonide , five-membered lactones such as α-methylene-γ-butyrolactone, α-methacryloxy-γ-butyrolactone, β-methacryloxy-γ-butyrolactone; -valerolactone, δ-caprolactone, δ-octanolactone, δ-decalactone, δ-decalactone, δ-undecanolide, δ-dodecanolactone, δ-tridecane Lactone, δ-tetradecane lactone, DL-methyl hydroxyvalerate, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, etc.; ε-caprolactone, etc. Seven-membered ring lactone; lactide, 1,5-dioxepane-2-one. Among them, ε-caprolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, δ-valerolactone, lactide, and more preferably ε-caprolactone are preferred.
作為內醯胺單體,例如可列舉:4-苯甲醯氧基-2-氮雜環丁酮等四員環內醯胺;γ-丁內醯胺、2-氮雜雙環[2.2.1]-5-庚烯-3-酮、5-甲基-2-吡咯啶酮等五員環內醯胺;2-哌啶酮-3-羧酸乙酯等六員環內醯胺、ε-己內醯胺、DL-α-胺基-ε-己內醯胺等七員環內醯胺;ω-庚內醯胺。其中,較佳為ε-己內醯胺、γ-丁內醯胺、DL-α-胺基-ε-己內醯胺,更佳為ε-己內醯胺。 Examples of the indoleamine monomer include a four-membered ring decylamine such as 4-benzylideneoxy-2-azetidinone; γ-butyrolactam and 2-azabicyclo[2.2.1 5-membered indoleamine such as 5-hepten-3-one or 5-methyl-2-pyrrolidone; 6-membered indoleamine such as 2-piperidone-3-carboxylic acid ethyl ester, ε - 7-membered ring decylamine such as caprolactam, DL-α-amino-ε-caprolactam; ω-heptanoin. Among them, ε-caprolactam, γ-butyrolactam, DL-α-amino-ε-caprolactam, and more preferably ε-caprolactam are preferred.
作為較佳之疏水性修飾基之具體例,可列舉以下之式(III)所表示之基。 Specific examples of the preferred hydrophobic modifying group include the groups represented by the following formula (III).
-L-M-A(式III) -L-M-A (Formula III)
於式(III)中,L為單鍵或任意適當之連接子,M為式(I)或式(II)所表示之結構,A為-OH或-OC(=O)HNH(CH2)n3X(X為(甲基)丙烯醯基,n3為碳數1~8之直鏈狀或支鏈狀伸烷基)。連接子例如可為碳數1~8之直鏈狀或支鏈狀伸烷基。 In formula (III), L is a single bond or any suitable linker, M is a structure represented by formula (I) or formula (II), and A is -OH or -OC(=O)HNH(CH 2 ) N3 X (X is a (meth) acrylonitrile group, and n3 is a linear or branched alkyl group having 1 to 8 carbon atoms). The linker may be, for example, a linear or branched alkyl group having 1 to 8 carbon atoms.
於使用環糊精作為環狀分子之情形時,上述疏水性修飾基代表 性而言導入至環糊精之羥基。疏水性修飾基對羥基之導入率(取代度)較佳為10%~90%,更佳為20%~80%,進而較佳為30%~70%。聚輪烷可於分子內具有相同之疏水性修飾基,亦可具有不同之疏水性修飾基(例如,A為作為羥基之基及包含(甲基)丙烯醯基之基之二者)。 In the case where a cyclodextrin is used as the cyclic molecule, the above hydrophobic modifying group represents Sexually introduced into the hydroxyl group of the cyclodextrin. The introduction rate (degree of substitution) of the hydrophobic modifying group to the hydroxyl group is preferably from 10% to 90%, more preferably from 20% to 80%, still more preferably from 30% to 70%. The polyrotaxane may have the same hydrophobic modifying group in the molecule, or may have different hydrophobic modifying groups (for example, A is a group serving as a hydroxyl group and a group containing a (meth)acrylylene group).
作為直鏈狀分子,只要為包藏於環狀分子,可利用機械結合而非共價鍵結等化學鍵結進行一體化之分子或物質,且為直鏈狀者,則並無特別限定。再者,於本說明書中,「直鏈狀分子」之「直鏈」意指實質上為「直鏈」。即,只要環狀分子可於直鏈狀分子上移動,則直鏈狀分子亦可具有支鏈。 The linear molecule is not particularly limited as long as it is a molecule or a substance which is incorporated in a cyclic molecule and can be integrated by chemical bonding such as mechanical bonding rather than chemical bonding, and is linear. Furthermore, in the present specification, "linear" of "linear molecule" means substantially "straight chain". That is, as long as the cyclic molecule can move on the linear molecule, the linear molecule may have a branch.
作為直鏈狀分子,例如較佳為聚乙二醇、聚丙二醇、聚異戊二烯、聚異丁烯、聚丁二烯、聚四氫呋喃、聚丙烯酸酯、聚二甲基矽氧烷、聚乙烯、聚丙烯等。直鏈狀分子亦可於接著劑中混合存在2種以上。 As the linear molecule, for example, polyethylene glycol, polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polytetrahydrofuran, polyacrylate, polydimethyl siloxane, polyethylene, or the like is preferable. Polypropylene, etc. The linear molecule may be mixed in two or more kinds in the adhesive.
直鏈狀分子之數量平均分子量較佳為3,000~300,000,更佳為10,000~200,000,進而較佳為20,000~100,000。若數量平均分子量未達3,000,則有如下之虞:環狀分子於直鏈狀分子上之移動量變小,無法對接著劑賦予充分之柔軟性,且因被接著體-接著劑間之密接性消失而無法充分獲得耐水性提高效果。又,若數量平均分子量超過300,000,則有與活性能量線硬化性成分之相溶性降低之虞。 The number average molecular weight of the linear molecules is preferably from 3,000 to 300,000, more preferably from 10,000 to 200,000, and still more preferably from 20,000 to 100,000. When the number average molecular weight is less than 3,000, there is a case where the amount of movement of the cyclic molecule on the linear molecule is small, sufficient flexibility is not imparted to the adhesive, and adhesion between the adherend and the adhesive is caused. It disappears and the water resistance improvement effect cannot be fully obtained. Further, when the number average molecular weight exceeds 300,000, the compatibility with the active energy ray-curable component is lowered.
封端基只要為可保持環狀分子因直鏈狀分子而成為扡串狀之形態之基,則並無特別限定。作為此種基,可列舉:二硝基苯基類、環糊精類、金剛烷基類、三苯甲基類、螢光素類、芘類、蒽類等、或數量平均分子量1,000~1,000,000之高分子之主鏈或側鏈等。封端基亦可於聚輪烷中或接著劑中混合存在2種以上。 The terminal group is not particularly limited as long as it is a group capable of maintaining a cyclic molecule in a form of a ruthenium chain. Examples of such a group include dinitrophenyls, cyclodextrins, adamantyls, trityls, fluoresceins, anthraquinones, anthracenes, etc., or a number average molecular weight of 1,000 to 1,000,000. The main chain or side chain of the polymer. The blocking group may be mixed in two or more kinds in the polyrotaxane or in the adhesive.
於上述聚輪烷中,於將環狀分子被直鏈狀分子呈扡串狀地包藏時環狀分子被最大限度地包藏之量(最大包藏量)設為100%的情形時, 環狀分子較佳為以0.1%~60%、更佳為以1%~50%、進而較佳為以5%~40%之量被直鏈狀分子呈扡串狀地包藏。再者,環狀分子之最大包藏量可根據直鏈狀分子之長度及環狀分子之厚度而決定。例如,於直鏈狀分子為聚乙二醇且環狀分子為α-環糊精分子之情形時,最大包藏量係藉由實驗求出(參照Macromolecules 1993,26,5698-5703)。 In the above-mentioned polyrotaxane, when the cyclic molecule is entangled in a string shape by a linear molecule, when the amount of the cyclic molecule is maximized (maximum occlusion amount) is set to 100%, The cyclic molecule is preferably contained in a ruthenium chain shape in an amount of 0.1% to 60%, more preferably 1% to 50%, still more preferably 5% to 40%. Furthermore, the maximum occlusion amount of the cyclic molecule can be determined according to the length of the linear molecule and the thickness of the cyclic molecule. For example, in the case where the linear molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum amount of occlusion is determined experimentally (refer to Macromolecules 1993, 26, 5698-5703).
上述聚輪烷例如可藉由日本專利特開2005-154675號公報、日本專利特開2009-270119號公報、WO2009/145073等中記載之方法而獲得。又,亦可購入市售品(例如,Advanced Softmaterials公司製造之「Serm Super Polymer」系列)。 The polyrotaxane can be obtained, for example, by the method described in JP-A-2005-154675, JP-A-2009-270119, WO2009/145073, and the like. Further, a commercially available product (for example, "Serm Super Polymer" series manufactured by Advanced Softmaterials Co., Ltd.) can be purchased.
本發明之接著劑中之聚輪烷之調配量之下限相對於全部硬化性成分(活性能量線硬化性成分與聚輪烷之合計)100重量份較佳為2重量份,例如可為3重量份、4重量份、5重量份、6重量份、7重量份、8重量份、9重量份或10重量份。另一方面,上限較佳為50重量份,更佳為40重量份,進而較佳為30重量份。若調配量未達2重量份,則耐水性提高效果可能不充分。又,若調配量超過50重量份,則存在接著力或透明性降低之情形。 The lower limit of the amount of the polyrotaxane in the adhesive of the present invention is preferably 2 parts by weight, and may be, for example, 3 parts by weight based on 100 parts by weight of all the curable components (the total of the active energy ray-curable component and the polyrotaxane). Parts, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight. On the other hand, the upper limit is preferably 50 parts by weight, more preferably 40 parts by weight, still more preferably 30 parts by weight. If the amount is less than 2 parts by weight, the water resistance improvement effect may be insufficient. Moreover, when the compounding amount exceeds 50 parts by weight, there is a case where the adhesion force or transparency is lowered.
作為光聚合起始劑,使用任意適當之光聚合起始劑。作為光聚合起始劑之具體例,可列舉:2,2-二甲氧基-2-苯基苯乙酮、苯乙酮、二苯甲酮、氧雜蒽酮、3-甲基苯乙酮、4-氯二苯甲酮、4,4'-二甲氧基二苯甲酮、安息香丙醚、苯偶醯二甲基縮酮、N,N,N',N'-四甲基-4,4'-二胺基二苯甲酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、9-氧硫系化合物等。 As the photopolymerization initiator, any appropriate photopolymerization initiator is used. Specific examples of the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, and 3-methylphenylethyl. Ketone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, benzoin propyl ether, benzoin dimethyl ketal, N, N, N', N'-tetramethyl -4,4'-diaminobenzophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 9-oxosulfur A compound or the like.
光聚合起始劑之調配量相對於全部硬化性成分(活性能量線硬化性成分及聚輪烷)100重量份通常為0.1~10重量份左右,較佳為0.5~5重量份,更佳為1~4重量份。 The amount of the photopolymerization initiator to be added is usually from 0.1 to 10 parts by weight, preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of all the curable components (active energy ray-curable component and polyrotaxane), more preferably 1 to 4 parts by weight.
本發明之接著劑可進而包含任意適當之添加劑。作為添加劑之具體例,可列舉:以羰基化合物等為代表之利用活性能量線之提高硬化速度或感度之增感劑、矽烷偶合劑或以環氧乙烷為代表之接著促進劑、提高與被接著體之潤濕性之添加劑、以丙烯醯氧基化合物或烴系(天然、合成樹脂)等為代表且提高機械性強度或加工性等之添加劑、紫外線吸收劑、防老化劑、染料、加工助劑、離子捕捉劑、抗氧化劑、黏著賦予劑、填充劑、金屬化合物填料、塑化劑、調平劑、發泡抑制劑、抗靜電劑等。 The adhesive of the present invention may further comprise any suitable additive. Specific examples of the additive include a sensitizer, a decane coupling agent, or an ethylene glycol-based sensitizer, which is represented by a carbonyl compound or the like, which is improved in curing rate or sensitivity by an active energy ray. Additives such as a wettability agent, an additive such as an acryl oxime compound or a hydrocarbon (natural, synthetic resin), etc., which improves mechanical strength or processability, an ultraviolet absorber, an anti-aging agent, a dye, and a process. Auxiliaries, ion trapping agents, antioxidants, adhesion-imparting agents, fillers, metal compound fillers, plasticizers, leveling agents, foaming inhibitors, antistatic agents, and the like.
本發明之偏光膜包括偏光元件、及經由接著劑層而設置於該偏光元件之至少單面之保護膜。 The polarizing film of the present invention includes a polarizing element and a protective film provided on at least one side of the polarizing element via an adhesive layer.
作為偏光元件,可採用任意適當之偏光元件。作為具體例,可列舉對聚乙烯醇系膜、部分縮甲醛化聚乙烯醇系膜、乙烯-乙酸乙烯酯共聚合物系部分皂化膜等親水性高分子膜實施利用碘或二色性染料等二色性物質之染色處理及延伸處理而成者,聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系配向膜等。就光學特性優異之方面而言,較佳為使用利用碘將聚乙烯醇系膜染色並進行單軸延伸而獲得之偏光元件。 As the polarizing element, any appropriate polarizing element can be employed. Specific examples of the hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partial saponified film are iodine or a dichroic dye. A dyeing treatment and elongation treatment of a dichroic substance, a polyene-based alignment film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. In terms of excellent optical characteristics, a polarizing element obtained by dyeing a polyvinyl alcohol-based film with iodine and performing uniaxial stretching is preferably used.
上述利用碘之染色例如藉由將聚乙烯醇系膜浸漬於碘水溶液而進行。上述單軸延伸之延伸倍率較佳為3~7倍。延伸可於染色處理後進行,亦可一面染色一面進行。又,亦可於延伸後染色。視需要對聚乙烯醇系膜實施膨潤處理、交聯處理、洗淨處理、乾燥處理等。例如,藉由於染色之前將聚乙烯醇系膜浸漬於水而進行水洗,不僅可洗淨聚乙烯醇系膜表面之污垢或抗黏連劑,而且可使聚乙烯醇系膜膨潤 而防止染色不均等。 The above dyeing with iodine is carried out, for example, by immersing a polyvinyl alcohol-based film in an aqueous iodine solution. The stretching ratio of the uniaxial stretching is preferably 3 to 7 times. The stretching can be carried out after the dyeing treatment, or can be carried out while dyeing one side. Also, it can be dyed after stretching. The polyvinyl alcohol-based film is subjected to a swelling treatment, a crosslinking treatment, a washing treatment, a drying treatment, and the like as necessary. For example, by washing the polyvinyl alcohol-based film with water before dyeing, it is possible to wash not only the dirt or anti-blocking agent on the surface of the polyvinyl alcohol film but also the polyvinyl alcohol film. And to prevent uneven dyeing.
偏光元件之厚度代表性而言為1μm~80μm左右,較佳為3μm~30μm,更佳為5μm~10μm。 The thickness of the polarizing element is typically from about 1 μm to about 80 μm, preferably from 3 μm to 30 μm, more preferably from 5 μm to 10 μm.
上述偏光元件之水分率可為20重量%以下,可為例如0~15重量%、或例如1~10重量%之水分率。若偏光元件之水分率為20重量%以下,則可獲得高溫下或高溫高濕下之尺寸變化受到抑制之偏光膜。 The polarizing element may have a water content of 20% by weight or less, and may be, for example, 0 to 15% by weight or, for example, 1 to 10% by weight. When the water content of the polarizing element is 20% by weight or less, a polarizing film in which dimensional change under high temperature or high temperature and high humidity is suppressed can be obtained.
偏光元件之水分率係利用以下方法進行測定。即,將偏光元件切成100×100mm之大小,測定該樣品之初始重量。繼而,將該樣品以120℃乾燥2小時,測定乾燥重量,並藉由下述式測定水分率。重量之測定係分別各進行3次,並使用其平均值。 The moisture content of the polarizing element was measured by the following method. That is, the polarizing element was cut into a size of 100 × 100 mm, and the initial weight of the sample was measured. Then, the sample was dried at 120 ° C for 2 hours, the dry weight was measured, and the water content was measured by the following formula. The weight was measured three times each and the average value was used.
水分率(重量%)={(初始重量-乾燥重量)/初始重量}×100 Moisture rate (% by weight) = {(initial weight - dry weight) / initial weight} × 100
作為保護膜,可採用能用作偏光元件之保護層之任意適當之膜。可為各向同性之膜,亦可為具有相位差且具備光學補償功能之膜。作為保護膜之形成材料,例如可列舉:(甲基)丙烯酸系樹脂、二乙醯纖維素、三乙醯纖維素等纖維素系樹脂、環烯烴系樹脂、聚丙烯等烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂等酯系樹脂、聚醯胺系樹脂、聚碳酸酯系樹脂、該等之共聚物樹脂等。於偏光元件之兩側設置保護膜之情形時,可對兩側使用包含相同材料之保護膜,亦可使用包含不同材料之保護膜。 As the protective film, any appropriate film which can be used as a protective layer of a polarizing element can be used. It may be an isotropic film or a film having a phase difference and having an optical compensation function. Examples of the material for forming the protective film include a cellulose resin such as a (meth)acrylic resin, a diethylpyruvyl cellulose or a triacetyl cellulose, a cycloolefin resin, an olefin resin such as polypropylene, and a poly pair. An ester resin such as an ethylene phthalate resin, a polyamide resin, a polycarbonate resin, or the like. When a protective film is provided on both sides of the polarizing element, a protective film containing the same material may be used for both sides, and a protective film containing different materials may be used.
保護膜之厚度較佳為1μm~300μm,更佳為3μm~100μm,進而較佳為5μm~40μm。 The thickness of the protective film is preferably from 1 μm to 300 μm, more preferably from 3 μm to 100 μm, still more preferably from 5 μm to 40 μm.
上述保護膜係經由接著劑層而積層於偏光元件之至少一個面。該接著劑層係藉由上述A項所記載之接著劑而形成。接著劑層之厚度較佳為0.01μm~7μm,更佳為0.1μm~5μm,進而較佳為0.5μm~3μm。 The protective film is laminated on at least one surface of the polarizing element via an adhesive layer. The adhesive layer is formed by the adhesive described in the above item A. The thickness of the subsequent layer is preferably from 0.01 μm to 7 μm, more preferably from 0.1 μm to 5 μm, still more preferably from 0.5 μm to 3 μm.
本發明之偏光膜例如藉由如下方法而獲得,該方法包括:對偏光元件之設置有保護膜之側之面或保護膜之設置有偏光元件之側之面塗佈接著劑;經由接著劑之塗佈層將偏光元件與保護膜貼合而獲得積層體;對所獲得之積層體照射活性能量線使接著劑硬化而形成接著劑層。 The polarizing film of the present invention is obtained, for example, by a method of applying an adhesive to a side of a polarizing element on a side where a protective film is provided or a side of a protective film provided with a polarizing element; The coating layer is bonded to the protective film to obtain a laminate, and the obtained laminate is irradiated with an active energy ray to cure the adhesive to form an adhesive layer.
亦可於塗敷接著劑之前對偏光元件及保護膜分別進行表面改質處理。作為具體之處理,可列舉電暈處理、電漿處理、皂化處理等。 The polarizing element and the protective film may be subjected to surface modification treatment before the application of the adhesive. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.
接著劑之塗佈方式係根據接著劑之黏度或目標之厚度而適當選擇。例如可列舉:反向塗佈機、凹版塗佈機(直接、反向或平版)、棒式反向塗佈機、輥式塗佈機、模嘴塗佈機、棒式塗佈機、桿式塗佈機等。此外,可適當地使用浸漬方式等塗佈方式。 The coating method of the subsequent agent is appropriately selected depending on the viscosity of the adhesive or the thickness of the target. For example, a reverse coater, a gravure coater (direct, reverse or lithographic), a bar reverse coater, a roll coater, a die coater, a bar coater, a rod Coating machine, etc. Further, a coating method such as an immersion method can be suitably used.
偏光元件與保護膜之貼合可利用覆膜機等而進行。 The bonding of the polarizing element and the protective film can be performed by a laminator or the like.
活性能量線可自任意適當之方向照射。較佳為自保護膜側照射。若自偏光元件側照射,則有偏光元件因活性能量線而劣化之虞。 The active energy ray can be illuminated from any suitable direction. It is preferred to irradiate from the side of the protective film. When the light is emitted from the side of the polarizing element, the polarizing element is deteriorated by the active energy ray.
活性能量線之照射條件只要為接著劑可硬化之條件則可採用任意適當之條件。例如,電子束照射之加速電壓較佳為5kV~300kV,進而較佳為10kV~250kV。照射線量為5~100kGy,進而較佳為10~75kGy。另一方面,紫外線之照射量較佳為380~430nm之累計光量為50~3000mJ/cm2,更佳為100~2000mJ/cm2。 The irradiation conditions of the active energy ray may be any suitable conditions as long as the adhesive can be cured. For example, the acceleration voltage of the electron beam irradiation is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. The amount of irradiation line is 5 to 100 kGy, and more preferably 10 to 75 kGy. On the other hand, the amount of ultraviolet rays to be irradiated is preferably from 380 to 430 nm, and the cumulative amount of light is from 50 to 3,000 mJ/cm 2 , more preferably from 100 to 2,000 mJ/cm 2 .
本發明之液晶面板包含液晶單元、及經由接著劑層而設置於該液晶單元之至少單面之偏光元件。當然,該偏光元件可僅設置於該液晶單元之一側,亦可設置於該液晶單元之兩側。 The liquid crystal panel of the present invention includes a liquid crystal cell and a polarizing element provided on at least one side of the liquid crystal cell via an adhesive layer. Of course, the polarizing element may be disposed only on one side of the liquid crystal unit, or may be disposed on both sides of the liquid crystal unit.
作為偏光元件,可採用任意適當之偏光元件。作為具體例,可 列舉B-1項所記載之偏光元件。 As the polarizing element, any appropriate polarizing element can be employed. As a specific example, The polarizing element described in item B-1 is listed.
作為液晶單元,可採用任意適當之液晶單元。作為具體例,可列舉扭轉向列(TN)模式、超扭轉向列(STN)模式、水平配向(ECB)模式、垂直配向(VA)模式、橫向電場效應(IPS)模式、彎曲向列(OCB)模式、鐵電性液晶(SSFLC)模式、及反鐵電液晶(AFLC)模式之液晶單元。再者,液晶面板之通常之構成為業界所周知,因此省略詳細之說明。 As the liquid crystal cell, any appropriate liquid crystal cell can be employed. Specific examples include a twisted nematic (TN) mode, a super twisted nematic (STN) mode, a horizontal alignment (ECB) mode, a vertical alignment (VA) mode, a transverse electric field effect (IPS) mode, and a curved nematic (OCB). ) Liquid crystal cell in mode, ferroelectric liquid crystal (SSFLC) mode, and antiferroelectric liquid crystal (AFLC) mode. Further, since the general configuration of the liquid crystal panel is well known in the art, detailed description thereof will be omitted.
根據本發明之另一態樣,提供一種光學膜。該光學膜具有藉由上述接著劑而形成之接著劑層。作為上述光學膜,可採用任意適當之光學膜。作為上述光學膜,例如可列舉用於圖像顯示裝置等之具有光學功能之膜。更具體而言,例如可列舉相位差膜、表面處理膜、及隔離膜。上述表面處理膜亦可具有硬塗層及/或防眩層。作為上述隔離膜,例如可列舉以保護表面直至使用作為目的之隔離膜。 According to another aspect of the present invention, an optical film is provided. The optical film has an adhesive layer formed by the above-mentioned adhesive. As the above optical film, any appropriate optical film can be employed. As the optical film, for example, a film having an optical function such as an image display device can be cited. More specifically, a retardation film, a surface treatment film, and a separator are mentioned, for example. The surface treatment film may also have a hard coat layer and/or an antiglare layer. As the above-mentioned separator, for example, a separator which protects the surface until use is intended.
本發明之圖像顯示裝置包含B項所記載之偏光膜、C項所記載之液晶面板、或D項所記載之光學膜。本發明之圖像顯示裝置可為液晶顯示器(LCD)、電致發光顯示器(ELD)等。 The image display device of the present invention includes the polarizing film described in item B, the liquid crystal panel described in item C, or the optical film described in item D. The image display device of the present invention may be a liquid crystal display (LCD), an electroluminescent display (ELD) or the like.
以下,藉由實施例具體地說明本發明,但本發明並不限定於該等實施例。又,於實施例中,只要無特別說明,則「份」及「%」為重量基準。 Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Further, in the examples, "parts" and "%" are based on weight unless otherwise specified.
將平均聚合度2400、皂化度99.9莫耳%、厚度75μm之聚乙烯醇膜於30℃之溫水中浸漬60秒鐘而使其膨潤。繼而,一面於0.3重量 %(重量比:碘/碘化鉀=0.5/8)之30℃之碘溶液中染色1分鐘,一面延伸至3.5倍。其後,一面於65℃之4重量%之硼酸水溶液中浸漬0.5分鐘一面延伸至綜合延伸倍率為6倍。延伸後,利用70℃之烘箱進行3分鐘乾燥,獲得厚度26μm之偏光元件。偏光元件之水分率為13.5重量%。 A polyvinyl alcohol film having an average degree of polymerization of 2,400, a degree of saponification of 99.9 mol%, and a thickness of 75 μm was immersed in warm water of 30 ° C for 60 seconds to swell. Then, one side at 0.3 weight % (weight ratio: iodine / potassium iodide = 0.5 / 8) was dyed in an iodine solution at 30 ° C for 1 minute and extended to 3.5 times on one side. Thereafter, the film was stretched to a total stretching ratio of 6 times while being immersed in a 4% by weight aqueous solution of boric acid at 65 ° C for 0.5 minutes. After stretching, it was dried in an oven at 70 ° C for 3 minutes to obtain a polarizing element having a thickness of 26 μm. The moisture content of the polarizing element was 13.5% by weight.
使用三乙醯纖維素膜(Konica Minolta公司製造,商品名「KC4UY」,厚度40μm)。 A triacetyl cellulose membrane (manufactured by Konica Minolta Co., Ltd., trade name "KC4UY", thickness: 40 μm) was used.
將羥基乙基丙烯醯胺(HEAA,興人公司製造)40.0份、丙烯醯基嗎啉(ACMO,興人公司製造)50.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SA3405P」,直鏈狀分子:PEG,環狀分子:α-環糊精,聚己內酯鏈相對於環狀分子上之全部羥基之導入比率為50~60%,所導入之聚己內酯鏈中之約70%為含丙烯醯基之聚己內酯鏈)10.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。 40.0 parts of hydroxyethyl acrylamide (manufactured by HEAA Co., Ltd.), 50.0 parts of acryloyl morpholine (ACMO, manufactured by Xingren Co., Ltd.), polyrotaxane (manufactured by Advanced Softmaterials Co., Ltd., product name "Serm Super Polymer SA3405P Linear polymer: PEG, cyclic molecule: α-cyclodextrin, the introduction ratio of polycaprolactone chain to all hydroxyl groups on the cyclic molecule is 50-60%, and the introduced polycaprolactone chain About 70% of the polycaprolactone chain containing propylene sulfonate is 10.0 parts, and the product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) as a photoinitiator is 1.5 parts and the product name "IRGACURE907" 1.5 parts (manufactured by BASF JAPAN Co., Ltd.) were mixed to prepare an adhesive.
於製造例2之保護膜上,使用微凹版塗佈機(凹版輥:# 700,旋轉速度140%/線速)以厚度成為1μm之方式塗敷上述接著劑,而獲得附接著劑之塗佈層之保護膜。繼而,利用滾壓機將附接著劑之塗佈層之保護膜貼合於製造例1之偏光元件之兩面。自所獲得之積層體(保護膜/塗佈層/偏光元件/塗佈層/保護膜)之保護膜側(兩側)藉由金屬鹵化物燈分別照射累計光量1000mJ/cm2之活性能量線而使接著劑硬化,從而獲得偏光膜。 The above-mentioned adhesive was applied to the protective film of Production Example 2 by using a micro gravure coater (gravure roll: #700, rotation speed of 140%/linear velocity) so as to have a thickness of 1 μm to obtain coating of the adhesive. Protective film of the layer. Then, the protective film of the coating layer of the adhesive agent was bonded to both surfaces of the polarizing element of Production Example 1 by a roller press. From the protective film side (both sides) of the obtained laminate (protective film/coating layer/polarizing element/coating layer/protective film), the active energy rays of the cumulative light amount of 1000 mJ/cm 2 were respectively irradiated by the metal halide lamps. The adhesive is hardened to obtain a polarizing film.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)35.0份、1,9-壬二醇二丙烯酸酯(共榮社化學公司製造,製品名「Light Acrylate 1,9ND-A」)40.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SA3405P」)25.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 35.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate 1, 9ND-A") 40.0 parts, 25.0 parts of polyrotaxane (product name "Serm Super Polymer SA3405P", manufactured by Advanced Softmaterials Co., Ltd.), and 1.5 parts of product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) as a photoinitiator 1.5 parts of "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) was mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)35.0份、丙烯醯基嗎啉(ACMO,興人公司製造)35.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SA3405P」)30.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 35.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 35.0 parts of acryloylmorpholine (ACMO, manufactured by Xingren Co., Ltd.), and polyrotaxane (manufactured by Advanced Softmaterials Co., Ltd., product name "Serm Super" 3 parts of Polymer SA3405P"), and 1.5 parts of the product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) and 1.5 parts of the product name "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) as a photoinitiator were prepared and mixed. Follow-up agent. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)40.0份、丙烯酸二環戊烯酯(日立化成公司製造,製品名「Fancryl FA-511AS」)58.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SA3405P」)2.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 40.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and dicyclopentenyl acrylate (manufactured by Hitachi Chemical Co., Ltd., product name "Fancryl FA-511AS") 58.0 parts, polyrotaxane (Advanced Softmaterials) 2.0 parts of the product name "Serm Super Polymer SA3405P" and the product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) and the product name "IRGACURE907" (manufactured by BASF JAPAN) 1.5 parts were mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)35.0份、1,9-壬二醇二丙烯酸酯(共榮社化學公司製造,製品名「Light Acrylate 1,9ND-A」)40.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SA2405P」)25.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 35.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate 1, 9ND-A") 20.0 parts, 25.0 parts of polyrotaxane (product name "Serm Super Polymer SA2405P", manufactured by Advanced Softmaterials Co., Ltd.), and 1.5 parts of product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) as a photoinitiator 1.5 parts of "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) was mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)35.0份、1,9-壬二醇二丙烯酸酯(共榮社化學公司製造,製品名「Light Acrylate 1,9ND-A」)40.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SA1315P」)25.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 35.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate 1, 9ND-A") 40.0 parts, 25.0 parts of polyrotaxane (product name "Serm Super Polymer SA1315P", manufactured by Advanced Softmaterials Co., Ltd.), and 1.5 parts of product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) as a photoinitiator 1.5 parts of "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) was mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)35.0份、1,9-壬二醇二丙烯酸酯(共榮社化學公司製造,製品名「Light Acrylate 1,9ND-A」)40.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SM3405P」)25.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 35.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate 1, 9ND-A") 40.0 parts, 25.0 parts of polyrotaxane (product name "Serm Super Polymer SM3405P", manufactured by Advanced Softmaterials Co., Ltd.), and 1.5 parts of product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) as a photoinitiator 1.5 parts of "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) was mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)35.0份、1,9-壬二醇二丙烯酸酯(共榮社化學公司製造,製品名「Light Acrylate 1,9ND-A」)40.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SM1315P」)25.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 35.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate 1, 9ND-A") 40.0 parts, 25.0 parts of polyrotaxane (product name "Serm Super Polymer SM1315P", manufactured by Advanced Softmaterials Co., Ltd.), and 1.5 parts of product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) as a photoinitiator 1.5 parts of "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) was mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將羥基乙基丙烯醯胺(HEAA,興人公司製造)50.0份、丙烯醯基嗎啉(ACMO,興人公司製造)50.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 50.0 parts of hydroxyethyl acrylamide (manufactured by HEAA Co., Ltd.), 50.0 parts of acryloylmorpholine (ACMO, manufactured by Xingren Co., Ltd.), and product name "KAYACURE DETX-S" as a photoinitiator ( 1.5 parts and 1.5 parts of the product name "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) were mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)40.0份、1.9-壬二醇二丙烯酸酯(共榮社化學公司製造,製品名「Light Acrylate 1,9ND-A」)40.0份、聚丙二醇二丙烯酸酯(東亞合成公司製造,製品名「Aronix M-220」、平均聚合度3)20.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 40.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 40.0 parts of 1.9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate 1, 9ND-A") , polypropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., product name "Aronix M-220", average degree of polymerization 3) 20.0 parts, and 1.5 parts of the product name "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.) and 1.5 parts of the product name "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) as a photoinitiator were mixed to prepare an adhesive. . A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
將丙烯酸4-羥基丁酯(4HBA,大阪有機化學工業公司製造)35.0份、1,9-壬二醇二丙烯酸酯(共榮社化學公司製造,製品名「Light Acrylate 1,9ND-A」)40.0份、聚輪烷(Advanced Softmaterials公司製造,製品名「Serm Super Polymer SH3400P」直鏈狀分子:PEG、環狀分子:α-環糊精)25.0份、以及作為光起始劑之製品名「KAYACURE DETX-S」(日本化藥公司製造)1.5份及製品名「IRGACURE907」(BASF JAPAN公司製造)1.5份加以混合,而製備接著劑。除使用如此獲得之接著劑以外,以與實施例1相同之方式獲得偏光膜。 35.0 parts of 4-hydroxybutyl acrylate (4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate 1, 9ND-A") 40.0 parts, polyrotaxane (manufactured by Advanced Softmaterials Co., Ltd., product name "Serm Super Polymer SH3400P" linear molecule: PEG, cyclic molecule: α-cyclodextrin) 25.0 parts, and the name of the product as a photoinitiator" 1.5 parts of KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) and 1.5 parts of the product name "IRGACURE 907" (manufactured by BASF JAPAN Co., Ltd.) were mixed to prepare an adhesive. A polarizing film was obtained in the same manner as in Example 1 except that the thus obtained adhesive was used.
對實施例及比較例中所獲得之偏光膜進行耐水性評價。將評價結果與接著劑之調配一併示於表1。 The polarizing films obtained in the examples and the comparative examples were evaluated for water resistance. The evaluation results are shown in Table 1 together with the formulation of the adhesive.
將所獲得之偏光板裁斷成25mm×150mm之尺寸而製成樣品。將樣品於60℃之溫水中浸漬6小時之後,測定偏光板之自端部之剝離量(mm)。剝離量為10mm以下者為良好。 The obtained polarizing plate was cut into a size of 25 mm × 150 mm to prepare a sample. After the sample was immersed in warm water of 60 ° C for 6 hours, the peeling amount (mm) from the end portion of the polarizing plate was measured. The peeling amount is preferably 10 mm or less.
將所獲得之偏光膜裁斷成100mm×15mm之尺寸而製成樣品。將樣品於25℃之水中浸漬3小時,並自水中提拉樣品。其後,使用手及指甲抓撓樣品之端部,觀察保護膜是否自偏光元件剝離。利用以下之基準評價觀察之結果。 The obtained polarizing film was cut into a size of 100 mm × 15 mm to prepare a sample. The sample was immersed in water at 25 ° C for 3 hours and the sample was pulled from the water. Thereafter, the end of the sample was scratched with a hand and a nail to observe whether or not the protective film was peeled off from the polarizing element. The results of the observations were evaluated using the following criteria.
◎:利用手及指甲無法剝離保護膜 ◎: The protective film cannot be peeled off by hand and nail
○:利用手及指甲可剝離保護膜之端部,但無法剝離中央部 ○: The end of the protective film can be peeled off by hand and nail, but the center part cannot be peeled off.
×:使用手及指甲可容易地剝離保護膜 ×: The protective film can be easily peeled off using hands and nails
如表1所示,使用包括含有活性能量線聚合性基之聚輪烷之接著劑所製造之實施例1~8之偏光膜之耐水性優異。另一方面,使用不含聚輪烷之接著劑所製造之比較例1及2之偏光膜之耐水性不充分。進而,使用包括不含有活性能量線聚合性基之聚輪烷之接著劑所製造之比較例3之偏光膜之耐水性不充分。藉由添加含有活性能量線聚合性基之聚輪烷而提高偏光膜之耐水性之原因並不確定,作出如下推測。 即,認為因聚輪烷之環狀分子之可動性從而交聯點可移動(所謂滑輪效應),藉此對硬化後之接著劑賦予柔軟性,對偏光元件之表面凹凸之密接性增加,結果防止水滲入至偏光元件與接著劑層之界面。進而,認為藉由聚輪烷具有疏水性修飾基而對接著劑賦予疏水性之情況亦有助於防止水滲入至偏光元件與接著劑層之界面。 As shown in Table 1, the polarizing films of Examples 1 to 8 produced by using an adhesive containing a polyrotaxane containing an active energy ray-polymerizable group were excellent in water resistance. On the other hand, the polarizing films of Comparative Examples 1 and 2 produced by using an adhesive containing no polyrotaxane were insufficient in water resistance. Further, the polarizing film of Comparative Example 3 produced by using an adhesive containing a polyrotaxane containing no active energy ray-polymerizable group was insufficient in water resistance. The reason why the water resistance of the polarizing film is improved by adding the polyrotaxane containing the active energy ray-polymerizable group is not determined, and the following estimation is made. In other words, it is considered that the crosslinking point of the polyrotaxane is movable (the so-called pulley effect), thereby imparting flexibility to the adhesive after curing, and the adhesion of the surface unevenness of the polarizing element is increased. Water is prevented from penetrating into the interface between the polarizing element and the adhesive layer. Further, it is considered that the fact that the polyrotaxane has a hydrophobic modifying group to impart hydrophobicity to the adhesive also contributes to preventing water from penetrating into the interface between the polarizing element and the adhesive layer.
本發明之接著劑可尤其適宜地用於偏光膜、各種光學膜及液晶單元之積層。 The adhesive of the present invention can be particularly suitably used for a laminate of a polarizing film, various optical films, and liquid crystal cells.
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- 2015-01-14 KR KR1020167018332A patent/KR102265481B1/en active IP Right Grant
- 2015-01-14 TW TW104101226A patent/TWI667314B/en active
- 2015-01-14 WO PCT/JP2015/050770 patent/WO2015108063A1/en active Application Filing
- 2015-01-14 CN CN201580004032.1A patent/CN105899980B/en active Active
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2019
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20090281213A1 (en) * | 2005-08-31 | 2009-11-12 | The University Of Tokyo | Hydrophobic modified polyrotaxane and crosslinked polyrotaxane |
TW201339263A (en) * | 2012-03-30 | 2013-10-01 | Lintec Corp | Adhesive composition, adhesive and adhesive sheet |
Also Published As
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CN105899980A (en) | 2016-08-24 |
TW201531545A (en) | 2015-08-16 |
CN105899980B (en) | 2020-06-09 |
JP2015155530A (en) | 2015-08-27 |
JP6526972B2 (en) | 2019-06-05 |
WO2015108063A1 (en) | 2015-07-23 |
JP2019144593A (en) | 2019-08-29 |
KR20160108330A (en) | 2016-09-19 |
KR102265481B1 (en) | 2021-06-15 |
JP6832977B2 (en) | 2021-02-24 |
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