TWI535813B - Adhesive resin composition for image display device, adhesive sheet for image display device, image display device and fabricating method thereof - Google Patents
Adhesive resin composition for image display device, adhesive sheet for image display device, image display device and fabricating method thereof 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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
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Description
本發明是有關於影像顯示裝置用黏著性樹脂組成物、影像顯示裝置用黏著片及影像顯示裝置。 The present invention relates to an adhesive resin composition for an image display device, an adhesive sheet for an image display device, and an image display device.
代表性的影像顯示裝置之例子可例示液晶顯示裝置(液晶顯示器(Liquid Crystal Display，LCD))。於液晶顯示裝置之液晶顯示單元等光學部件中通常貼附有偏光板或偏光板與相位差板之積層體等，但近年來內置有觸控面板之液晶顯示裝置之需要不斷增長。將該結構之略圖例示於圖1中。內置有觸控面板之液晶顯示裝置包含透明保護板(玻璃或塑膠基材)1、觸控面板2、偏光板3、液晶顯示單元4，於最近之液晶顯示裝置中，為了防止液晶顯示裝置之破裂、緩和應力及衝擊、以及提高視認性，設有用以貼附透明保護板與觸控面板之黏著層5，另外設有用以貼合觸控面板與偏光板之黏著層6。此種液晶顯示裝置開始用於車載用、室外計量儀器、行動電話、個人電腦等多種用途中，因此隨之帶來使用環境亦變得非常嚴酷。於此種嚴酷之條件下，產生對各部件進行貼合之黏著層5及黏著層6之黏著力降低，且變得容易產生氣泡、剝落等。因此，要求即使於如上所述之嚴酷條件下亦不產生氣泡、剝落等之耐久性高的黏著片。 An example of a representative image display device is a liquid crystal display device (Liquid Crystal Display (LCD)). In an optical component such as a liquid crystal display unit of a liquid crystal display device, a polarizing plate, a laminate of a polarizing plate and a phase difference plate, and the like are usually attached, but in recent years, there has been an increasing demand for a liquid crystal display device incorporating a touch panel. A schematic diagram of the structure is shown in Fig. 1. The liquid crystal display device with the touch panel includes a transparent protection plate (glass or plastic substrate), a touch panel 2, a polarizing plate 3, and a liquid crystal display unit 4. In the recent liquid crystal display device, in order to prevent the liquid crystal display device The adhesive layer 5 is attached to the transparent protective plate and the touch panel, and the adhesive layer 6 for attaching the touch panel and the polarizing plate is provided for rupturing, mitigating stress and impact, and improving visibility. Such liquid crystal display devices have been used in various applications such as in-vehicle use, outdoor measuring instruments, mobile phones, and personal computers, and as a result, the use environment has become very severe. Under such severe conditions, the adhesion between the adhesive layer 5 and the adhesive layer 6 which are bonded to the respective members is lowered, and bubbles, peeling, and the like are likely to occur. Therefore, it is required that an adhesive sheet having high durability such as air bubbles or peeling does not occur even under severe conditions as described above.
對於該要求，作為即使於高溫下、高溫高濕下長時間暴露亦不於貼合界面產生發泡、***、剝落等之黏著材料 組成物，於日本專利特開2007-238853號公報中有所例示。 For this requirement, as an adhesive material which does not cause foaming, bulging, peeling, etc. at the bonding interface even after exposure to high temperature and high humidity for a long time. The composition is exemplified in Japanese Patent Laid-Open Publication No. 2007-238853.
然而，作為日本專利特開2007-238853號公報中所記載之材料，為了使密接性提高而含有具有羧基之成分，存在酸成分腐蝕觸控面板之ITO透明電極之虞。而且，日本專利特開2007-238853號公報中所記載之材料之玻璃轉移溫度低，因此預測其使用性差。 However, as a material described in Japanese Laid-Open Patent Publication No. 2007-238853, in order to improve the adhesion, a component having a carboxyl group is contained, and an acid component is used to etch the ITO transparent electrode of the touch panel. Further, since the material described in Japanese Laid-Open Patent Publication No. 2007-238853 has a low glass transition temperature, it is predicted to have poor usability.
本發明之目的在於提供對於防止破裂、緩和應力及衝擊而言有用，透明性優異，改善顯示影像之模糊、閃爍等，且抑制特別是於高溫條件下(例如80℃以上)及高濕條件下(例如85℃/85%RH以上)所產生之氣泡、***、剝落等的使用性優異之影像顯示裝置用黏著性樹脂組成物、使用該影像顯示裝置用黏著性樹脂組成物之影像顯示裝置用黏著片及影像顯示裝置。 An object of the present invention is to provide a method for preventing cracking, mitigating stress and impact, and having excellent transparency, improving blurring, flickering, and the like of a display image, and suppressing it particularly under high temperature conditions (for example, 80 ° C or higher) and high humidity conditions. (for example, 85° C./85% RH or more), an adhesive resin composition for an image display device, which is excellent in the use property, such as a bubble, a bulge, or a peeling, and an image display device using the adhesive resin composition for an image display device. Adhesive sheet and image display device.
本發明者等人為了解決上述課題而進行了銳意研究，結果發現藉由於(甲基)丙烯酸系衍生物聚合物、於分子內具有1個(甲基)丙烯醯基之(甲基)丙烯酸系衍生物單體中含有特定之具有2官能之(甲基)丙烯醯基之交聯劑、及光聚合起始劑的樹脂組成物，可解決上述課題。基於該發現而完成本發明。 In order to solve the above problems, the inventors of the present invention conducted intensive studies and found that a (meth)acrylic derivative polymer and a (meth)acrylic acid group having one (meth)acrylonium group in the molecule The resin composition containing a specific bifunctional (meth)acryl fluorenyl group-containing crosslinking agent and a photopolymerization initiator can solve the above problems. The present invention has been completed based on this finding.
亦即，本發明提供：(1)一種影像顯示裝置用黏著性樹脂組成物，含有(A)(甲基)丙烯酸系衍生物聚合物、(B)於分子內具有1個(甲基)丙烯醯基之(甲基)丙烯酸系衍生物單體、(C)具 有2官能之(甲基)丙烯醯基之交聯劑及(D)光聚合起始劑，所述(C)具有2官能之(甲基)丙烯醯基之交聯劑包含重量平均分子量為2.0×104~4.0×104之交聯劑(以下，有時記載為「交聯劑Y」)，該交聯劑Y之調配量相對於該黏著性樹脂組成物總量而言為4質量%~8質量%；(2)一種影像顯示裝置用黏著片，其是將如上述(1)所述之影像顯示裝置用黏著性樹脂組成物硬化為片材狀而獲得；以及(3)一種影像顯示裝置，其於視認側具有由如上述(1)所述之影像顯示裝置用黏著性樹脂組成物所形成之層。 In other words, the present invention provides: (1) an adhesive resin composition for an image display device comprising (A) a (meth)acrylic derivative polymer and (B) having one (meth)acryl in the molecule. a mercapto (meth)acrylic derivative monomer, (C) a bifunctional (meth)acrylonyl group-containing crosslinking agent, and (D) a photopolymerization initiator, wherein the (C) has a bifunctional group The (meth)acrylonitrile-based crosslinking agent contains a crosslinking agent having a weight average molecular weight of from 2.0 × 10 4 to 4.0 × 10 4 (hereinafter sometimes referred to as "crosslinking agent Y"), and the crosslinking agent Y The amount of the composition is 4% by mass to 8% by mass based on the total amount of the adhesive resin composition; and (2) an adhesive sheet for an image display device, which is used for the image display device according to (1) above. And (3) an image display device having a layer formed of the adhesive resin composition for an image display device according to (1) above, wherein the adhesive resin composition is cured in a sheet form.
藉由本發明，可提供具有耐衝擊性，視認性優異之影像顯示裝置。特別是可提供視認側之透明保護板(例如玻璃)與黏著性樹脂組成物之密接力高，即使暴露於如85℃/85%RH這樣的高溫高濕下，亦不產生剝落、***、氣泡等，且不使顯示器之視認性降低之影像顯示裝置用黏著性樹脂組成物及影像顯示裝置用黏著片。 According to the present invention, it is possible to provide an image display device which is excellent in impact resistance and excellent in visibility. In particular, the transparent protective sheet (for example, glass) on the viewing side can be provided with a high adhesion force to the adhesive resin composition, and even if exposed to high temperature and high humidity such as 85 ° C / 85% RH, no peeling, bulging, or bubbles are generated. An adhesive resin composition for an image display device and an adhesive sheet for an image display device, which do not reduce the visibility of the display.
亦即，藉由本發明可提供能夠將例如液晶顯示單元與觸控面板、液晶顯示單元與透明保護板、觸控面板與透明保護板等、影像顯示單元與其他影像顯示裝置中所必需的部件、或者位於較影像顯示裝置之影像顯示單元更靠視認側之部件彼此貼合的影像顯示裝置用黏著片。 That is, the present invention can provide components necessary for, for example, a liquid crystal display unit and a touch panel, a liquid crystal display unit and a transparent protective panel, a touch panel, a transparent protective panel, and the like, and an image display unit and other image display devices, Or an adhesive sheet for an image display device in which the components on the viewing side of the image display unit of the image display device are attached to each other.
本發明之影像顯示裝置用黏著性樹脂組成物含有(A)(甲基)丙烯酸系衍生物聚合物、(B)(甲基)丙烯酸系衍生 物單體、特定之(C)具有2官能之(甲基)丙烯醯基之交聯劑及(D)聚合起始劑，本發明之影像顯示裝置用黏著片是將該黏著性樹脂組成物加工為片材狀後進行硬化而成的，影像顯示裝置是使用該黏著性樹脂組成物或該黏著片而製造的。以下，對本發明之實施形態加以詳細說明。 The adhesive resin composition for an image display device of the present invention contains (A) a (meth)acrylic derivative polymer and (B) a (meth)acrylic derivative. The monomer, the specific (C) crosslinker having a bifunctional (meth) acrylonitrile group, and (D) a polymerization initiator, the adhesive sheet for an image display device of the present invention is the adhesive resin composition The image display device is manufactured by using the adhesive resin composition or the adhesive sheet after being processed into a sheet shape and then hardened. Hereinafter, embodiments of the present invention will be described in detail.
<影像顯示裝置用黏著性樹脂組成物> <Adhesive resin composition for image display device>
以下，對本發明之影像顯示裝置用黏著性樹脂組成物(以下有時簡稱為「黏著性樹脂組成物」)中所含有之成分逐一加以說明。 Hereinafter, the components contained in the adhesive resin composition (hereinafter sometimes simply referred to as "adhesive resin composition") for the image display device of the present invention will be described one by one.
[(A)(甲基)丙烯酸系衍生物聚合物] [(A) (meth)acrylic derivative polymer]
本發明中之(A)(甲基)丙烯酸系衍生物聚合物是指使1種於分子內具有1個(甲基)丙烯醯基之單體聚合或者將2種以上之於分子內具有1個(甲基)丙烯醯基之單體組合而共聚而成者。另外，若為不損及本發明之效果之範圍內，則亦可共聚於分子內具有2個以上(甲基)丙烯醯基之化合物或不具(甲基)丙烯醯基之聚合性化合物(例如丙烯腈、苯乙烯、乙酸乙烯酯、乙烯、丙烯等於分子內具有1個聚合性不飽和鍵之化合物或者二乙烯基苯等於分子內具有2個以上聚合性不飽和鍵之化合物)。 In the (A) (meth)acrylic derivative polymer of the present invention, one type of monomer having one (meth)acryloyl group in the molecule is polymerized or two or more kinds are contained in the molecule. A monomer obtained by combining a monomer of (meth)acrylonitrile group. Further, in the range which does not impair the effects of the present invention, it may be copolymerized with a compound having two or more (meth)acryl fluorenyl groups in the molecule or a polymerizable compound having no (meth) acryl fluorenyl group (for example). Acrylonitrile, styrene, vinyl acetate, ethylene, and propylene are equal to a compound having one polymerizable unsaturated bond in the molecule or divinylbenzene is equivalent to a compound having two or more polymerizable unsaturated bonds in the molecule).
形成(A)(甲基)丙烯酸系衍生物聚合物之單體例如可列舉：(甲基)丙烯酸、(甲基)丙烯醯胺、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正月桂基酯、(甲基)丙 烯酸硬脂基酯等碳數為1~18之(甲基)丙烯酸烷基酯；(甲基)丙烯酸苄基酯、(甲基)丙烯酸苯氧基乙酯等具有芳香環(甲基)丙烯酸酯；丁氧基乙二醇(甲基)丙烯酸酯、丁氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯等具有烷氧基之(甲基)丙烯酸酯；(甲基)丙烯酸環己基酯、(甲基)丙烯酸異冰片基酯、(甲基)丙烯酸二環戊基酯等具有脂環族基之(甲基)丙烯酸酯；(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-3-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯等具有羥基之(甲基)丙烯酸酯；(甲基)丙烯酸四氫呋喃甲基酯；四乙二醇單甲醚(甲基)丙烯酸酯、六乙二醇單甲醚(甲基)丙烯酸酯、八乙二醇單甲醚(甲基)丙烯酸酯、九乙二醇甲醚(甲基)丙烯酸酯等聚乙二醇單甲醚(甲基)丙烯酸酯；七丙二醇單甲醚(甲基)丙烯酸酯等聚丙二醇單甲醚(甲基)丙烯酸酯；四乙二醇***(甲基)丙烯酸酯等聚乙二醇***(甲基)丙烯酸酯；四乙二醇(甲基)丙烯酸酯、六乙二醇(甲基)丙烯酸酯、八乙二醇(甲基)丙烯酸酯等。 Examples of the monomer forming the (A) (meth)acrylic derivative polymer include (meth)acrylic acid, (meth)acrylamide, methyl (meth)acrylate, and ethyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate , n-lauryl (meth)acrylate, (methyl) propyl An alkyl (meth)acrylate having a carbon number of from 1 to 18 such as stearyl enoate; an aromatic ring (methyl) such as benzyl (meth)acrylate or phenoxyethyl (meth)acrylate Acrylate; butoxyethylene glycol (meth) acrylate, butoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, etc. a (meth) acrylate having an alicyclic group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or dicyclopentyl (meth) acrylate; a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl methacrylate, 3-hydroxypropyl (meth) acrylate, or 4-hydroxybutyl (meth) acrylate; (meth)acrylic acid Tetrahydrofuran methyl ester; tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nine ethylene Polyethylene glycol monomethyl ether (meth) acrylate such as alcohol methyl ether (meth) acrylate; polypropylene glycol monomethyl ether (meth) acrylate such as heptapropanediol monomethyl ether (meth) acrylate; Glycol ether (methyl) Acid esters of polyethylene glycol ethyl ether (meth) acrylate; tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, octaethyleneglycol (meth) acrylate.
於上述化合物中，較佳的是含有具有碳數為4~18之烷基的(甲基)丙烯酸酯，於將共聚之1分子之聚合物設為100質量%之情形時，具有碳數為4~18之烷基的(甲基)丙烯酸酯之比例較佳的是5質量%~95質量%，更佳的是10質量%~90質量%。若為5質量%~95質量%，則存在於形成黏著片後之加工性中，玻璃或塑膠等之透明基材之密接性提高之傾向。 Among the above-mentioned compounds, a (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is preferred, and when the polymer of one molecule of the copolymer is 100% by mass, the carbon number is The proportion of the (meth) acrylate of the alkyl group of 4 to 18 is preferably from 5% by mass to 95% by mass, more preferably from 10% by mass to 90% by mass. When it is 5% by mass to 95% by mass, the adhesiveness after the formation of the pressure-sensitive adhesive sheet tends to improve the adhesion of a transparent substrate such as glass or plastic.
此種共聚比例之聚合物通常可藉由以與上述共聚比例 相同之比例而調配各單體，使其共聚而獲得，較佳的是使聚合率實質上接近100質量%。 The polymer of such copolymerization ratio can usually be obtained by copolymerization ratio with the above The monomers are blended in the same ratio and copolymerized to obtain them. It is preferred that the polymerization rate be substantially close to 100% by mass.
作為與具有碳數為4~18之烷基的(甲基)丙烯酸酯共聚之單體，並不限定於上述所記載之化合物，較佳的是具有羥基、嗎啉基、胺基、羧基、氰基、羰基、硝基等極性基之單體，亦即，較佳的是具有該些極性基之(甲基)丙烯酸酯具有使與塑膠等透明基材之黏著性提高之傾向。 The monomer copolymerized with the (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is not limited to the above-described compound, and preferably has a hydroxyl group, a morpholinyl group, an amine group, a carboxyl group, or the like. A monomer having a polar group such as a cyano group, a carbonyl group or a nitro group, that is, a (meth) acrylate having such a polar group preferably has an advantage of improving adhesion to a transparent substrate such as plastic.
(A)(甲基)丙烯酸系衍生物聚合物之重量平均分子量是藉由凝膠滲透色譜法，使用標準聚苯乙烯之校準曲線而換算之值，較佳的是1×105~1×106，更佳的是1×105~5×105。藉由使重量平均分子量為1×105以上，可於高溫(例如80℃以上)、高溫高濕(例如85℃/85%RH)之環境下獲得相對於透明基材等而言並不產生剝落之黏著力；藉由使其為1×106以下，則影像顯示裝置用黏著性樹脂組成物之黏度並不過於變高，製成黏著片時之加工性變良好。 The weight average molecular weight of the (A) (meth)acrylic derivative polymer is a value converted by a gel permeation chromatography using a calibration curve of standard polystyrene, preferably 1 × 10 5 - 1 × 10 6 , more preferably 1 × 10 5 ~ 5 × 10 5 . By making the weight average molecular weight to be 1×10 5 or more, it can be obtained in an environment of high temperature (for example, 80° C. or higher), high temperature and high humidity (for example, 85° C./85% RH), and does not occur with respect to a transparent substrate or the like. When the adhesiveness is 1 × 10 6 or less, the viscosity of the adhesive resin composition for an image display device is not too high, and the workability when the adhesive sheet is formed becomes good.
而且，(甲基)丙烯酸衍生物聚合物之聚合方法可使用溶液聚合、乳化聚合、懸浮聚合、本體聚合等已知之聚合方法。 Further, as the polymerization method of the (meth)acrylic acid derivative polymer, known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can be used.
聚合起始劑可使用由於熱而產生自由基之化合物，具體而言可列舉：如過氧化苯甲醯、過氧苯甲酸第三丁酯、氫過氧化異丙苯、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、過氧化二碳酸二(2-乙氧基乙基)酯、過氧化新癸酸第三丁酯、過氧化特戊酸第三丁酯、過氧化(3,5,5-三甲基己醯基)、過氧化二丙醯基、過氧化二乙醯基、過氧化 二(十二烷基)這樣的有機過氧化物，或者如2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、1,1'-偶氮雙(環己烷-1-甲腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、2,2'-偶氮雙(2-甲基丙酸)二甲酯、4,4'-偶氮雙(4-氰基戊酸)、2,2'-偶氮雙(2-羥基甲基丙腈)、2,2'-偶氮雙[2-(咪唑啉-2-基)丙烷]這樣的偶氮系化合物等。 As the polymerization initiator, a compound which generates a radical due to heat can be used, and specific examples thereof include: benzamidine peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisocarbonate Propyl ester, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy neodecanoate, tert-butyl peroxypivalate, peroxidation (3,5,5-trimethylhexyl), dipropenyl peroxide, diethylperoxy peroxide, peroxidation An organic peroxide such as di(dodecyl) or such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'- Azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl -4-methoxyvaleronitrile), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2 An azo compound such as azo-bis(2-hydroxymethylpropionitrile) or 2,2'-azobis[2-(imidazolin-2-yl)propane.
(甲基)丙烯酸系衍生物聚合物之調配量相對於黏著性樹脂組成物之總量而言較佳的是10質量%~70質量%，更佳的是15質量%~60質量%。若(A)(甲基)丙烯酸系衍生物聚合物之調配量為10質量%~70質量%，則影像顯示裝置用黏著性樹脂組成物之黏度進入製作黏著片時之適當的黏度範圍中，加工性良好。而且，所得之黏著片對於玻璃或塑膠等透明基材之黏著性良好。 The blending amount of the (meth)acrylic derivative polymer is preferably 10% by mass to 70% by mass, and more preferably 15% by mass to 60% by mass based on the total amount of the adhesive resin composition. When the blending amount of the (A) (meth)acrylic derivative polymer is from 10% by mass to 70% by mass, the viscosity of the adhesive resin composition for an image display device enters an appropriate viscosity range at the time of producing the adhesive sheet, Good processability. Moreover, the obtained adhesive sheet has good adhesion to a transparent substrate such as glass or plastic.
[(B)(甲基)丙烯酸系衍生物單體] [(B) (meth)acrylic derivative monomer]
本發明之影像顯示裝置用黏著性樹脂組成物中之(B)(甲基)丙烯酸系衍生物單體若為於分子內具有1個(甲基)丙烯醯基之單體則並無特別限定，可使用公知之材料，亦可將2種以上組合使用。其具體例可列舉(甲基)丙烯酸、(甲基)丙烯醯胺、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正月桂基酯、(甲基)丙烯酸硬脂基酯等碳數為1~18之(甲基)丙烯酸烷基酯；(甲基)丙烯酸苄基酯、(甲基)丙烯酸苯氧基乙酯等具有芳香環之(甲基)丙烯酸酯；丁氧 基乙二醇(甲基)丙烯酸酯、丁氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯等具有烷氧基的(甲基)丙烯酸酯；(甲基)丙烯酸環己基酯、(甲基)丙烯酸異冰片基酯、(甲基)丙烯酸二環戊基酯等具有脂環族基之(甲基)丙烯酸酯；(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-3-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯等具有羥基之(甲基)丙烯酸酯；(甲基)丙烯酸四氫呋喃甲基酯；(甲基)丙烯酸-N,N-二甲基胺基乙酯、N,N-二甲基胺基丙基丙烯醯胺、N,N-二甲基丙烯醯胺、(甲基)丙烯醯嗎啉、N-異丙基丙烯醯胺、N,N-二乙基丙烯醯胺、N-羥基乙基丙烯醯胺等具有醯胺基之(甲基)丙烯酸酯；2-(2-甲基丙烯醯氧基乙基氧基)乙基異氰酸酯、2-(甲基)丙烯醯氧基乙基異氰酸酯等具有異氰酸酯基之(甲基)丙烯酸酯；四乙二醇單甲醚(甲基)丙烯酸酯、六乙二醇單甲醚(甲基)丙烯酸酯、八乙二醇單甲醚(甲基)丙烯酸酯、九乙二醇甲醚(甲基)丙烯酸酯等聚乙二醇單甲醚(甲基)丙烯酸酯；七丙二醇單甲醚(甲基)丙烯酸酯等聚丙二醇單甲醚(甲基)丙烯酸酯；四乙二醇***(甲基)丙烯酸酯等聚乙二醇***(甲基)丙烯酸酯；四乙二醇(甲基)丙烯酸酯、六乙二醇(甲基)丙烯酸酯、八乙二醇(甲基)丙烯酸酯等。 The (B) (meth)acrylic derivative monomer in the adhesive resin composition for an image display device of the present invention is not particularly limited as long as it has one (meth)acryloyl group in the molecule. A known material may be used, or two or more types may be used in combination. Specific examples thereof include (meth)acrylic acid, (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, (meth)acrylic acid a (meth)acrylic acid alkyl ester having a carbon number of 1 to 18 such as stearyl ester; (meth)acrylic acid having an aromatic ring such as benzyl (meth)acrylate or phenoxyethyl (meth)acrylate Ester (meth) acrylate having alkoxy group such as ethylene glycol (meth) acrylate, butoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate (meth) acrylate having an alicyclic group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate; (meth) acrylate - a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl ester, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; tetrahydrofuran methyl (meth)acrylate; (Meth)acrylic acid-N,N-dimethylaminoethyl ester, N,N-dimethylaminopropyl acrylamide, N,N-dimethyl decylamine, (meth) propylene oxime (meth) acrylate having decylamino group such as morpholine, N-isopropylacrylamide, N,N-diethyl acrylamide, N-hydroxyethyl acrylamide, etc.; 2-(2-A (meth) acrylate having an isocyanate group such as acryloyloxyethyloxy)ethylisocyanate or 2-(meth)acryloxyethyl isocyanate; tetraethylene glycol monomethyl ether (methyl) Acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate such as ethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol methyl ether (meth) acrylate; heptapropanediol monomethyl ether (meth) acrylate Polypropylene glycol monomethyl ether (meth) acrylate such as ester; polyethylene glycol ether (meth) acrylate such as tetraethylene glycol diethyl ether (meth) acrylate; tetraethylene glycol (meth) acrylate, six Ethylene glycol (meth) acrylate, octaethylene glycol (meth) acrylate, and the like.
特別是將烷基之碳數為4~18之(甲基)丙烯酸烷基酯與下述通式(b)所表示之含有羥基之丙烯酸酯併用之方法較佳。 In particular, a method in which an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is used together with a hydroxy group-containing acrylate represented by the following formula (b) is preferred.
CH2=CXCOO(CmH2mO)nH…(b) CH 2 =CXCOO(C m H 2m O) n H...(b)
(於式中，X為H或CH3，m表示2~4之整數，n表 示1~10之整數。) (In the formula, X is H or CH 3 , m represents an integer of 2 to 4, and n represents an integer of 1 to 10.)
烷基之碳數為4~18之(甲基)丙烯酸烷基酯可列舉(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸硬脂基酯等，較佳的是(甲基)丙烯酸正丁酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯等，特佳的是2-(甲基)丙烯酸乙基己酯。 Examples of the alkyl (meth)acrylate having 4 to 18 carbon atoms in the alkyl group include n-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, and (methyl). N-octyl acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, etc. Preferred are n-butyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, etc., particularly preferably 2- Ethylhexyl (meth)acrylate.
而且，丙烯酸酯較甲基丙烯酸酯更佳。該些(甲基)丙烯酸酯亦可將2種以上組合使用。 Moreover, acrylates are preferred over methacrylates. These (meth)acrylates may be used in combination of two or more kinds.
通式(b)所表示之含有羥基之(甲基)丙烯酸酯可列舉(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-1-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-3-羥基丙酯、(甲基)丙烯酸-1-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-3-羥基丁酯、(甲基)丙烯酸-2-羥基丁酯、(甲基)丙烯酸-1-羥基丁酯等含有羥基之(甲基)丙烯酸酯；二乙二醇單(甲基)丙烯酸酯或三乙二醇單(甲基)丙烯酸酯等聚乙二醇單(甲基)丙烯酸酯；二丙二醇單(甲基)丙烯酸酯或三丙二醇單(甲基)丙烯酸酯等聚丙二醇單(甲基)丙烯酸酯；二丁二醇單(甲基)丙烯酸酯或三丁二醇單(甲基)丙烯酸酯等聚丁二醇單(甲基)丙烯酸酯等。該些化合物中較佳的是(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-1-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-3-羥基丙酯、(甲基)丙烯酸-1-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-3-羥 基丁酯、(甲基)丙烯酸-2-羥基丁酯、(甲基)丙烯酸-1-羥基丁酯等，特佳的是(甲基)丙烯酸-2-羥基乙酯及(甲基)丙烯酸-4-羥基丁酯，極佳的是(甲基)丙烯酸-4-羥基丁酯。而且，該些(甲基)丙烯酸酯亦可將2種以上組合使用。 Examples of the hydroxyl group-containing (meth) acrylate represented by the formula (b) include 2-hydroxyethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, and (meth)acrylic acid-2. -hydroxypropyl ester, 3-hydroxypropyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxyl (meth)acrylate a hydroxyl group-containing (meth) acrylate such as butyl ester, 2-hydroxybutyl (meth) acrylate or 1-hydroxybutyl (meth) acrylate; diethylene glycol mono (meth) acrylate or three Polyethylene glycol mono(meth)acrylate such as ethylene glycol mono(meth)acrylate; polypropylene glycol mono(methyl) such as dipropylene glycol mono(meth)acrylate or tripropylene glycol mono(meth)acrylate Acrylate; polybutylene glycol mono(meth)acrylate such as dibutylene glycol mono(meth)acrylate or tributyl glycol mono(meth)acrylate. Preferred among these compounds are 2-hydroxyethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid- 3-hydroxypropyl ester, 1-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxyl (meth)acrylate Butyl ester, 2-hydroxybutyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, etc., particularly preferably 2-hydroxyethyl (meth)acrylate and (meth)acrylic acid 4-Hydroxybutyl ester, very preferred is 4-hydroxybutyl (meth)acrylate. Further, these (meth) acrylates may be used in combination of two or more kinds.
而且，自可使本發明之效果進一步提高之觀點考慮，較佳的是(B)(甲基)丙烯酸系衍生物單體含有(甲基)丙烯醯嗎啉。 Further, from the viewpoint of further improving the effects of the present invention, it is preferred that the (B) (meth)acrylic derivative monomer contains (meth)acryloquinone morpholine.
使用(甲基)丙烯醯嗎啉之情形時之含量相對於黏著性樹脂組成物之總量而言較佳的是5質量%~40質量%，更佳的是10質量%~30質量%，特佳的是15質量%~25質量%。 The content in the case of using (meth) propylene hydrazine is preferably from 5% by mass to 40% by mass, more preferably from 10% by mass to 30% by mass, based on the total amount of the adhesive resin composition. Particularly preferred is 15% by mass to 25% by mass.
本發明中之(B)(甲基)丙烯酸系衍生物單體之含量對於黏著性樹脂組成物之總量而言較佳的是15質量%~80質量%。若(B)(甲基)丙烯酸衍生物單體之含量為15質量%~80質量%之範圍，則將所得之黏著片貼合於玻璃基板與玻璃基板之間後，抑制實施高溫下(80℃以上)及高溫高濕下(85℃/85%RH)之可靠性試驗後之氣泡的產生、剝落。自以上觀點考慮，(B)(甲基)丙烯酸衍生物單體之含量更佳的是30質量%~80質量%，特佳的是40質量%~80質量%。 The content of the (B) (meth)acrylic derivative monomer in the present invention is preferably 15% by mass to 80% by mass based on the total amount of the adhesive resin composition. When the content of the (B) (meth)acrylic acid derivative monomer is in the range of 15% by mass to 80% by mass, the obtained adhesive sheet is bonded between the glass substrate and the glass substrate, and then the high temperature is suppressed (80). The generation and peeling of bubbles after the reliability test under high temperature and high humidity (85 ° C / 85% RH). From the above viewpoints, the content of the (B) (meth)acrylic acid derivative monomer is more preferably 30% by mass to 80% by mass, particularly preferably 40% by mass to 80% by mass.
[(C)具有2官能之(甲基)丙烯醯基之交聯劑] [(C) Crosslinker having a bifunctional (meth) acrylonitrile group]
本發明中之(C)具有2官能之(甲基)丙烯醯基之交聯劑是於分子內具有2個(甲基)丙烯醯基之單體。於本發明中，必須包含特定量之重量平均分子量為2.0×104~4.0×104 之交聯劑Y。藉此可抑制高溫條件下及高濕條件下之氣泡、***、剝落等之產生。 The (C) crosslinker having a bifunctional (meth) acrylonitrile group in the present invention is a monomer having two (meth) acrylonitrile groups in the molecule. In the present invention, it is necessary to contain a specific amount of the crosslinking agent Y having a weight average molecular weight of from 2.0 × 10 4 to 4.0 × 10 4 . Thereby, generation of bubbles, bulging, peeling, and the like under high temperature conditions and high humidity conditions can be suppressed.
製造具有此種重量平均分子量之具有2官能之(甲基)丙烯醯基之交聯劑Y之方法可使用公知之方法，例如可藉由使如異佛爾酮二異氰酸酯、甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯等各種二異氰酸酯，與烷二醇、聚烷二醇、聚酯多元醇等各種二醇，與(甲基)丙烯酸羥基烷基酯、內酯改質(甲基)丙烯酸羥烷基酯、異氰酸酯(甲基)丙烯酸烷基酯等各種(甲基)丙烯酸酯以兩末端成為(甲基)丙烯醯基之方式進行反應而合成。 A method of producing a cross-linking agent Y having a bifunctional (meth) acrylonitrile group having such a weight average molecular weight can be carried out by a known method, for example, by using, for example, isophorone diisocyanate, toluene diisocyanate, or Various diisocyanates such as phenylmethane diisocyanate and hexamethylene diisocyanate, and various diols such as alkanediol, polyalkylene glycol, and polyester polyol, and hydroxyalkyl (meth)acrylate and lactone Various (meth) acrylates such as a hydroxyalkyl (meth) acrylate or an alkyl isocyanate (meth) acrylate are synthesized by reacting at the both ends to form a (meth) acrylonitrile group.
其中，若為具有起因於異佛爾酮二異氰酸酯之骨架、亦即下述通式(a)所表示之骨架的二(甲基)丙烯酸胺基甲酸酯，則本發明之氣泡、***、剝落等之產生抑制效果優異而較佳。 In the case of the di(meth)acrylic acid urethane having a skeleton derived from isophorone diisocyanate, that is, a skeleton represented by the following formula (a), the bubbles, bulges, and It is preferable that the effect of suppressing peeling or the like is excellent.
而且，所述交聯劑Y相對於黏著性樹脂組成物總量而言必須為4質量%~8質量%，較佳的是5質量%~7質量%。於不足4質量%之情形時，交聯密度低，黏著片於高溫下之尺寸穩定性差；於超過8質量%之情形時，交聯密 度過於變高，於將所得之黏著片貼合於玻璃基板等透明保護板與觸控面板、液晶單元等貼合對象部件之間後，於實施高溫下(80℃以上)及高濕下(85℃/85%RH)之可靠性試驗後產生氣泡或產生剝落。 Further, the crosslinking agent Y must be 4% by mass to 8% by mass, and preferably 5% by mass to 7% by mass based on the total amount of the adhesive resin composition. When the content is less than 4% by mass, the crosslinking density is low, and the dimensional stability of the adhesive sheet at a high temperature is poor; when it exceeds 8% by mass, the crosslinked density is When the adhesive sheet is attached to a transparent protective sheet such as a glass substrate and a member to be bonded such as a touch panel or a liquid crystal cell, the adhesive sheet is placed at a high temperature (above 80 ° C) and high humidity ( After the reliability test of 85 ° C / 85% RH), bubbles were generated or peeling occurred.
另外，於本發明中，作為(C)成分，除了所述交聯劑Y以外，亦可於不損及本發明之效果的範圍內併用其他交聯劑，亦即偏離所述重量平均分子量之分子量之具有2官能之(甲基)丙烯醯基之交聯劑或具有3官能以上之(甲基)丙烯醯基之交聯劑等。 Further, in the present invention, as the component (C), in addition to the crosslinking agent Y, other crosslinking agents may be used in combination with the effect of not impairing the effects of the present invention, that is, deviating from the weight average molecular weight. A crosslinking agent having a bifunctional (meth)acryl fluorenyl group having a molecular weight or a crosslinking agent having a trifunctional or higher (meth) acrylonitrile group.
[(D)光聚合起始劑] [(D) Photopolymerization initiator]
本發明中所使用之(D)光聚合起始劑是藉由活性能量線之照射而促進硬化反應之化合物，此處所謂活性能量線是指紫外線、電子束、α射線、β射線、γ射線等。 The (D) photopolymerization initiator used in the present invention is a compound which promotes a hardening reaction by irradiation with an active energy ray. Here, the active energy ray means ultraviolet ray, electron beam, α ray, β ray, γ ray. Wait.
光聚合起始劑之選定並無特別限定，可使用二苯甲酮系、蒽醌系、苯甲醯系、鋶鹽、重氮鹽、鎓鹽等公知之材料。 The selection of the photopolymerization initiator is not particularly limited, and a known material such as a benzophenone-based, an anthraquinone-based, a benzamidine-based, an anthracene salt, a diazonium salt or a phosphonium salt can be used.
具體而言可列舉：二苯甲酮、N,N'-四甲基-4,4'-二胺基二苯甲酮(米其勒酮)、N,N-四乙基-4,4'-二胺基二苯甲酮、4-甲氧基-4,4'-二甲基胺基二苯甲酮、α-羥基異丁基苯酮、2-乙基蒽醌、第三丁基蒽醌、1,4-二甲基蒽醌、1-氯蒽醌、2,3-二氯蒽醌、3-氯-2-甲基蒽醌、1,2-苯并蒽醌、2-苯基蒽醌、1,4-萘醌、9,10-菲醌、噻噸酮、2-氯噻噸酮、1-羥基環己基苯基酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2,2-二乙氧基苯乙酮等芳香族酮化 合物；安息香、甲基安息香、乙基安息香等安息香化合物；安息香甲醚、安息香***、安息香異丁醚、安息香苯醚等安息香醚化合物；苯偶醯、苯偶醯二甲基縮酮等苯偶醯化合物；β-(吖啶-9-基)(甲基)丙烯酸之酯化合物；9-苯基吖啶、9-吡啶基吖啶、1,7-二吖啶基庚烷等吖啶化合物、2-(鄰氯苯基)-4,5-二苯基咪唑二聚體、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)咪唑二聚體、2-(鄰氟苯基)-4,5-二苯基咪唑二聚體、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚體、2-(對甲氧基苯基)-4,5-二苯基咪唑二聚體、2,4-二(對甲氧基苯基)-5-苯咪唑二聚體、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑二聚體、2-(對甲基巰基苯基)-4,5-二苯基咪唑二聚體等2,4,5-三芳基咪唑二聚體、2-苄基-2-二甲基胺基-1-(4-N-嗎啉基苯基)-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-N-嗎啉基-1-丙烷、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、寡(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)等。 Specific examples thereof include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Mitchler), and N,N-tetraethyl-4,4. '-Diaminobenzophenone, 4-methoxy-4,4'-dimethylaminobenzophenone, α-hydroxyisobutyl benzophenone, 2-ethyl hydrazine, third butyl Base, 1,4-dimethylhydrazine, 1-chloroindole, 2,3-dichloropurine, 3-chloro-2-methylindole, 1,2-benzopyrene, 2 -phenylhydrazine, 1,4-naphthoquinone, 9,10-phenanthrenequinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1 Aromatic ketoneization of 2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone Compound; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin phenyl ether; benzophenone, benzophenone dimethyl ketal and the like Even oxime compound; β-(acridin-9-yl)(meth)acrylic acid ester compound; acridine such as 9-phenyl acridine, 9-pyridyl acridine, 1,7-diacridine heptane a compound, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxy Phenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-benzimidazole dimer, 2-(2,4-dimethoxy 2,4,5-triarylimidazole dimerization of phenyl)-4,5-diphenylimidazole dimer, 2-(p-methylphenylphenyl)-4,5-diphenylimidazole dimer , 2-benzyl-2-dimethylamino-1-(4-N-morpholinylphenyl)-1-butanone, 2-methyl-1-[4-(methylthio)benzene ]]-2-N-morpholinyl-1-propane, bis(2,4,6-trimethylbenzylidene)-phenyl oxidation , Oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.
而且，特別是不使黏著性樹脂組成物著色之聚合起始劑較佳的是1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-[4-(2-羥乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮等α-羥基烷基苯酮系化合物；雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基-二苯基氧化膦等醯基氧化膦系化合物；寡(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)及該些化合物組合而成者。 Further, in particular, a polymerization initiator which does not color the adhesive resin composition is preferably 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-propan-1-one. Α-hydroxyalkylphenone compound such as 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one; double (2, 4 ,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2, A fluorenylphosphine oxide compound such as 4,6-trimethylbenzylidene-diphenylphosphine oxide; oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)benzene) Base) Acetone) and combinations of these compounds.
而且，特別是為了製作厚的片材，較佳的是包含雙 (2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基-二苯基氧化膦等醯基氧化膦系化合物的光聚合起始劑。 Moreover, especially in order to make a thick sheet, it is preferred to include a double (2,4,6-Trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl oxidation A photopolymerization initiator of a fluorenylphosphine oxide compound such as phosphine or 2,4,6-trimethylbenzylidene-diphenylphosphine oxide.
而且，為了減少片材之臭氣，較佳的是寡(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)。該些光聚合起始劑亦可組合使用多種。 Further, in order to reduce the odor of the sheet, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone) is preferred. These photopolymerization initiators may also be used in combination of plural kinds.
本發明中之(D)光聚合起始劑之含量相對於黏著性樹脂組成物之總量而言較佳的是0.1質量%~5質量%。藉由設為5質量%以下，所得之黏著片之透射率高，且色調亦不泛黃。自以上觀點考慮，更佳的是3質量%以下。 The content of the (D) photopolymerization initiator in the present invention is preferably from 0.1% by mass to 5% by mass based on the total amount of the adhesive resin composition. When it is set to 5% by mass or less, the obtained adhesive sheet has a high transmittance and the color tone is not yellowed. From the above viewpoints, it is more preferably 3% by mass or less.
[其他添加劑] [Other additives]
本發明之影像顯示用黏著性樹脂組成物中，除了上述(A)、(B)、(C)及(D)以外，亦可視需要而調配各種添加劑。本發明中可調配之各種添加劑例如可列舉：以提高調配(A)、(B)、(C)及(D)而所得之黏著性樹脂組成物之保存穩定性為目的而添加之對甲氧基苯酚等聚合抑制劑，以提高藉由光使黏著性樹脂組成物硬化而所得之黏著片的耐熱性為目的而添加之三苯基膦等抗氧化劑，以提高對於紫外線等光之耐受性為目的而添加的HALS(Hindered Amine Light Stabilizer，受阻胺光穩定劑)等光穩定劑，用以提高對玻璃等之密接性而添加的矽烷偶合劑等。 In addition to the above (A), (B), (C) and (D), the adhesive composition for image display of the present invention may be formulated with various additives as needed. The various additives which can be blended in the present invention include, for example, a methoxy group added for the purpose of improving the storage stability of the adhesive resin composition obtained by blending (A), (B), (C) and (D). A polymerization inhibitor such as a phenol to increase the resistance to light such as ultraviolet rays by adding an antioxidant such as triphenylphosphine for the purpose of improving the heat resistance of the adhesive sheet obtained by curing the adhesive resin composition by light. A light stabilizer such as a HALS (Hindered Amine Light Stabilizer) to be added for the purpose of improving the adhesion to glass or the like, and the like.
而且，於使用本發明之影像顯示用黏著性樹脂組成物而獲得黏著片時，成為以聚對苯二甲酸乙二酯膜等夾持的 構成，但為了控制與該聚對苯二甲酸乙二酯膜等基材之剝離性，可調配聚二甲基矽氧烷系、氟系等界面活性劑。 Further, when the adhesive sheet is obtained by using the adhesive resin composition for image display of the present invention, it is sandwiched between polyethylene terephthalate film or the like. In order to control the releasability with a substrate such as the polyethylene terephthalate film, a surfactant such as a polydimethylsiloxane or a fluorine-based surfactant may be blended.
該些添加劑可單獨使用，且亦可組合調配多種添加劑。另外，該些其他添加劑之含量通常情況下小於上述(A)、(B)、(C)及(D)之合計含量，一般情況下相對於黏著性樹脂組成物之總量而言為0.01質量%~5質量%左右。 These additives may be used singly, and a plurality of additives may be formulated in combination. Further, the content of the other additives is usually less than the total content of the above (A), (B), (C) and (D), and is generally 0.01 mass with respect to the total amount of the adhesive resin composition. %~5 mass% or so.
<黏著片> <adhesive sheet>
其次，於以下說明對影像顯示用黏著性樹脂組成物照射活性能量線，使其硬化而所得之黏著片。本發明之影像顯示用黏著性樹脂組成物可直接以液狀之狀態而作為黏著劑使用，較佳的製成片材狀之黏著片而使用。 Next, an adhesive sheet obtained by irradiating an active energy ray to an adhesive resin composition for image display and hardening it will be described below. The adhesive resin composition for image display of the present invention can be used as an adhesive directly in a liquid state, and is preferably used as a sheet-like adhesive sheet.
於以下例示本發明中之黏著片之製作方法。 The method of producing the adhesive sheet of the present invention is exemplified below.
本發明中之黏著片可藉由於基材上，將黏著性樹脂組成物塗佈為片材狀，對其照射活性能量線使其硬化而獲得。活性能量線之光源較佳的是於波長為400nm以下具有發光分布者，例如可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、金屬鹵素燈及微波激發水銀燈。而且，照射能量並無特別限定，通常為500mJ/cm2~5000mJ/cm2左右。 The adhesive sheet of the present invention can be obtained by coating an adhesive resin composition into a sheet shape on a substrate, irradiating it with an active energy ray and hardening it. The light source of the active energy ray preferably has a luminescent distribution at a wavelength of 400 nm or less. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light lamp, a metal halide lamp, and a microwave excited mercury lamp can be used. Further, the irradiation energy is not particularly limited, and is usually about 500 mJ/cm 2 to 5000 mJ/cm 2 .
本發明之影像顯示裝置用黏著片(以下有時簡稱為「黏著片」)兼具適度之黏著力與二次加工性，且對於所期望之厚度而言不含氣泡等，而且可設為能夠發揮優異之衝擊緩和性的厚度。本發明之黏著片之厚度並不由於使用用途及 方法而特別限定，較佳的是0.05mm~2mm左右之厚度。於該範圍內使用之情形時，作為用以將光學部件貼合於顯示器上的透明黏著片而發揮出特別優異之效果。 The adhesive sheet for an image display device of the present invention (hereinafter sometimes simply referred to as "adhesive sheet") has both an appropriate adhesive force and secondary workability, and does not contain bubbles or the like for a desired thickness, and can be made capable of The thickness that exerts excellent impact relaxation. The thickness of the adhesive sheet of the present invention is not due to the use and The method is particularly limited, and is preferably a thickness of about 0.05 mm to 2 mm. When it is used in this range, it is particularly excellent as a transparent adhesive sheet for bonding an optical member to a display.
而且，黏著片之玻璃轉移溫度較佳的是10℃~30℃。 Moreover, the glass transition temperature of the adhesive sheet is preferably from 10 ° C to 30 ° C.
<影像顯示裝置> <Image display device>
其次，對使用本發明之黏著性樹脂組成物或黏著片之影像顯示裝置加以說明。 Next, an image display apparatus using the adhesive resin composition or the adhesive sheet of the present invention will be described.
本發明之黏著性樹脂組成物及黏著片可適用於各種影像顯示裝置中。作為影像顯示裝置，可列舉電漿顯示器(PDP)、液晶顯示器(LCD)、陰極射線管(CRT)、場發射顯示器(FED)、有機電激發光顯示器(OELD)、3D顯示器、電子紙(EP)等。本發明之黏著性樹脂組成物及黏著片例如可用以將所述影像顯示裝置之抗反射層、防污層、色素層、硬塗層等具有功能性之功能層，或將該層成膜或積層於聚乙烯膜、聚酯膜等基材膜等之光學濾光片基材上而成之多層物，玻璃、壓克力、聚碳酸酯等之透明保護板或於其上成膜或積層有具有各種功能之功能層而成的多層物等加以組合而貼合。而且，亦可製成與此種多層物組合之光學濾光片而使用。另外，本發明之黏著性樹脂組成物亦可於該些多層物上塗佈、填充等之後而加以硬化。 The adhesive resin composition and the adhesive sheet of the present invention can be applied to various image display devices. Examples of the image display device include a plasma display (PDP), a liquid crystal display (LCD), a cathode ray tube (CRT), a field emission display (FED), an organic electroluminescent display (OELD), a 3D display, and an electronic paper (EP). )Wait. The adhesive resin composition and the adhesive sheet of the present invention can be used, for example, to have a functional functional layer such as an antireflection layer, an antifouling layer, a pigment layer, a hard coat layer or the like of the image display device, or to form a film or a multilayered layer laminated on an optical filter substrate such as a base film such as a polyethylene film or a polyester film, or a transparent protective sheet of glass, acrylic, polycarbonate, or the like, or formed thereon or laminated thereon. A multilayer or the like having a functional layer having various functions is combined and bonded. Further, an optical filter combined with such a multilayer may be used. Further, the adhesive resin composition of the present invention may be cured after being coated, filled, or the like on the plurality of layers.
所述抗反射層若為具有可見光反射率成為5%以下之抗反射性之層即可，可使用藉由已知之抗反射方法對透明之塑膠膜等之透明基材進行了處理之層。 The antireflection layer may be a layer having an antireflection property in which the visible light reflectance is 5% or less, and a layer obtained by treating a transparent substrate such as a transparent plastic film by a known antireflection method may be used.
所述防污層是用以使表面上難以附著污垢之層，可使 用為了使表面張力降低而由氟系樹脂或矽酮系樹脂所構成之已知之層。 The antifouling layer is a layer for making it difficult to adhere to dirt on the surface, and A known layer composed of a fluorine-based resin or an anthrone-based resin in order to lower the surface tension.
所述色素層是用以提高色純度之層，用以於自液晶顯示單元等影像顯示單元所發出之光的色純度低之情形時減低所不需要之光。可藉由如下方式而獲得：使吸收不需要之部分之光的色素溶解於樹脂中，於聚乙烯膜、聚酯膜等基材膜上進行成膜或積層。 The pigment layer is a layer for improving color purity, and is used to reduce unnecessary light when the color purity of light emitted from an image display unit such as a liquid crystal display unit is low. It can be obtained by dissolving a dye which absorbs unnecessary light, in a resin, and forming a film or laminating on a base film such as a polyethylene film or a polyester film.
所述硬塗層用以提高表面硬度。硬塗層可使用將丙烯酸胺基甲酸酯或環氧丙烯酸酯等丙烯酸樹脂或環氧樹脂等成膜或積層於聚乙烯膜等基材膜上而成者。同樣地，為了提高表面硬度，亦可使用玻璃、壓克力、聚碳酸酯等透明保護基板或者於該些板上成膜或積層有硬塗層者。 The hard coat layer is used to increase the surface hardness. The hard coat layer may be formed by laminating or laminating an acrylic resin such as acryl amide or epoxy acrylate, or laminating it on a base film such as a polyethylene film. Similarly, in order to increase the surface hardness, a transparent protective substrate such as glass, acryl, or polycarbonate may be used, or a film may be formed on the plates or a hard coat layer may be laminated.
本發明之黏著性樹脂組成物及黏著片可積層於偏光板上而使用。於此情形時，可積層於偏光板之視認面側，亦可積層於其相反側。 The adhesive resin composition and the adhesive sheet of the present invention can be used by laminating on a polarizing plate. In this case, it may be laminated on the side of the viewing surface of the polarizing plate, or may be laminated on the opposite side.
於偏光板之視認面側使用之情形時，可於黏著片之視認面側進一步積層抗反射層、防污層、硬塗層；且於偏光板與液晶單元之間使用之情形時，可於偏光板之視認面側積層具有功能性之層。 When used on the viewing side of the polarizing plate, an antireflection layer, an antifouling layer, and a hard coat layer may be further laminated on the viewing side of the adhesive sheet; and when used between the polarizing plate and the liquid crystal cell, The layer on the side of the polarizing plate has a functional layer.
於製成此種積層物之情形時，黏著片可使用輥層壓機或真空貼合機、及單片貼合機而進行積層。 In the case of producing such a laminate, the adhesive sheet can be laminated using a roll laminator, a vacuum laminator, and a single sheet bonding machine.
較佳的是黏著片配置於影像顯示裝置之影像顯示單元與視認側最前面之透明保護板(前面板)之間，視認側之適宜位置。具體而言，較佳的是應用(use)於影像顯示單 元與透明保護板之間。 Preferably, the adhesive sheet is disposed between the image display unit of the image display device and the transparent protective plate (front panel) at the forefront of the viewing side, and the visible position of the viewing side. Specifically, it is preferred to apply to the image display list. Between the element and the transparent protection board.
而且，於將觸控面板組合於影像顯示單元中而成的影像顯示裝置中，較佳的是應用(use)於觸控面板與影像顯示單元之間及/或觸控面板與所述透明保護板(前面板)之間，如果在影像顯示裝置之構成上可適用本發明之黏著片，則並不限於上述所記載之位置。 Moreover, in the image display device in which the touch panel is combined in the image display unit, it is preferably applied between the touch panel and the image display unit and/or the touch panel and the transparent protection. The adhesive sheet of the present invention can be applied to the configuration of the image display device between the panels (front panel), and is not limited to the position described above.
另外，於透明保護板、觸控面板、或影像顯示單元中具有10μm~80μm之階差之情形時，於藉由黏著片而將透明保護板與觸控面板之間、觸控面板與影像顯示單元之間、或透明保護板與影像顯示單元之間貼合之步驟後，自能夠進一步除去階差附近之氣泡的觀點考慮，較佳的是於40℃~80℃(較佳的是50℃~70℃)、0.3MPa~0.8MPa(較佳的是0.4MPa~0.7MPa)、5分鐘~60分鐘(較佳的是10分鐘~50分鐘)之條件下進行加熱加壓處理(高壓釜處理)。 In addition, when the transparent protection board, the touch panel, or the image display unit has a step of 10 μm to 80 μm, the transparent protection board and the touch panel, the touch panel, and the image display are displayed by the adhesive sheet. After the steps of bonding between the cells or between the transparent protective plate and the image display unit, it is preferably from 40 ° C to 80 ° C (preferably 50 ° C) from the viewpoint of further removing bubbles in the vicinity of the step. Heat treatment at ~70 ° C), 0.3 MPa to 0.8 MPa (preferably 0.4 MPa to 0.7 MPa), and 5 minutes to 60 minutes (preferably 10 minutes to 50 minutes) (autoclave treatment) ).
影像顯示裝置之透明保護板(前面板)可使用一般的光學用透明基板。具體而言可列舉：玻璃板、石英等無機物之板，壓克力板、聚碳酸酯板、聚對苯二甲酸乙二酯板等塑膠(有機物)板，厚的聚酯片材等樹脂片材等。 As the transparent protective plate (front panel) of the image display device, a general optical transparent substrate can be used. Specific examples include inorganic plates such as glass plates and quartz, plastic (organic) plates such as acrylic sheets, polycarbonate sheets, and polyethylene terephthalate sheets, and resin sheets such as thick polyester sheets. Materials and so on.
於所述影像顯示裝置為液晶顯示裝置之情形時，液晶顯示單元可使用一般的液晶顯示單元。液晶顯示單元根據液晶材料之控制方法而分類為TN(Twisted Nematic，扭轉向列)方式、STN(Super-twisted nematic，超扭轉向列)方式、VA(Vertical Alignment，垂直配向)方式、IPS (In-Plane-Switching，橫向電場切換)方式等，於本發明中，可為使用任意控制方法之液晶顯示單元。 In the case where the image display device is a liquid crystal display device, the liquid crystal display unit can use a general liquid crystal display unit. The liquid crystal display unit is classified into a TN (Twisted Nematic) method, an STN (Super-twisted nematic) method, a VA (Vertical Alignment) method, and an IPS according to a control method of a liquid crystal material. (In-Plane-Switching), etc., in the present invention, a liquid crystal display unit using any control method can be used.
[實例] [Example]
以下，藉由實例對本發明加以說明。另外，本發明並不限制於該些實例。 Hereinafter, the present invention will be described by way of examples. In addition, the invention is not limited to the examples.
<評價> <evaluation>
關於各實例及比較例中所得之各黏著片，藉由以下之試驗方法進行評價。 Each of the adhesive sheets obtained in each of the examples and the comparative examples was evaluated by the following test method.
1.玻璃轉移溫度 Glass transition temperature
製作厚度為0.5mm、寬度為10mm、長度為10mm之黏著片，使用廣域動態黏彈性測定裝置(Pheometric Scientific公司製造、Solids Analyzer RSA-II)，於剪切三明治模式(shear sandwich mode)、頻率為1.0Hz、測定溫度範圍為-40℃~80℃、升溫速度為5℃/min下測定玻璃轉移溫度。 An adhesive sheet having a thickness of 0.5 mm, a width of 10 mm, and a length of 10 mm was produced, and a wide-area dynamic viscoelasticity measuring apparatus (Pheometric Scientific, Solids Analyzer RSA-II) was used in a shear sandwich mode and frequency. The glass transition temperature was measured at 1.0 Hz, the measurement temperature range was -40 ° C to 80 ° C, and the temperature increase rate was 5 ° C / min.
玻璃轉移溫度(Tg)是於上述測定溫度範圍中，tanδ顯示為峰值之溫度。於該溫度範圍中觀測到2個以上tanδ峰值時，將tanδ之值顯示為最大值的溫度作為玻璃轉移溫度。 The glass transition temperature (Tg) is a temperature at which the tan δ is a peak in the above-described measurement temperature range. When two or more tan δ peaks were observed in this temperature range, the temperature at which the value of tan δ was shown as the maximum value was taken as the glass transition temperature.
2.外觀評價 2. Appearance evaluation
將所製作之黏著片切出為寬50mm、長100mm之尺寸，使用輥而貼附於50mm×100mm×0.7mm之尺寸的玻璃基板上。其次，使用輥而於其上貼合同樣之玻璃基板，製作於玻璃基板與玻璃基板之間夾持有黏著片之結構。其 後，進行30分鐘之高壓釜處理(60℃、0.5MPa)而製成樣品。 The prepared adhesive sheet was cut into a size of 50 mm in width and 100 mm in length, and attached to a glass substrate having a size of 50 mm × 100 mm × 0.7 mm using a roller. Next, the same glass substrate was bonded thereto by using a roll, and a structure in which an adhesive sheet was sandwiched between the glass substrate and the glass substrate was produced. its Thereafter, autoclaving treatment (60 ° C, 0.5 MPa) was carried out for 30 minutes to prepare a sample.
將所完成之樣品於以下之環境條件下放置設定之時間，進行取出後之外觀評價(氣泡、剝落)。評價基準是藉由目視觀察未產生氣泡及剝落之情形記為A，產生氣泡及剝落之情形記為B。 The finished sample was placed under the following environmental conditions for a set time, and the appearance evaluation (bubble, peeling) after taking out was performed. The evaluation criteria were as follows: A case where no bubbles were generated and peeled off by visual observation was recorded, and a case where bubbles were generated and peeled off was recorded as B.
‧高溫高濕試驗(以下記載為「85/85」)； ‧ High temperature and high humidity test (hereinafter referred to as "85/85");
將樣品於85℃、85%RH之條件下放置24小時。 The sample was allowed to stand at 85 ° C, 85% RH for 24 hours.
‧高溫試驗(以下記載為「100」) ‧High temperature test (hereinafter referred to as "100")
將樣品於100℃之條件下放置24小時。 The sample was allowed to stand at 100 ° C for 24 hours.
‧熱循環試驗(以下記載為「TCT」) ‧ Thermal cycle test (hereinafter referred to as "TCT")
實施100次之將樣品於-40℃之環境下放置30分鐘，於100℃之環境下放置30分鐘之熱循環。 The sample was placed 100 times in an environment of -40 ° C for 30 minutes, and placed in a temperature of 100 ° C for 30 minutes.
3.剪力評價 3. Shear evaluation
將所製作之黏著片切出為寬25mm×長25mm之尺寸。將該黏著片貼於25mm×100mm之不鏽鋼板上，自其上貼合切為25mm×100mm之PET膜，於PET膜之端附上100g之鉛垂。其後，於80℃之恆溫乾燥機內，以100g之鉛垂吊垂之方式固定不鏽鋼板，測定24小時後之黏著片之尺寸變化量。若該尺寸變化量為0.5mm以下，則記為OK。 The prepared adhesive sheet was cut into a size of 25 mm in width × 25 mm in length. The adhesive sheet was attached to a 25 mm × 100 mm stainless steel plate, and a PET film cut into 25 mm × 100 mm was attached thereto, and 100 g of the plumb was attached to the end of the PET film. Thereafter, the stainless steel plate was fixed in a constant temperature drier at 80 ° C with a hanging gage of 100 g, and the amount of change in the size of the adhesive sheet after 24 hours was measured. If the dimensional change amount is 0.5 mm or less, it is marked as OK.
製造例1<(A)(甲基)丙烯酸系衍生物聚合物之合成> Production Example 1 <Synthesis of (A) (meth)acrylic derivative polymer>
於附有冷凝管、溫度計、攪拌裝置、滴液漏斗及氮氣 導入管之反應容器中稱取丙烯酸-2-乙基己酯84.0g、丙烯酸-2-羥基乙酯36.0g及丁酮150.0g作為初始單體，一面藉由100ml/min之風量進行氮氣置換，一面以15分鐘自常溫(25℃)加熱至70℃。 With condenser tube, thermometer, stirring device, dropping funnel and nitrogen In the reaction vessel of the introduction tube, 84.0 g of 2-ethylhexyl acrylate, 36.0 g of 2-hydroxyethyl acrylate and 150.0 g of methyl ethyl ketone were weighed as initial monomers, and nitrogen substitution was performed by air volume of 100 ml/min. One side was heated from normal temperature (25 ° C) to 70 ° C in 15 minutes.
其後，一面保持為該溫度，一面使用丙烯酸-2-乙基己酯21.0g及丙烯酸-2-羥基乙酯9.0g作為追加單體，準備於該些化合物中溶解有過氧化月桂醯1.0g之溶液，以60分鐘滴加該溶液，於滴加結束後進一步反應2小時。 Thereafter, while maintaining the temperature, 21.0 g of 2-ethylhexyl acrylate and 9.0 g of 2-hydroxyethyl acrylate were used as additional monomers, and 1.0 g of oxidized laurel was dissolved in the compounds. The solution was added dropwise over 60 minutes, and further reacted for 2 hours after the completion of the dropwise addition.
繼而，藉由餾去丁酮而獲得丙烯酸-2-乙基己酯與丙烯酸-2-羥基乙酯之共聚物(重量平均分子量為150,000)(以下將該共聚物稱為「丙烯酸系衍生物聚合物」)。 Then, a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight: 150,000) was obtained by distilling off butanone (hereinafter, the copolymer is referred to as "acrylic derivative polymerization" ")").
另外，重量平均分子量之測定是使用以THF為溶劑之凝膠滲透層析法而進行，使用下述裝置及測定條件而使用標準聚苯乙烯之校準曲線而決定。 Further, the measurement of the weight average molecular weight was carried out by gel permeation chromatography using THF as a solvent, and was determined using a calibration curve of standard polystyrene using the following apparatus and measurement conditions.
裝置：日立製作所股份有限公司 Device: Hitachi, Ltd.
RI偵測器：L-3350 RI detector: L-3350
使用溶劑：THF Use solvent: THF
管柱：日立化成工業股份有限公司製造之Gelpac GL-R420+R430+R440 Pipe column: Gelpac GL-R420+R430+R440 manufactured by Hitachi Chemical Co., Ltd.
管柱溫度：40℃ Column temperature: 40 ° C
流量：2.0ml/min Flow rate: 2.0ml/min
比較製造例1 Comparative manufacturing example 1
<(C)具有2官能之(甲基)丙烯醯基之交聯劑之合成1> <(C) Synthesis of a crosslinking agent having a bifunctional (meth) acrylonitrile group 1>
於附有冷凝管、溫度計、攪拌裝置、滴液漏斗及空氣注入管之反應容器中稱取聚丙二醇(分子量為2,000)223.12g、內酯改質丙烯酸羥基乙酯76.29g、丙烯酸-2-乙基己酯99.68g、作為聚合抑制劑之對甲氧基苯酚0.12g及作為觸媒之二丁基二月桂酸錫0.5g，一面流通空氣一面升溫至75℃後，於75℃下一面攪拌一面以2小時均勻地滴加異佛爾酮二異氰酸酯49.35g，進行反應。 In the reaction vessel with a condenser, a thermometer, a stirring device, a dropping funnel and an air injection tube, 133.12 g of polypropylene glycol (molecular weight: 2,000), 76.29 g of hydroxyethyl acrylate modified by lactone, and 2-ethyl acrylate were weighed. 99.68 g of hexyl hexyl ester, 0.12 g of p-methoxyphenol as a polymerization inhibitor, and 0.5 g of dibutyltin dilaurate as a catalyst, and the temperature was raised to 75 ° C while flowing air, and then stirred at 75 ° C. 49.35 g of isophorone diisocyanate was uniformly added dropwise over 2 hours to carry out a reaction.
於滴加結束後，使其反應5小時，然後進一步追加丙烯酸-2-羥基乙酯44.85g，使其反應1小時。進行IR測定之結果，確認異氰酸酯消失而結束反應，獲得具有聚丙二醇與異佛爾酮二異氰酸酯作為重複單元，且於兩末端具有聚合性不飽和鍵之聚丙烯酸胺基甲酸酯(重量平均分子量為8,500)(以下將該聚丙烯酸胺基甲酸酯稱為「聚二丙烯酸胺基甲酸酯1」)。 After completion of the dropwise addition, the mixture was reacted for 5 hours, and then 44.85 g of 2-hydroxyethyl acrylate was further added thereto, and the mixture was reacted for 1 hour. As a result of the IR measurement, it was confirmed that the isocyanate disappeared and the reaction was terminated, and a polyacrylamide having a polyacrylic acid and isophorone diisocyanate as a repeating unit and having a polymerizable unsaturated bond at both terminals (weight average molecular weight) was obtained. It is 8,500) (hereinafter, this polyacrylic acid urethane is called "polydiacrylate urethane 1").
製造例2 Manufacturing Example 2
<(C)具有2官能之(甲基)丙烯醯基之交聯劑之合成2> <(C) Synthesis of a crosslinking agent having a bifunctional (meth) acrylonitrile group 2>
於附有冷凝管、溫度計、攪拌裝置、滴液漏斗及空氣注入管之反應容器中稱取聚丙二醇(分子量為2,000)303.92g、內酯改質丙烯酸羥基乙酯8.66g、丙烯酸-2-乙基己酯99.74g、作為聚合抑制劑之對甲氧基苯酚0.12g及作為觸媒之二丁基二月桂酸錫0.5g，一面流通空氣一面升溫至75℃後，一面於75℃下攪拌一面以2小時均勻地滴加異佛爾酮二異氰酸酯36.41g，進行反應。 In the reaction vessel with a condenser, a thermometer, a stirring device, a dropping funnel and an air injection tube, propylene glycol (molecular weight: 2,000) 303.92 g, lactone modified hydroxyethyl acrylate (8.66 g), acrylic acid-2-B were weighed. 99.74 g of hexyl hexyl ester, 0.12 g of p-methoxyphenol as a polymerization inhibitor, and 0.5 g of dibutyltin dilaurate as a catalyst, and the mixture was heated to 75 ° C while flowing air, and then stirred at 75 ° C. 36.41 g of isophorone diisocyanate was uniformly added dropwise over 2 hours to carry out a reaction.
於滴加結束後，使其反應5小時，然後進一步追加丙烯酸-2-羥基乙酯44.88g，使其反應1小時。進行IR測定之結果，確認異氰酸酯消失而結束反應，獲得具有聚丙二醇與異佛爾酮二異氰酸酯作為重複單元，且於兩末端具有聚合性不飽和鍵之聚丙烯酸胺基甲酸酯(重量平均分子量為20,000)(以下將該聚丙烯酸胺基甲酸酯稱為「聚二丙烯酸胺基甲酸酯2」)。 After completion of the dropwise addition, the mixture was reacted for 5 hours, and then 44.88 g of 2-hydroxyethyl acrylate was further added thereto, and the mixture was reacted for 1 hour. As a result of the IR measurement, it was confirmed that the isocyanate disappeared and the reaction was terminated, and a polyacrylamide having a polyacrylic acid and isophorone diisocyanate as a repeating unit and having a polymerizable unsaturated bond at both terminals (weight average molecular weight) was obtained. It is 20,000) (hereinafter, this polyacrylic acid urethane is referred to as "polydiacrylate urethane 2").
製造例3 Manufacturing Example 3
<(C)具有2官能之(甲基)丙烯醯基之交聯劑之合成3> <(C) Synthesis of a crosslinker having a bifunctional (meth) acrylonitrile group 3>
於附有冷凝管、溫度計、攪拌裝置、滴液漏斗及空氣注入管之反應容器中稱取聚丙二醇(分子量為2,000)285.3g、丙烯酸-2-乙基己酯100g、作為聚合抑制劑之對甲氧基苯酚0.13g及作為觸媒之二丁基二月桂酸錫0.5g，一面流通空氣一面升溫至75℃後，一面於75℃下攪拌一面以2小時均勻地滴加異佛爾酮二異氰酸酯39.6g，進行反應。 In a reaction vessel with a condenser, a thermometer, a stirring device, a dropping funnel and an air injection tube, 285.3 g of polypropylene glycol (molecular weight: 2,000) and 100 g of 2-ethylhexyl acrylate were weighed as a polymerization inhibitor. 0.13 g of methoxyphenol and 0.5 g of dibutyltin dilaurate as a catalyst, and the temperature was raised to 75 ° C while flowing air, and then isophorone was uniformly added dropwise over 2 hours while stirring at 75 ° C. 39.6 g of isocyanate was reacted.
於滴加結束後，使其反應4小時後，投入內酯改質丙烯酸羥基乙酯24.5g，然後進一步於1小時後追加丙烯酸-2-羥基乙酯45.0g，使其反應1小時。進行IR測定之結果，確認異氰酸酯消失而結束反應，獲得具有聚丙二醇與異佛爾酮二異氰酸酯作為重複單元，且於兩末端具有聚合性不飽和鍵之聚丙烯酸胺基甲酸酯(重量平均分子量為35,000)(以下將該聚丙烯酸胺基甲酸酯稱為「聚二丙烯酸胺基甲酸酯3」)。 After the completion of the dropwise addition, the mixture was reacted for 4 hours, and 24.5 g of a hydroxyethyl acrylate was added to the lactone. Then, 45.0 g of 2-hydroxyethyl acrylate was further added thereto for 1 hour, and the mixture was reacted for 1 hour. As a result of the IR measurement, it was confirmed that the isocyanate disappeared and the reaction was terminated, and a polyacrylamide having a polyacrylic acid and isophorone diisocyanate as a repeating unit and having a polymerizable unsaturated bond at both terminals (weight average molecular weight) was obtained. It is 35,000) (hereinafter, this polyacrylic acid urethane is called "polydiacrylate urethane 3").
比較製造例2 Comparative manufacturing example 2
<(C)具有2官能之(甲基)丙烯醯基之交聯劑之合成4> <(C) Synthesis of a crosslinker having a bifunctional (meth) acrylonitrile group 4>
於附有冷凝管、溫度計、攪拌裝置、滴液漏斗及空氣注入管之反應容器中稱取聚丙二醇(分子量為2,000)285.3g、丙烯酸-2-乙基己酯100g、作為聚合抑制劑之對甲氧基苯酚0.13g及作為觸媒之二丁基二月桂酸錫0.5g，一面流通空氣一面升溫至75℃後，一面於75℃下攪拌一面以2小時均勻地滴加異佛爾酮二異氰酸酯39.6g，進行反應。 In a reaction vessel with a condenser, a thermometer, a stirring device, a dropping funnel and an air injection tube, 285.3 g of polypropylene glycol (molecular weight: 2,000) and 100 g of 2-ethylhexyl acrylate were weighed as a polymerization inhibitor. 0.13 g of methoxyphenol and 0.5 g of dibutyltin dilaurate as a catalyst, and the temperature was raised to 75 ° C while flowing air, and then isophorone was uniformly added dropwise over 2 hours while stirring at 75 ° C. 39.6 g of isocyanate was reacted.
於滴加結束後，使其反應5小時後，投入內酯改質丙烯酸羥基乙酯24.5g，然後進一步於1小時後追加丙烯酸-2-羥基乙酯45.0g，使其反應1小時。進行IR測定之結果，確認異氰酸酯消失而結束反應，獲得具有聚丙二醇與異佛爾酮二異氰酸酯作為重複單元，且於兩末端具有聚合性不飽和鍵之聚丙烯酸胺基甲酸酯(重量平均分子量為56,000)(以下將該聚丙烯酸胺基甲酸酯稱為「聚二丙烯酸胺基甲酸酯4」)。 After the completion of the dropwise addition, the mixture was reacted for 5 hours, and 24.5 g of a hydroxyethyl acrylate was added to the lactone. Then, 4 hours after the addition of 45.0 g of 2-hydroxyethyl acrylate, the reaction was carried out for 1 hour. As a result of the IR measurement, it was confirmed that the isocyanate disappeared and the reaction was terminated, and a polyacrylamide having a polyacrylic acid and isophorone diisocyanate as a repeating unit and having a polymerizable unsaturated bond at both terminals (weight average molecular weight) was obtained. It is 56,000) (hereinafter, this polyacrylic acid urethane is referred to as "polydiacrylate urethane 4").
實例1 Example 1
<樣品調配及黏著片製作> <Sample preparation and adhesive sheet production>
稱量製造例1中所得之丙烯酸系衍生物聚合物30.8g、丙烯酸-2-乙基己酯(EHA)38.7g、丙烯醯基嗎啉(ACMO)18.5g、丙烯酸-4-羥基丁酯(4-HBA)5.0g、製造例2中所得之聚二丙烯酸胺基甲酸酯2 6.5g、1-羥基環己基苯基酮(I-184)0.5g，進行攪拌混合而獲得黏著性 樹脂組成物。 30.8 g of the acrylic derivative polymer obtained in Production Example 1 , 38.7 g of 2-ethylhexyl acrylate (EHA), 18.5 g of acryloylmorpholine (ACMO), and 4-hydroxybutyl acrylate (weighed) were weighed ( 4-HBA) 5.0 g, 6.5 g of polydiacrylate urethane obtained in Production Example 2, and 0.5 g of 1-hydroxycyclohexyl phenyl ketone (I-184) were stirred and mixed to obtain adhesiveness. Resin composition.
其後，於聚對苯二甲酸乙二酯膜上滴加上述所得之黏著片用黏著性樹脂組成物，進一步自其上覆蓋聚對苯二甲酸乙二酯，藉由輥而將黏著性樹脂組成物塗佈為片材狀，使用紫外線照射裝置，照射2,000mJ/cm2之紫外線而獲得透明黏著片。 Thereafter, the adhesive resin composition for an adhesive sheet obtained above is dropped onto the polyethylene terephthalate film, and further, polyethylene terephthalate is coated thereon, and the adhesive resin is applied by a roll. The composition was applied in the form of a sheet, and an ultraviolet ray of 2,000 mJ/cm 2 was irradiated with an ultraviolet irradiation device to obtain a transparent adhesive sheet.
實例2、實例3及比較例1~比較例4 Example 2, Example 3, and Comparative Example 1 to Comparative Example 4
以表1及表2中所記載之調配成分及調配量，藉由與實例1同樣之方法而製作黏著性樹脂組成物及黏著片。 The adhesive resin composition and the adhesive sheet were produced in the same manner as in Example 1 using the blending components and the blending amounts described in Tables 1 and 2.
[產業上之可利用性] [Industrial availability]
藉由使用本發明之影像顯示裝置用黏著性樹脂組成物，可提供具有耐衝擊性、視認性優異之影像顯示裝置。特別是視認側之透明保護板(例如玻璃)與黏著性樹脂組成物之密接力高，即使暴露於如85℃/85%RH這樣的高溫高濕下亦不產生剝落、***、氣泡等，不使顯示器之視認性降低。亦即，可將影像顯示單元與影像顯示裝置所必需之部件貼合，且可將較影像顯示裝置之影像顯示單元更靠近視認側之部件彼此貼合。特別是可用作使液晶顯示單元與觸控面板、液晶顯示單元與透明保護板、觸控面板與透明保護板等貼著之黏著片。 By using the adhesive resin composition for an image display device of the present invention, it is possible to provide an image display device having excellent impact resistance and visibility. In particular, the transparent protective sheet (for example, glass) on the viewing side has a high adhesion to the adhesive resin composition, and does not peel off, bulge, bubbles, etc. even when exposed to high temperature and high humidity such as 85 ° C / 85% RH. Reduce the visibility of the display. That is, the image display unit can be attached to the components necessary for the image display device, and the components closer to the viewing side than the image display unit of the image display device can be attached to each other. In particular, it can be used as an adhesive sheet for adhering a liquid crystal display unit to a touch panel, a liquid crystal display unit, a transparent protective plate, a touch panel, a transparent protective plate, and the like.
1‧‧‧透明保護板(玻璃或塑膠基材) 1‧‧‧Transparent protective sheet (glass or plastic substrate)
2‧‧‧觸控面板 2‧‧‧ touch panel
3‧‧‧偏光板 3‧‧‧Polar plate
4‧‧‧液晶顯示單元 4‧‧‧LCD unit
5‧‧‧用以貼合透明保護板與觸控面板之黏著層 5‧‧‧Adhesive layer for bonding transparent protection board and touch panel
6‧‧‧用以貼合觸控面板與偏光板之黏著層 6‧‧‧Adhesive layer for bonding touch panel and polarizing plate
圖1是表示本發明之影像顯示裝置之剖面結構的概略圖。 Fig. 1 is a schematic view showing a cross-sectional structure of a video display device of the present invention.
1‧‧‧透明保護板(玻璃或塑膠基材) 1‧‧‧Transparent protective sheet (glass or plastic substrate)
2‧‧‧觸控面板 2‧‧‧ touch panel
3‧‧‧偏光板 3‧‧‧Polar plate
4‧‧‧液晶顯示單元 4‧‧‧LCD unit
5‧‧‧用以貼合透明保護板與觸控面板之黏著層 5‧‧‧Adhesive layer for bonding transparent protection board and touch panel
6‧‧‧用以貼合觸控面板與偏光板之黏著層6‧‧‧Adhesive layer for bonding touch panel and polarizing plate
Claims (9)
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| CN104755517B (en) * | 2012-10-31 | 2017-12-08 | 昭和电工株式会社 | Polymerizable composition, polymerizable composition, polymer, optical-use pressure-sensitive adhesive sheet, image display device and its manufacture method |
| JP6038660B2 (en) * | 2013-01-10 | 2016-12-07 | 日立マクセル株式会社 | Curable adhesive composition, adhesive and adhesive sheet |
| JP6163824B2 (en) * | 2013-03-28 | 2017-07-19 | 日立化成株式会社 | Adhesive resin composition for image display device, adhesive sheet for image display device, method for producing image display device, and image display device |
| JP6155778B2 (en) * | 2013-04-08 | 2017-07-05 | 日立化成株式会社 | Adhesive composition |
| KR102245657B1 (en) * | 2014-07-22 | 2021-04-28 | 미쯔비시 케미컬 주식회사 | Active energy ray-curable pressure sensitive adhesive composition, and pressure sensitive adhesive and pressure sensitive adhesive sheet using same |
| JP6583991B2 (en) * | 2015-05-18 | 2019-10-02 | 藤森工業株式会社 | Adhesive resin layer and adhesive resin film |
| JP5997405B1 (en) * | 2016-04-06 | 2016-09-28 | 大日精化工業株式会社 | Adhesive composition and laminate |
| JP7160838B2 (en) * | 2017-12-18 | 2022-10-25 | 株式会社クラレ | Method for manufacturing liquid crystal display protection plate |
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| JP3660462B2 (en) * | 1997-03-26 | 2005-06-15 | トッパン・フォームズ株式会社 | Pressure-sensitive adhesive printing sheet |
| KR20110002857A (en) * | 2008-04-11 | 2011-01-10 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Transparent adhesive sheet and image display device including the same |
| JP2010189545A (en) * | 2009-02-18 | 2010-09-02 | Nitto Denko Corp | Double-sided self-adhesive sheet and self-adhesive optical member |
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