JP5540394B2 - Adhesive composition for polarizing plate - Google Patents
Adhesive composition for polarizing plate Download PDFInfo
- Publication number
- JP5540394B2 JP5540394B2 JP2009115735A JP2009115735A JP5540394B2 JP 5540394 B2 JP5540394 B2 JP 5540394B2 JP 2009115735 A JP2009115735 A JP 2009115735A JP 2009115735 A JP2009115735 A JP 2009115735A JP 5540394 B2 JP5540394 B2 JP 5540394B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- mass
- monomer
- polarizing plate
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 43
- 239000000853 adhesive Substances 0.000 title claims description 10
- 230000001070 adhesive effect Effects 0.000 title claims description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 53
- 229920001577 copolymer Polymers 0.000 claims description 47
- -1 isocyanate compound Chemical class 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 24
- 239000013522 chelant Substances 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 15
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 14
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 claims description 12
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 229920003050 poly-cycloolefin Polymers 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
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- 241000519995 Stachys sylvatica Species 0.000 description 24
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- 238000011156 evaluation Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 9
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- 229910052782 aluminium Inorganic materials 0.000 description 6
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- 150000003384 small molecules Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
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- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 4
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- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 4
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- 238000001035 drying Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YHSYGCXKWUUKIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C=C YHSYGCXKWUUKIK-UHFFFAOYSA-N 0.000 description 3
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、液晶表示装置の液晶セルなどの光学部品に偏光板を貼着するために用いる粘着剤組成物に関する。 The present invention relates to an adhesive composition used for attaching a polarizing plate to an optical component such as a liquid crystal cell of a liquid crystal display device.
液晶表示装置を構成する液晶セルは、所定の方向に配向した液晶成分を２枚のガラス基板で挟み、これらのガラス基板の外側に光学用粘着剤組成物から形成された粘着剤層を介して偏光板または偏光板と位相差板との積層体などの光学機能性フィルムを貼着してなるものである。近年、車両搭載用、屋外計器用およびパソコンなどのディスプレイまたはテレビなどの表示装置の軽量化および薄型化により、液晶表示装置が広く使用されるようになり、その需要はますます増加傾向にある。それに伴い液晶表示装置の使用環境も、屋内外を問わず非常に過酷になってきている。 A liquid crystal cell constituting a liquid crystal display device includes a liquid crystal component oriented in a predetermined direction sandwiched between two glass substrates, and an adhesive layer formed from an optical adhesive composition on the outside of these glass substrates. An optical functional film such as a polarizing plate or a laminate of a polarizing plate and a retardation plate is attached. In recent years, liquid crystal display devices have been widely used due to the reduction in weight and thickness of displays for vehicles, outdoor instruments, displays such as personal computers, and televisions, and their demand is increasing. As a result, the usage environment of liquid crystal display devices has become extremely harsh, both indoors and outdoors.
液晶表示装置に使用される偏光板は、ポリビニルアルコール系偏光子の両面をトリアセチルセルロース系保護フィルムで挟んだ３層構造を有しているが、それらの材料の特性から寸法安定性に乏しい。また、偏光板などの光学機能性フィルムは延伸によって成形されているため、経時による伸縮が起こり易い。このため、液晶表示装置においては、光学機能性フィルムの伸縮により生じる内部応力を、粘着剤層が吸収・緩和することができないと、光学機能性フィルムに作用する残留応力の分布が不均一となり、特にその周縁部に応力が集中する。その結果、液晶表示装置の周縁部が中央より明るくなったり、または暗くなったりし、液晶表示装置に色むら・白抜け現象が発生する原因になる。 A polarizing plate used in a liquid crystal display device has a three-layer structure in which both surfaces of a polyvinyl alcohol polarizer are sandwiched between triacetyl cellulose protective films, but has poor dimensional stability due to the characteristics of these materials. In addition, since an optical functional film such as a polarizing plate is formed by stretching, it tends to expand and contract over time. For this reason, in the liquid crystal display device, the internal stress generated by the expansion and contraction of the optical functional film cannot be absorbed and relaxed by the adhesive layer, and the distribution of residual stress acting on the optical functional film becomes non-uniform, In particular, stress concentrates on the peripheral edge. As a result, the peripheral edge of the liquid crystal display device becomes brighter or darker than the center, which causes color unevenness and white spots in the liquid crystal display device.
また、液晶表示装置に色むら・白抜け現象が発生する他の要因として、応力によって光学機能性フィルムや粘着剤層に発生する光学的な歪（複屈折の発生など）が考えられる。 Further, as another factor that causes color unevenness and white spot phenomenon in the liquid crystal display device, optical distortion (such as generation of birefringence) generated in the optical functional film or the pressure-sensitive adhesive layer due to stress can be considered.
上記の問題点を解決するために多くの手段が検討されてきた。例えば、特許文献１では、（メタ）アクリル酸エステルを主成分とするポリマーと架橋剤とからなる粘着剤組成物であって、硬化後のゲル分率が３０〜６０％のものが開示されている。しかしながら、この技術では、偏光板が、ディスコティック液晶がコートされている偏光板、延伸トリアセチルセルロース系フィルム、延伸ポリシクロオレフィン系フィルムまたは延伸セルロースアセテートプロピオネートフィルムを基材とする偏光板である場合には、十分に色むらおよび白抜けを抑えることができない。 Many means have been studied to solve the above problems. For example, Patent Document 1 discloses a pressure-sensitive adhesive composition comprising a polymer mainly composed of (meth) acrylic acid ester and a cross-linking agent and having a gel fraction of 30 to 60% after curing. Yes. However, in this technique, the polarizing plate is a polarizing plate coated with a discotic liquid crystal, a stretched triacetyl cellulose film, a stretched polycycloolefin film, or a stretched cellulose acetate propionate film. In some cases, color unevenness and white spots cannot be sufficiently suppressed.
特許文献２では、特定の分子量を有する（メタ）アクリル酸エステルを主成分とするポリマーと架橋剤とからなる粘着剤組成物であって、硬化後のゲル分率が４５〜９５％（実施例では５５〜７２％）のものが開示されている。しかしながら、この技術では、偏光板が、ディスコティック液晶がコートされている偏光板、延伸トリアセチルセルロース系フィルム、延伸ポリシクロオレフィン系フィルムまたは延伸セルロースアセテートプロピオネートフィルムを基材とする偏光板である場合には、十分に色むらおよび白抜けを抑えることができない。 In patent document 2, it is an adhesive composition which consists of a polymer which has (meth) acrylic acid ester which has specific molecular weight as a main component, and a crosslinking agent, Comprising: The gel fraction after hardening is 45-95% (Example) In this case, 55-72%) is disclosed. However, in this technique, the polarizing plate is a polarizing plate coated with a discotic liquid crystal, a stretched triacetyl cellulose film, a stretched polycycloolefin film, or a stretched cellulose acetate propionate film. In some cases, color unevenness and white spots cannot be sufficiently suppressed.
本発明の目的は、液晶表示装置を構成する偏光板に使用する粘着剤組成物であって、偏光板の伸縮に起因する液晶表示装置のサイズ依存性のない色むら・白抜け現象の発生を防止できる粘着剤層を形成するための粘着剤組成物を提供することである。 An object of the present invention is a pressure-sensitive adhesive composition used for a polarizing plate constituting a liquid crystal display device, and the occurrence of color unevenness and white spot phenomenon without size dependency of the liquid crystal display device due to expansion and contraction of the polarizing plate. It is providing the adhesive composition for forming the adhesive layer which can be prevented.
上記の課題を解決するために、本発明者らは鋭意研究を重ねた結果、以下の本発明によって上記目的が達成されることを見いだした。
すなわち、本発明は、（メタ）アクリル酸エステル単量体ａと、カルボキシル基含有単量体ｂと、アセトアセチル基含有単量体ｃと、ジアルキル置換アクリルアミド単量体ｄとの共重合体Ａと硬化剤Ｂとからなり、上記共重合体Ａにおける単量体の使用割合が、単量体ａ〜ｄの合計を１００質量％としたときに、単量体ｂが０．５〜８質量％、単量体ｃが０．５〜５質量％、単量体ｄが１〜１０質量％、および残りが単量体ａであり、硬化後のゲル分率８０〜９９％であり、かつ粘着剤層を形成した場合の２０℃におけるその貯蔵弾性率が１．０×１０5Ｐａ以上であり、ガラス転移点温度（Ｔｇ）が−５０℃以上であることを特徴とする偏光板用粘着剤組成物を提供する。
In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that the above-described object can be achieved by the present invention described below.
That is, the present invention relates to a copolymer A of a (meth) acrylic acid ester monomer a, a carboxyl group-containing monomer b, an acetoacetyl group-containing monomer c, and a dialkyl-substituted acrylamide monomer d. And the curing agent B, and the use ratio of the monomer in the copolymer A is such that the monomer b is 0.5 to 8 mass when the total of the monomers a to d is 100 mass%. %, Monomer c is 0.5 to 5 mass%, monomer d is 1 to 10 mass%, and the remainder is monomer a, and the gel fraction after curing is 80 to 99%, and A pressure-sensitive adhesive for a polarizing plate characterized by having a storage elastic modulus at 20 ° C. of 1.0 × 10 5 Pa or more when a pressure-sensitive adhesive layer is formed and a glass transition temperature (Tg) of −50 ° C. or more. An agent composition is provided.
上記本発明においては、前記硬化剤Ｂが、金属キレート化合物、エポキシ系化合物、イソシアネート系化合物およびアジリジン系化合物から選ばれる少なくとも１種であり、その使用量が共重合体Ａ１００質量部当たりそれぞれ０．０１〜５質量部であること；前記硬化剤Ｂとして、共重合体Ａ１００質量部当たり０．０１〜１質量部の金属キレート化合物と、共重合体Ａ１００質量部当たり０．１〜５質量部のビスフェノールＦ型化合物（化合物Ｘ）またはビフェニル型化合物（化合物Ｙ）とを併用すること；前記化合物Ｘまたは化合物Ｙの重量平均分子量が、２０００未満であり、エポキシ当量が、２００以下であること；および前記偏光板が、ディスコティック液晶がコートされている偏光板、延伸トリアセチルセルロース系フィルム、延伸ポリシクロオレフィン系フィルムまたは延伸セルロースアセテートプロピオネートフィルムを基材とする偏光板であることが好ましい。 In the above-described present invention, before Symbol curing agent B is a metal chelate compound, an epoxy compound is at least one selected from an isocyanate compound and an aziridine compound, each of which usage copolymer A100 parts by weight per 0 0.01 to 5 parts by mass; 0.01 to 1 part by mass of metal chelate compound per 100 parts by mass of copolymer A and 0.1 to 5 parts by mass per 100 parts by mass of copolymer A as the curing agent B A bisphenol F-type compound (compound X) or a biphenyl-type compound (compound Y), wherein the compound X or the compound Y has a weight average molecular weight of less than 2000 and an epoxy equivalent of 200 or less; And the polarizing plate is a polarizing plate coated with a discotic liquid crystal, a stretched triacetyl cellulose-based film It is preferred to stretch polycycloolefin-based film or stretched cellulose acetate propionate film is a polarizing plate to the substrate.
本発明によれば、本発明の粘着剤組成物を液晶表示装置の液晶セルを構成するガラス基板と偏光板、特に図１に示す如き層構成のディスコティック液晶がコートされている偏光板、および図２に示す如き延伸フィルム、例えば、延伸トリアセチルセルロース系フィルム、延伸ポリシクロオレフィン系フィルムまたは延伸セルロースアセテートプロピオネートフィルムを基材とする偏光板との間の粘着剤層の形成に用いることにより、液晶表示装置において、図３に示すような特有の額縁型或いは対角型の色むら・白抜け現象の発生を装置のサイズに依存することなく効果的に防止することができる。図３ａは黒表示画面の周辺部が図のように白くなる現象を示し、図３ｂは黒表示画面の対角部が図のように白くなる現象を示している。なお、図２では便宜上ヨウ素ドープＰＶＡの両面が延伸フィルムに接しているが、この図２に限定されず、延伸フィルムの一方が未延伸フィルムであってもよい。
本発明の粘着剤組成物は、上記偏光板の伸縮によって発生する応力を緩和するだけでなく、同時にその応力によって上記偏光板に発生した光学的な歪をバランスよく補正すると思われる。
According to the present invention, the pressure-sensitive adhesive composition of the present invention comprises a glass substrate and a polarizing plate constituting a liquid crystal cell of a liquid crystal display device, in particular, a polarizing plate coated with a discotic liquid crystal having a layer structure as shown in FIG. Used for forming a pressure-sensitive adhesive layer between a stretched film as shown in FIG. 2, such as a stretched triacetylcellulose-based film, a stretched polycycloolefin-based film, or a stretched cellulose acetate propionate film as a base material. Thus, in the liquid crystal display device, it is possible to effectively prevent the occurrence of a unique frame-type or diagonal-type color unevenness / whiteout phenomenon as shown in FIG. 3 without depending on the size of the device. FIG. 3a shows a phenomenon in which the peripheral part of the black display screen becomes white as shown in the figure, and FIG. 3b shows a phenomenon in which the diagonal part of the black display screen becomes white as shown in the figure. In FIG. 2, both sides of the iodine-doped PVA are in contact with the stretched film for convenience, but the present invention is not limited to FIG. 2, and one of the stretched films may be an unstretched film.
The pressure-sensitive adhesive composition of the present invention not only relieves the stress generated by the expansion and contraction of the polarizing plate, but also seems to correct the optical distortion generated in the polarizing plate by the stress in a well-balanced manner.
次に発明を実施するための最良の形態を挙げて本発明をさらに詳しく説明する。なお、本発明の特許請求の範囲および明細書における「（メタ）アクリル」という用語は、「アクリル」および「メタクリル」の双方を意味し、また、「（メタ）アクリレート」という用語は、「アクリレート」および「メタクリレート」の双方を意味する。 Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention. The term “(meth) acryl” in the claims and the specification of the present invention means both “acryl” and “methacryl”, and the term “(meth) acrylate” ”And“ methacrylate ”.
本発明で使用する共重合体Ａは、（メタ）アクリル酸エステル単量体ａと、カルボキシル基含有単量体ｂと、アセトアセチル基含有単量体ｃと、ジアルキル置換アクリルアミド単量体ｄとの共重合体である。該共重合体Ａを構成する単量体の割合は、単量体ａ〜ｄの合計を１００質量％としたときに、単量体ｂが０．５〜８質量％、単量体ｃが０．５〜５質量％、単量体ｄが１〜１０質量％、および残りが単量体ａであることが好ましい。 Copolymer A used in the present invention comprises (meth) acrylic acid ester monomer a, carboxyl group-containing monomer b, acetoacetyl group-containing monomer c, dialkyl-substituted acrylamide monomer d, It is a copolymer. The proportion of the monomers constituting the copolymer A is such that when the total of the monomers a to d is 100% by mass, the monomer b is 0.5 to 8% by mass and the monomer c is It is preferable that 0.5-5 mass%, monomer d is 1-10 mass%, and the remainder is monomer a.
前記単量体ｂの使用割合が０．５質量％未満であると、共重合体Ａの架橋剤による架橋度合いが少なく、ゲル分率が８０％以上にならなくなり、十分に色むらおよび白抜けを抑えることができない。一方、前記単量体ｂの使用割合が８質量％を超えると架橋剤添加後のゲル化を促進して、ゲル分率を８０〜９９％の範囲に制御することが難しく、さらに耐久性において剥がれ易くなるため好ましくない。前記単量体ｃの使用割合が０．５質量％未満であると、十分に色むらおよび白抜けを抑えることができない。一方、前記単量体ｃの使用割合が５質量％を超えると重合後の共重合体Ａの粘度安定性に劣るため好ましくない。前記単量体ｄの使用割合が１質量％未満であると、弾性率が下がるため、色むらおよび白抜けを十分抑えることができなく、耐久性も劣り、一方、前記単量体ｄの使用割合が１０質量％を超えると重合後の共重合体Ａの粘度安定性に劣るため好ましくない。 When the proportion of the monomer b used is less than 0.5% by mass, the degree of crosslinking by the crosslinking agent of the copolymer A is small, the gel fraction does not become 80% or more, and color unevenness and white spots are sufficiently obtained. Can not be suppressed. On the other hand, when the proportion of the monomer b used exceeds 8% by mass, it is difficult to control the gel fraction within the range of 80 to 99% by promoting gelation after the addition of the cross-linking agent. Since it becomes easy to peel off, it is not preferable. When the proportion of the monomer c used is less than 0.5% by mass, uneven color and white spots cannot be sufficiently suppressed. On the other hand, if the proportion of the monomer c used exceeds 5% by mass, the viscosity stability of the copolymer A after polymerization is inferior. When the proportion of the monomer d used is less than 1% by mass, the elastic modulus decreases, so that color unevenness and white spots cannot be sufficiently suppressed, and the durability is inferior. If the ratio exceeds 10% by mass, the viscosity stability of the copolymer A after polymerization is inferior, which is not preferable.
前記単量体ａとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、ラウリル（メタ）アクリレートなどのアルキル（メタ）アクリレート、フェノキシ（メタ）アクリレート、ベンジル（メタ）アクリレートなどの芳香族環を有するモノマーが挙げられる。これらは単独でも或いは組み合わせてもよい。前記単量体ｂとしては、例えば、（メタ）アクリル酸、カルボキシエチルアクリレートなどが挙げられ、これらのモノマーｂはいずれも粘着剤の分野において公知であり、公知のモノマーｂはいずれも本発明で使用することができる。さらにモノマーｂとしてはヒドロキシエチル（メタ）アクリレートなどの水酸基含有モノマーも使用することができる。 Examples of the monomer a include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Monomers having an aromatic ring such as octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, alkyl (meth) acrylate such as lauryl (meth) acrylate, phenoxy (meth) acrylate, and benzyl (meth) acrylate Is mentioned. These may be used alone or in combination. Examples of the monomer b include (meth) acrylic acid, carboxyethyl acrylate, and the like, and these monomers b are all known in the field of pressure-sensitive adhesives. Can be used. Further, as the monomer b, a hydroxyl group-containing monomer such as hydroxyethyl (meth) acrylate can also be used.
前記単量体ｃとしては、例えば、アセトアセチル基含有単量体としては、アセトアセトキシエチルアクリレート、アセトアセトキシエチルメタクリレート、アセトアセトキシエチルクロトナート、アセトアセトキシプロピルアクリレート、アセトアセトキシプロピルメタクリレート、アセトアセトキシプロピルクロトナート、２−シアノアセトアセトキシエチルメタクリレート、Ｎ−（２−アセトアセトキシエチル）アクリルアミド、Ｎ−（２−アセトアセトキシエチル）メタクリルアミド、アセト酢酸アリル、アセト酢酸ビニルなどが挙げられる。このうち特にアセトアセトキシエチルアクリレートおよびアセトアセトキシエチルメタクリレートが好ましい。
前記単量体ｄとしては、例えば、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミドなどが挙げられる。その他、必要に応じてヒドロキシエチルアクリレートなどの水酸基含有モノマーも本発明で使用することができる。
Examples of the monomer c include acetoacetyl group-containing monomers such as acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl croto Nalto, 2-cyanoacetoacetoxyethyl methacrylate, N- (2-acetoacetoxyethyl) acrylamide, N- (2-acetoacetoxyethyl) methacrylamide, allyl acetoacetate, vinyl acetoacetate and the like. Of these, acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate are particularly preferred.
Examples of the monomer d include N, N-dimethylacrylamide, N, N-dimethylmethacrylamide and the like. In addition, if necessary, a hydroxyl group-containing monomer such as hydroxyethyl acrylate can also be used in the present invention.
上記単量体ａ〜ｄを共重合して得られる共重合体Ａの重量平均分子量（ＧＰＣ測定、標準ポリスチレン換算）が１００万〜２００万であり、好ましい重量平均分子量は１３０万〜１８０万である。重量平均分子量が１００万未満であると、粘着剤組成物とし、かつ粘着剤層を形成した場合、その粘着剤層の耐久性が不十分となる。一方、重量平均分子量が、２００万を超えると色むら・白抜け現象の発生の抑制が不十分であるので好ましくない。 The copolymer A obtained by copolymerizing the monomers a to d has a weight average molecular weight (GPC measurement, standard polystyrene conversion) of 1,000,000 to 2,000,000, and a preferable weight average molecular weight of 1,300,000 to 1,800,000. is there. When the weight average molecular weight is less than 1,000,000, when the pressure-sensitive adhesive composition is formed and the pressure-sensitive adhesive layer is formed, the durability of the pressure-sensitive adhesive layer becomes insufficient. On the other hand, if the weight average molecular weight exceeds 2 million, it is not preferable because the suppression of the occurrence of uneven color and white spots is insufficient.
本発明で使用する共重合体Ａは、上記分子量を有するとともに、ガラス転移点温度（Ｔｇ）（計算値）が、−５０℃以上であり、−５０℃〜０℃であることが好ましい。共重合体ＡのＴｇが−５０℃よりも低いと、該共重合体Ａに低分子量化合物（可塑剤）を添加したときに共重合体Ａが軟化しすぎて、該共重合体Ａを用いて粘着剤組成物とし、かつ粘着剤層を形成した場合、その粘着剤層の耐久性が不十分となる。 The copolymer A used in the present invention has the above-described molecular weight, and has a glass transition temperature (Tg) (calculated value) of -50 ° C or higher, preferably -50 ° C to 0 ° C. If the Tg of the copolymer A is lower than −50 ° C., when the low molecular weight compound (plasticizer) is added to the copolymer A, the copolymer A becomes too soft and the copolymer A is used. When the pressure-sensitive adhesive composition is formed and the pressure-sensitive adhesive layer is formed, the durability of the pressure-sensitive adhesive layer becomes insufficient.
一方、共重合体ＡのＴｇが０℃を超えると、共重合体Ａの分子量を１００万以上にしたときに、該共重合体Ａに低分子量化合物を添加しても、共重合体Ａに粘着性が発現せず、好ましい粘着剤としての性能が得られない。なお、本発明におけるＴｇとは、共重合体Ａの合成に使用したモノマーからの計算値である。 On the other hand, when the Tg of the copolymer A exceeds 0 ° C., even if a low molecular weight compound is added to the copolymer A when the molecular weight of the copolymer A is 1 million or more, Adhesiveness is not expressed, and the performance as a preferable adhesive cannot be obtained. In addition, Tg in this invention is a calculated value from the monomer used for the synthesis | combination of the copolymer A. FIG.
上記条件を満たす共重合体Ａは、通常の溶液重合、塊状重合、乳化重合または懸濁重合などにより製造することができるが、上記共重合体Ａが溶液として得られる溶液重合により製造することが好ましい。上記共重合体Ａが溶液として得られることにより、そのまま本発明の粘着剤組成物の製造に使用することができる。この溶液重合に使用する溶剤としては、例えば、酢酸エチル、トルエン、ｎ−ヘキサン、アセトン、メチルエチルケトンなどの有機溶剤を挙げることができる。 The copolymer A satisfying the above conditions can be produced by ordinary solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, or the like, but can be produced by solution polymerization in which the copolymer A is obtained as a solution. preferable. By obtaining the copolymer A as a solution, it can be used as it is for producing the pressure-sensitive adhesive composition of the present invention. Examples of the solvent used for the solution polymerization include organic solvents such as ethyl acetate, toluene, n-hexane, acetone, and methyl ethyl ketone.
また、重合に使用する重合開始剤としては、例えば、ベンゾイルパーオキシド、ラウリルパーオキシドなどの過酸化物、アゾビスイソブチロニトリル、アゾビスバレロニトリルなどのアゾビス化合物または高分子アゾ重合開始剤などを挙げることができ、これらは単独でもまたは組み合わせても使用することができる。また、上記重合においては、共重合体Ａの分子量を調整するために従来公知の連鎖移動剤を使用することができる。 Examples of the polymerization initiator used in the polymerization include peroxides such as benzoyl peroxide and lauryl peroxide, azobis compounds such as azobisisobutyronitrile and azobisvaleronitrile, and polymer azo polymerization initiators. These can be used alone or in combination. Moreover, in the said superposition | polymerization, in order to adjust the molecular weight of the copolymer A, a conventionally well-known chain transfer agent can be used.
本発明で使用する硬化剤Ｂとしては、例えば、１分子中にグリシジル基を２個以上有するポリグリシジル化合物、１分子中にイソシアネート基を２個以上有するポリイソシアネート化合物、１分子中にアジリジニル基を２個以上有するポリアジリジン化合物、１分子中にオキサゾリン基を２個以上有するポリオキサゾリン化合物、金属キレート化合物、エポキシ系化合物またはブチル化メラミン化合物などを使用することができる。粘着剤組成物の耐久性をより優れたものとできる点において、金属キレート化合物とビスフェノールＦ型化合物（化合物Ｘ）との併用、または金属キレート化合物と２官能以上のグリシジル基を有するビフェニル型化合物（化合物Ｙ）との併用が好ましい。 Examples of the curing agent B used in the present invention include a polyglycidyl compound having two or more glycidyl groups in one molecule, a polyisocyanate compound having two or more isocyanate groups in one molecule, and an aziridinyl group in one molecule. A polyaziridine compound having two or more, a polyoxazoline compound having two or more oxazoline groups in a molecule, a metal chelate compound, an epoxy compound, a butylated melamine compound, or the like can be used. In the point that the durability of the pressure-sensitive adhesive composition can be further improved, a combined use of a metal chelate compound and a bisphenol F-type compound (compound X), or a biphenyl-type compound having a glycidyl group having a bifunctional or higher functionality and a metal chelate compound The combined use with compound Y) is preferred.
上記金属キレート化合物としては、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロムおよびジルコニウムなどの多価金属がアセチルアセトンやアセト酢酸エチルに配位した化合物が挙げられ、好ましくはアルミキレート化合物およびチタンキレート化合物が挙げられる。その使用量は共重合体Ａ１００質量部当たり０．０１〜１質量部が好ましい。 Examples of the metal chelate compound include compounds in which a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium is coordinated to acetylacetone or ethyl acetoacetate. Preferably, an aluminum chelate compound and a titanium chelate compound are mentioned. The amount used is preferably 0.01 to 1 part by mass per 100 parts by mass of copolymer A.
前記化合物Ｘとしては、ビス（４−ヒドロキシフェニル）メタン化合物のジグリシジルエーテルおよびこれらの縮重合物が挙げられ、前記ビフェニル型化合物（化合物Ｙ）としては、２官能以上のグリシジル基を有するビフェニル型化合物が挙げられる。上記化合物Ｘおよび化合物Ｙとしては、重量平均分子量２，０００未満、エポキシ当量２００以下の化合物が好ましく、重量平均分子量が２，０００以上となると、粘着剤組成物との相溶性が悪くなり、架橋密度も下がり耐久性が劣るので好ましくない。また、エポキシ当量が２００を超える場合も粘着剤組成物との相溶性が悪くなり架橋密度も下がるため好ましくない。上記化合物Ｘ、Ｙの使用量は共重合体Ａ１００質量部当たり０．１〜５質量部が好ましい。使用量が０．１質量部未満であると、架橋密度が下がり、色むらも悪くなり、一方、使用量が５質量部を超えると架橋過剰になるため耐久性に劣る。 Examples of the compound X include diglycidyl ethers of bis (4-hydroxyphenyl) methane compounds and polycondensates thereof, and examples of the biphenyl type compound (compound Y) include biphenyl type having a glycidyl group having two or more functions. Compounds. As the compound X and the compound Y, compounds having a weight average molecular weight of less than 2,000 and an epoxy equivalent of 200 or less are preferable. When the weight average molecular weight is 2,000 or more, compatibility with the pressure-sensitive adhesive composition is deteriorated and crosslinking is performed. The density is lowered and the durability is inferior. Moreover, when the epoxy equivalent exceeds 200, the compatibility with the pressure-sensitive adhesive composition is deteriorated and the crosslinking density is also lowered, which is not preferable. The amount of the compounds X and Y used is preferably 0.1 to 5 parts by mass per 100 parts by mass of the copolymer A. When the amount used is less than 0.1 parts by mass, the crosslinking density decreases and the color unevenness also deteriorates. On the other hand, when the amount used exceeds 5 parts by mass, the crosslinking becomes excessive, resulting in poor durability.
上記化合物Ｘの具体例としては、例えば、商品名ＪＥＲ８０７（ビスフェノールＦ型エポキシ樹脂：エポキシ当量１７０、Ｍｗ３５０）、商品名ＪＥＲ８０６（ビスフェノールＦ型エポキシ樹脂：エポキシ当量１６５、Ｍｗ３５０）などが挙げられる。また、前記化合物Ｙとしては、例えば、商品名ＪＥＲＹＸ４０００（ビフェニル型エポキシ樹脂：エポキシ当量１８６、Ｍｗ３５４）などが挙げられる。 Specific examples of the compound X include trade name JER807 (bisphenol F type epoxy resin: epoxy equivalent 170, Mw350), trade name JER806 (bisphenol F type epoxy resin: epoxy equivalent 165, Mw350), and the like. Moreover, as said compound Y, brand name JERRY4000 (biphenyl type epoxy resin: epoxy equivalent 186, Mw354) etc. are mentioned, for example.
上記ポリイソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアナート、テトラメチレンジイソシアナート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネートなどのイソシアネート化合物及びこれらイソシアネート化合物をトリメチロールプロパンなどと付加したイソシアネート化合物やイソシアヌレート化合物、ビュレット型化合物、さらにポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどを付加反応させたウレタンプレポリマー型のイソシアネートなどが挙げられる。その使用量は共重合体Ａ１００質量部当たり０．０１〜５質量部が好ましい。 Examples of the polyisocyanate compound include isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and trimethylolpropane. And the like, and isocyanate compounds, isocyanurate compounds, burette type compounds, and urethane prepolymer type isocyanates obtained by addition reaction of polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like. The amount used is preferably 0.01 to 5 parts by mass per 100 parts by mass of copolymer A.
上記硬化剤Ｂの含有量は、前記共重合体Ａ１００質量部あたり０．０１〜５質量部であることが好ましく、より好ましくは０．１〜１質量部である。上記含有量が、０．０１質量部未満の場合は、粘着剤組成物の凝集力が低くなり、上記範囲内と比べて耐久性が劣る。一方、その使用量が５質量部を超える場合は、得られる粘着剤組成物が凝集力過多となり、貼着する偏光板の剥れの原因になる。 It is preferable that content of the said hardening | curing agent B is 0.01-5 mass parts per 100 mass parts of said copolymers A, More preferably, it is 0.1-1 mass part. When the said content is less than 0.01 mass part, the cohesion force of an adhesive composition becomes low and durability is inferior compared with the said range. On the other hand, when the amount used exceeds 5 parts by mass, the resulting pressure-sensitive adhesive composition has excessive cohesive force, which causes peeling of the polarizing plate to be attached.
本発明の粘着剤組成物は、さらに低分子量化合物を含み得る。好ましい低分子量化合物は、芳香族基を２個含有する化合物であり、例えば、安息香酸エステル系としてのジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、ベンジルベンゾエート、１，４−シクロヘキサンジメタノールジベンゾエートなどが挙げられる。なお、「芳香族基」の個数の数え方は、ナフタレン環などの縮合環は１個と数える。上記低分子量化合物の含有量は、上記共重合体Ａ１００質量部あたり３〜５０質量部であり、好ましい含有量は、共重合体Ａ１００質量部あたり２０〜５０質量部である。 The pressure-sensitive adhesive composition of the present invention may further contain a low molecular weight compound. Preferred low molecular weight compounds are compounds containing two aromatic groups, such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, benzyl benzoate, 1,4-cyclohexanedimethanol dibenzoate as benzoate esters. Can be mentioned. The number of “aromatic groups” is counted as one condensed ring such as a naphthalene ring. The content of the low molecular weight compound is 3 to 50 parts by mass per 100 parts by mass of the copolymer A, and a preferable content is 20 to 50 parts by mass per 100 parts by mass of the copolymer A.
本発明の粘着剤組成物は、さらに帯電防止剤を含有し得る。帯電防止剤としては、例えば、界面活性剤、アルカリ金属塩、イオン性液体などが挙げられ、これらの群から選ばれる少なくとも１種を使用することができる。帯電防止剤の使用量は、上記共重合体Ａ１００質量部あたり０．２〜１０質量部であり、好ましくは１〜５質量部である。 The pressure-sensitive adhesive composition of the present invention may further contain an antistatic agent. Examples of the antistatic agent include surfactants, alkali metal salts, ionic liquids, and the like, and at least one selected from these groups can be used. The usage-amount of an antistatic agent is 0.2-10 mass parts per 100 mass parts of said copolymers A, Preferably it is 1-5 mass parts.
本発明の粘着剤組成物は、さらにシランカップリング剤を含有し得る。これらのシランカップリング剤はいずれも粘着剤の分野において公知であり、公知のシランカップリング剤はいずれも本発明で使用することができる。シランカップリング剤の含有量は、共重合体Ａ１００質量部に対して０．０１〜５質量部であることが好ましい。 The pressure-sensitive adhesive composition of the present invention may further contain a silane coupling agent. These silane coupling agents are all known in the field of pressure-sensitive adhesives, and any known silane coupling agent can be used in the present invention. The content of the silane coupling agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the copolymer A.
本発明の粘着剤組成物は、さらに粘着力を調整する目的など、必要な特性に応じて、本発明の効果を損なわない範囲において、種々の添加剤を配合してもよい。例えば、テルペン系、テルペン−フェノール系、クマロンインデン系、スチレン系、ロジン系、キシレン系、フェノール系または石油系などの粘着付与樹脂、酸化防止剤、紫外線吸収剤、充填剤、顔料などを配合することができる。また、本発明の粘着剤組成物の製造方法自体は公知の方法でよく特に限定されないが、有機溶剤を含んだ溶液形態であることが好ましく、この場合、粘着剤層の形成が容易となる。 The pressure-sensitive adhesive composition of the present invention may further contain various additives in accordance with necessary characteristics such as the purpose of adjusting the pressure-sensitive adhesive force, as long as the effects of the present invention are not impaired. For example, terpene, terpene-phenol, coumarone indene, styrene, rosin, xylene, phenol, or petroleum tackifier resins, antioxidants, UV absorbers, fillers, pigments, etc. can do. The production method of the pressure-sensitive adhesive composition of the present invention may be a known method and is not particularly limited, but is preferably in the form of a solution containing an organic solvent. In this case, the pressure-sensitive adhesive layer can be easily formed.
本発明の粘着剤組成物の硬化後のゲル分率は８０〜９９％である。このような非常に高いゲル分率は、弾性率を高くすることが可能であるが、従来の粘着剤ではゲル分率８０〜９９％の範囲に設定すると、架橋が過剰になる傾向があるため耐久性において剥がれが生じていた。しかし、本発明では鋭意検討した結果、前記単量体ａと、前記単量体ｂと、前記単量体ｃと、前記単量体ｄとの共重合体Ａと硬化剤として金属キレート化合物、エポキシ系化合物、イソシアネート系化合物、アジリジン系化合物を最適な範囲で選択すること、または金属キレート化合物と前記化合物Ｘまたは化合物Ｙとを併用することで、ゲル分率が８０〜９９％の範囲内でも耐久性が良好であり、さらに弾性率を高くすることで偏光板の収縮を抑えて色むらおよび白抜け防止性の優れた粘着剤を提供することを可能にした。上記ゲル分率が８０％未満であると、弾性率も低くなり、偏光板の収縮を抑えることができずに必然的に色むらおよび白抜けの劣る粘着剤になる。 The gel fraction after curing of the pressure-sensitive adhesive composition of the present invention is 80 to 99%. Such a very high gel fraction can increase the elastic modulus. However, in the case of the conventional pressure-sensitive adhesive, if the gel fraction is set in the range of 80 to 99%, crosslinking tends to be excessive. Peeling occurred in durability. However, as a result of intensive studies in the present invention, the monomer A, the monomer b, the monomer c, the copolymer A of the monomer d and a metal chelate compound as a curing agent, By selecting an epoxy compound, an isocyanate compound, or an aziridine compound within an optimum range, or by using the metal chelate compound and the compound X or compound Y in combination, the gel fraction is within the range of 80 to 99%. It was possible to provide a pressure-sensitive adhesive having excellent durability and suppressing the shrinkage of the polarizing plate by increasing the elastic modulus, and having excellent color unevenness and white spot prevention. When the gel fraction is less than 80%, the elastic modulus is also low, and the pressure-sensitive adhesive is inevitably inferior in color unevenness and white spots without suppressing the contraction of the polarizing plate.
本発明の粘着剤組成物は、粘着剤層を形成した場合におけるその貯蔵弾性率が１．０×１０5Ｐａ以上である。このような非常に高い貯蔵弾性率は、前記単量体ａと、前記単量体ｂと、前記単量体ｃと、前記単量体ｄとの共重合体Ａと硬化剤Ｂとして金属キレート化合物、エポキシ系化合物、イソシアネート系化合物、アジリジン系化合物を最適な範囲で選択こと、または金属キレート化合物と前記化合物Ｘまたは化合物Ｙとを併用することで、ゲル分率が８０〜９９％の範囲に設定することによって達成された。上記貯蔵弾性率が１．０×１０5Ｐａ未満であると、偏光板の収縮を抑えきれずに、装置のサイズに依存することなく、色むらおよび白抜けが劣るため好ましくない。 The pressure-sensitive adhesive composition of the present invention has a storage elastic modulus of 1.0 × 10 5 Pa or more when a pressure-sensitive adhesive layer is formed. Such a very high storage modulus is obtained by using a metal chelate as a copolymer A and a curing agent B of the monomer a, the monomer b, the monomer c, and the monomer d. By selecting a compound, an epoxy compound, an isocyanate compound, or an aziridine compound within an optimal range, or by using a metal chelate compound in combination with the compound X or compound Y, the gel fraction is in the range of 80 to 99%. Achieved by setting. When the storage elastic modulus is less than 1.0 × 10 5 Pa, the contraction of the polarizing plate cannot be suppressed and the color unevenness and white spots are inferior without depending on the size of the apparatus, which is not preferable.
本発明の粘着剤組成物は、偏光板用の粘着剤として適しており、本発明の粘着剤組成物を用いて粘着剤層を形成した偏光板は、高温或いは高温高湿下においてもガラス基板などから剥れることなく、粘着剤層に発泡が生じることのない特性（耐久性）と、長期間時間が経過しても容易に剥離でき、また、剥離後において基板などに残留物が生じない特性（リワーク性）とを併せ持つ。 The pressure-sensitive adhesive composition of the present invention is suitable as a pressure-sensitive adhesive for polarizing plates, and a polarizing plate in which a pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition of the present invention is a glass substrate even at high temperature or high temperature and high humidity. The pressure-sensitive adhesive layer does not cause foaming and does not cause foaming (durability), and can be easily peeled off even after a long period of time, and there is no residue on the substrate after peeling. Combined with characteristics (reworkability).
すなわち、上記偏光板が、ディスコティック液晶がコートされている偏光板である場合には、コートされていない偏光板（一般的には、無処理トリアセチルセルロース（ＴＡＣ）フィルム、通常接触角は６０〜７０°）に比べて、８５〜９５°と接触角が高く、粘着剤との密着性が劣るため、粘着剤層とパネルガラス表面との間の発泡または偏光板の浮き、剥がれが発生しやすく、かつ白抜けが発生しやすいなどの課題があるが、本発明の粘着剤組成物の使用により上記課題が解決された。 That is, when the polarizing plate is a polarizing plate coated with a discotic liquid crystal, an uncoated polarizing plate (generally an untreated triacetylcellulose (TAC) film, usually having a contact angle of 60 ~ 70 °), the contact angle is high at 85-95 °, and the adhesiveness with the adhesive is inferior. Therefore, foaming between the adhesive layer and the panel glass surface, or floating and peeling of the polarizing plate occurs. However, the use of the pressure-sensitive adhesive composition of the present invention has solved the above problem.
ディスコティック液晶がコートされている偏光板とは、ＴＡＣフィルム上に、下記に示すような側鎖の末端に架橋基を有しているトリフェニレン系のディスコティック化合物が架橋し、配向状態に保たれたディスコティック層が有する視野角拡大フィルムと偏光フィルムとが一体化してなる偏光板であり、例えば、ポリビニルアルコール系偏光子（ＰＶＡ）の両面に、それぞれＴＡＣフィルムを貼り合わせてなる偏光フィルムの片面に、例えば、ディスコティック液晶からなる視野角拡大機能層を塗布により設けたもの、あるいは視野角拡大フィルムを接着剤で貼り合わせたものなどを挙げることができる。特に、ディスコティック液晶がコートされた偏光板は、モニター（通常７〜２６インチ）用に使用され、上記で説明したように視野角を拡大するために使用されている。 A polarizing plate coated with a discotic liquid crystal means that a triphenylene discotic compound having a cross-linking group at the end of a side chain as shown below is cross-linked on a TAC film and maintained in an aligned state. The polarizing plate formed by integrating the viewing angle widening film and the polarizing film of the discotic layer, for example, one side of a polarizing film obtained by laminating a TAC film on both sides of a polyvinyl alcohol polarizer (PVA). In addition, for example, a viewing angle widening functional layer made of a discotic liquid crystal is provided by coating, or a viewing angle widening film is bonded with an adhesive. In particular, a polarizing plate coated with a discotic liquid crystal is used for a monitor (usually 7 to 26 inches) and is used to expand a viewing angle as described above.
また、上記偏光板が、延伸フィルム、例えば、延伸トリアセチルセルロース系フィルム、延伸ポリシクロオレフィン系フィルムまたは延伸セルロースアセテートプロピオネートフィルムを基材とした偏光板である場合には、一般的な偏光板（無処理ＴＡＣフィルムを使用したもの）に比べて、フィルムが延伸されているために収縮率が大きく、特に、対角型に色むら・白抜け現象が発生し、それを抑制するのに不十分であるなどの課題がある。上記偏光板は、テレビ（通常１５〜６０インチ）用に使用され、色相、コントラストを向上させ、位相差をなくすためのものであり、このような課題が本発明の粘着剤組成物の使用により解決された。 When the polarizing plate is a polarizing plate based on a stretched film, for example, a stretched triacetyl cellulose-based film, a stretched polycycloolefin-based film, or a stretched cellulose acetate propionate film, Compared to the plate (which uses untreated TAC film), the film is stretched, so the shrinkage rate is large. In particular, the color irregularity and white spot phenomenon occurs in the diagonal type to suppress it. There are problems such as insufficient. The polarizing plate is used for a television (usually 15 to 60 inches) to improve hue and contrast and eliminate a phase difference. Such a problem is caused by the use of the pressure-sensitive adhesive composition of the present invention. It was solved.
本発明の粘着剤組成物は、通常使用されている塗布装置、例えば、ロール塗布装置などを用いて、上記偏光板の片面或いは両面に塗工し、塗工層を乾燥することにより粘着剤層を形成するのに使用する。また、必要に応じて、粘着剤層を加熱架橋または紫外線などの光による硬化をすることもできる。また、本発明の粘着剤組成物を、まず、シリコーン樹脂などの剥離剤を表面にコートしたポリエチレンテレフタレートフィルム（ＰＥＴフィルム）などの保護フィルムに粘着剤組成物を塗布して乾燥し粘着剤層を形成した後に、該粘着剤層に上記偏光板を貼り合わせる方法でも使用できる。 The pressure-sensitive adhesive composition of the present invention is coated on one or both sides of the polarizing plate using a commonly used coating device, for example, a roll coating device, and the coating layer is dried to dry the pressure-sensitive adhesive layer. Used to form If necessary, the pressure-sensitive adhesive layer can be cured by heat crosslinking or light such as ultraviolet rays. In addition, the pressure-sensitive adhesive composition of the present invention is first applied to a protective film such as a polyethylene terephthalate film (PET film) whose surface is coated with a release agent such as a silicone resin, and then dried to form a pressure-sensitive adhesive layer. After forming, it can also be used by a method of bonding the polarizing plate to the pressure-sensitive adhesive layer.
本発明の粘着剤組成物の塗布量は、乾燥後の粘着剤層の厚さが、１０〜５０μｍとなる程度であることが好ましい。上記粘着剤層の厚さを上記範囲内とすることにより、より耐久性とリワーク性のバランスがとれた偏光板となる。以上の本発明の粘着剤組成物を用いた偏光板は、通常使用されている手段にて、液晶表示装置のガラス基板上に貼着することができる。 The coating amount of the pressure-sensitive adhesive composition of the present invention is preferably such that the thickness of the pressure-sensitive adhesive layer after drying is 10 to 50 μm. By setting the thickness of the pressure-sensitive adhesive layer within the above range, the polarizing plate is more balanced between durability and reworkability. The polarizing plate using the above-mentioned pressure-sensitive adhesive composition of the present invention can be stuck on a glass substrate of a liquid crystal display device by means usually used.
次ぎに実施例および比較例を挙げて本発明をさらに具体的に説明する。なお、文中「部」とあるのは質量基準である。
＜共重合体溶液の調製＞
［共重合体溶液１〜２５］
攪拌機、温度計、還流冷却器および窒素導入管を備えた反応装置に、窒素ガスを導入して、この反応装置内の空気を窒素ガスに置換した。その後、この反応装置中に、ブチルアクリレート１００部、アクリル酸１部、Ｎ，Ｎ−ジメチルアクリルアミド５部、アセトアセトエトキシメタクリレート１部、アゾビスイソブチロニトリル０．１部および酢酸エチル１００部を加えた。これを攪拌させながら、窒素ガス気流中において、６８℃で８時間反応させ、重量平均分子量１５０万のアクリル共重合体の溶液を得た。さらに酢酸エチルで希釈して固形分２０％の共重合体溶液１を得た。同様にして表１に記載のモノマー組成で共重合体溶液２〜２５を得た。これらの共重合体溶液には、シリコンおよび低分子量化合物を含む例も含まれている。
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, “part” is based on mass.
<Preparation of copolymer solution>
[Copolymer solution 1-25]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Thereafter, 100 parts of butyl acrylate, 1 part of acrylic acid, 5 parts of N, N-dimethylacrylamide, 1 part of acetoacetoethoxymethacrylate, 0.1 part of azobisisobutyronitrile and 100 parts of ethyl acetate were added to the reactor. added. While stirring this, reaction was carried out at 68 ° C. for 8 hours in a nitrogen gas stream to obtain a solution of an acrylic copolymer having a weight average molecular weight of 1,500,000. Further, this was diluted with ethyl acetate to obtain a copolymer solution 1 having a solid content of 20%. Similarly, copolymer solutions 2 to 25 were obtained with the monomer compositions shown in Table 1. Examples of these copolymer solutions include silicon and low molecular weight compounds.
ＢＡ：アクリル酸ブチル
ＡＡ：アクリル酸
ＤＭＡＡ：Ｎ，Ｎ−ジメチルアクリルアミド
ＤＭＭＡ：Ｎ，Ｎ−ジメチルメタクリルアミド
ＡＡＥＭ：メタクリル酸アセトアセトキシエチル
ＡＡＥＡ：アクリル酸アセトアセトキシエチル
ＭＡ：アクリル酸メチル
ＥＡ：アクリル酸エチル
ＰＨＥＡ：アクリル酸フェノキシエチル
ＭＡＡｃ：メタクリル酸
ＢＺＡ：ベンジルアクリレート
２ＥＨＡ：２−エチルヘキシルアクリレート
低分子量化合物Ａ：ベンジルベンゾエート
低分子量化合物Ｂ：ジプロピレングリコールジベンゾエート
低分子量化合物Ｃ：ジエチレングリコールジベンゾエート
低分子量化合物Ｄ：ブチルベンジルフタレート
＊：さらにシリコンＸ−２２−２４７５の０．１部を含む
BA: butyl acrylate AA: acrylic acid DMAA: N, N-dimethylacrylamide DMMA: N, N-dimethylmethacrylamide AAEM: acetoacetoxyethyl methacrylate AAEA: acetoacetoxyethyl acrylate MA: methyl acrylate EA: ethyl acrylate PHEA: phenoxyethyl acrylate MAAc: methacrylic acid BZA: benzyl acrylate 2EHA: 2-ethylhexyl acrylate low molecular weight compound A: benzyl benzoate low molecular weight compound B: dipropylene glycol dibenzoate low molecular weight compound C: diethylene glycol dibenzoate low molecular weight compound D: Butyl benzyl phthalate *: further contains 0.1 part of silicon X-22-2475
上記において、重量平均分子量（Ｍｗ）の値は、GPC(GEL Permeation Chromatography)法により測定したポリスチレン換算分子量である。詳しくは、共重合体を常温で乾燥させて得られた塗膜をテトラヒドロフランに溶解し、高速液体クロマトグラフ（島津製作所製、ＬＣ−１０ＡＤｖｐ、カラムＫＦ−Ｇ＋ＫＦ−８０６×２本）で測定し、ポリスチレン換算での重量平均分子量（Ｍｗ）を求めた。 In the above, the value of the weight average molecular weight (Mw) is a molecular weight in terms of polystyrene measured by GPC (GEL Permeation Chromatography) method. Specifically, the coating film obtained by drying the copolymer at room temperature was dissolved in tetrahydrofuran, and measured with a high performance liquid chromatograph (manufactured by Shimadzu Corporation, LC-10ADvp, column KF-G + KF-806 × 2). The weight average molecular weight (Mw) in terms of polystyrene was determined.
＜粘着剤組成物、偏光板の作製および評価＞
［実施例１〜１４、比較例１〜１１］
共重合体１の固形分１００部に対して、コロネートＬ０．１部、アルミキレートＡ０．１部、ＫＢＭ−８０３の０．１部を混合した溶液をシリコーン樹脂コートされたＰＥＴフィルム上に塗布後、９０℃で乾燥することによって溶媒を除去し、厚さ２５μｍの粘着剤層を形成した。この粘着剤層を形成した面に、厚さ１８０μｍの偏光板（ＥＷＶ）を貼り合わせた後、２３℃、５０％ＲＨの雰囲気で７日間養生することにより、実施例１の偏光板を作製した。該実施例１と同様にして表２に記載の成分を混合して実施例２〜１４および比較例１〜１１の偏光板を得た。なお、各例の内ではＡＳ剤を含む例もある。
<Preparation and evaluation of pressure-sensitive adhesive composition and polarizing plate>
[Examples 1-14, Comparative Examples 1-11]
After applying a solution prepared by mixing 0.1 part of coronate L, 0.1 part of aluminum chelate A and 0.1 part of KBM-803 to 100 parts of solid content of copolymer 1 on a PET film coated with silicone resin The solvent was removed by drying at 90 ° C. to form a pressure-sensitive adhesive layer having a thickness of 25 μm. After the 180 μm-thick polarizing plate (EWV) was bonded to the surface on which the pressure-sensitive adhesive layer was formed, the polarizing plate of Example 1 was produced by curing for 7 days in an atmosphere of 23 ° C. and 50% RH. . In the same manner as in Example 1, the components shown in Table 2 were mixed to obtain polarizing plates of Examples 2 to 14 and Comparative Examples 1 to 11. Each example includes an AS agent.
コロネートＬ：日本ポリウレタン工業（株）製ポリイソシアネート
テトラッドＣ：三菱瓦斯化学（株）製ポリグリシジル化合物
アルミキレートＡ：川研ファインケミカル（株）製アルミニウムトリスアセチルアセトネート
アルミキレートＤ：アルミニウムモノアセチルアセテートビス（エチルアセトアセテート）
チタンキレート：松本ファインケミカル（株）製 チタンアセチルアセトネート
ＴＡＺＭ：相互薬工（株）製 トリメチロールプロパン−トリス−（β−アジリジニルプロピオナート
ＫＢＭ−８０３：信越化学工業（株）製γ−メルカプトプロピルメチルジメトキシシラン
ＫＢＭ−８０２：信越化学工業（株）製γ−メルカプトプロピルメチルトリメトキシシラン
ＫＢＭ−４０３：信越化学工業（株）製３−グリシドキシプロピルトリエトキシシラン
Ｘ−４１−１８１０：信越化学工業（株）製メチルメルカプト系アルコキシオリゴマー
Ｘ−４１−１８０５：信越化学工業（株）製メルカプト系アルコキシオリゴマー
ＡＳ剤：トリフルオロメタンスルフォン酸リチウム（帯電防止剤）
ＪＥＲ８０７：ビスフェノールＦ型エポキシ樹脂（エポキシ当量１７０、Ｍｗ３５０）
ＪＥＲ８０６：ビスフェノールＦ型エポキシ樹脂（エポキシ当量１６５、Ｍｗ３５０）
ＪＥＲＹＸ４０００：ビフェニル型エポキシ樹脂（エポキシ当量１８６、Ｍｗ３５４）
ＥＷＶ：ディスコティック液晶がコートされている偏光板
延伸ＴＡＣ：延伸トリアセチルセルロースフィルムを使用した偏光板
延伸ＣＡＰ：延伸セルロースアセテートプロピオネートフィルムを使用した偏光板
延伸ＣＯＰ：延伸ポリシクロオレフィン系フィルムを使用した偏光板
Coronate L: Polyisocyanate tetrad manufactured by Nippon Polyurethane Industry Co., Ltd. C: Polyglycidyl compound aluminum chelate manufactured by Mitsubishi Gas Chemical Co., Ltd. A: Aluminum trisacetylacetonate aluminum chelate manufactured by Kawaken Fine Chemical Co., Ltd. D: Aluminum monoacetyl acetate Bis (ethyl acetoacetate)
Titanium chelate: Matsumoto Fine Chemical Co., Ltd. Titanium acetylacetonate TAZM: Mutual Yakumi Co., Ltd. Trimethylolpropane-Tris- (β-aziridinylpropionate KBM-803: Shin-Etsu Chemical Co., Ltd. γ- Mercaptopropylmethyldimethoxysilane KBM-802: Shin-Etsu Chemical Co., Ltd. γ-mercaptopropylmethyltrimethoxysilane KBM-403: Shin-Etsu Chemical Co., Ltd. 3-glycidoxypropyltriethoxysilane X-41-1810: Shin-Etsu Chemical Co., Ltd. methyl mercapto-based alkoxy oligomer X-41-1805: Shin-Etsu Chemical Co., Ltd. mercapto-based alkoxy oligomer AS agent: lithium trifluoromethanesulfonate (antistatic agent)
JER807: Bisphenol F type epoxy resin (epoxy equivalent 170, Mw350)
JER806: Bisphenol F type epoxy resin (epoxy equivalent 165, Mw 350)
JERRY4000: biphenyl type epoxy resin (epoxy equivalent 186, Mw354)
EWV: polarizing plate coated with discotic liquid crystal TAC: polarizing plate using a stretched triacetyl cellulose film CAP: polarizing plate using a stretched cellulose acetate propionate film COP: stretched polycycloolefin film Used polarizing plate
この偏光板を後述する試験方法にて耐久性、ゲル分率（％）、貯蔵弾性率（Ｐａ）および白抜けの評価を行った。実施例の評価結果は全ての項目で良好であった。評価結果を表３に示す。 This polarizing plate was evaluated for durability, gel fraction (%), storage elastic modulus (Pa), and white spots by the test methods described later. The evaluation results of the examples were good in all items. The evaluation results are shown in Table 3.
＜試験方法および評価基準＞
［耐久性試験］
実施例および比較例における偏光板を、それぞれ２００ｍｍ×３００ｍｍに断裁し、ＰＥＴフィルムを剥離した後、ガラス基板上に貼り付け、オートクレーブ処理を行い、評価用サンプルを作製した。得られた評価用サンプルについて、それぞれ下記項目の試験を行った。
<Test methods and evaluation criteria>
[Durability test]
Each of the polarizing plates in Examples and Comparative Examples was cut to 200 mm × 300 mm and the PET film was peeled off, followed by pasting on a glass substrate and performing an autoclave treatment to prepare an evaluation sample. About the obtained sample for evaluation, the test of the following item was performed, respectively.
（１）８０℃
上記評価用サンプルを、８０℃（ＤＲＹ）の雰囲気下に５００時間放置した後、発泡および剥れについて目視により確認した。評価基準は下記の通りである。
（２）６０℃・９０％ＲＨ
上記評価用サンプルを、６０℃・９０％ＲＨの雰囲気下に５００時間放置した後、発泡および剥れについて目視により確認した。評価基準は下記の通りである。
(1) 80 ° C
The sample for evaluation was allowed to stand in an atmosphere of 80 ° C. (DRY) for 500 hours, and then visually confirmed for foaming and peeling. The evaluation criteria are as follows.
(2) 60 ° C / 90% RH
The sample for evaluation was allowed to stand in an atmosphere of 60 ° C. and 90% RH for 500 hours, and then visually confirmed for foaming and peeling. The evaluation criteria are as follows.
・評価基準
（１）発泡
○：偏光板に発泡が確認されない。
△：偏光板に発泡が僅かに確認された。
×：偏光板に発泡が確認された。
（２）剥れ
○：偏光板に剥れが確認されない。
△：偏光板に剥れが僅かに確認された。
×：偏光板に剥れが確認された。
Evaluation criteria (1) Foaming ○: Foaming is not confirmed on the polarizing plate.
Δ: Slight foaming was confirmed on the polarizing plate.
X: Foaming was confirmed on the polarizing plate.
(2) Peeling ○: Peeling is not confirmed on the polarizing plate.
Δ: Slight peeling was confirmed on the polarizing plate.
X: Peeling was confirmed on the polarizing plate.
［ゲル分率］
架橋後の粘着剤皮膜を０．２ｇ正確に秤量（Ｗ１）して酢酸エチル５０ｍｌに１日間浸漬した後、２００メッシュの金網を秤量後（Ｗ２）ろ過をして可溶分を抽出した。その後乾燥させて不溶部分の重量（Ｗ３）を求めた。これら測定値から以下の式を使いゲル分率（重量％）を算出した。
ゲル分率（重量％）＝（（Ｗ３−Ｗ２）／Ｗ１）×１００
[Gel fraction]
After 0.2 g of the crosslinked adhesive film was accurately weighed (W1) and immersed in 50 ml of ethyl acetate for 1 day, a 200-mesh wire mesh was weighed (W2) and filtered to extract soluble components. Thereafter, drying was performed to determine the weight (W3) of the insoluble portion. The gel fraction (% by weight) was calculated from these measured values using the following formula.
Gel fraction (% by weight) = ((W3−W2) / W1) × 100
［貯蔵弾性率］
架橋後の粘着剤皮膜２５μｍを固体剪断治具に挟み、（株）ユービーエム製Rheogel-E4000を用いて２０℃の時の貯蔵弾性率（Ｇ´）を周波数１Ｈｚで測定した。
[Storage modulus]
The pressure-sensitive adhesive film 25 μm after crosslinking was sandwiched between solid shear jigs, and the storage elastic modulus (G ′) at 20 ° C. was measured at a frequency of 1 Hz using Rheogel-E4000 manufactured by UBM Co., Ltd.
［白抜け試験］
実施例および比較例における偏光板を用いた８０℃耐久試験後の同試料を２枚クロスニコルにして貼り合わせた後、８ｉｎｃｈ角および２６ｉｎｃｈ角の試料を作成し、それぞれ液晶モニターのバックライト上に置き、白抜けの状態を目視で観察した。
なお、従来は、小さいサイズの表示画面では、白抜け・色むらの発生が少なくても、表示画面が大きくなると白抜け・色むらの発生が多くなり、一方、大きいサイズの表示画面では、白抜け・色むらの発生が少なくても、表示画面が小さくなると白抜け・色むらの発生が多くなるという課題があり、上記試験を行った。その結果、本発明の粘着剤組成物を用いたものは、表示画面のサイズに依存することなく、白抜け・色むらの発生を有効に防止することができた。
[White spot test]
After the 80 ° C. endurance test using the polarizing plate in the example and the comparative example was bonded in a crossed Nicol form, 8 inch and 26 inch samples were prepared and placed on the backlight of the liquid crystal monitor, respectively. The white spots were observed visually.
Conventionally, even if the occurrence of white spots and color unevenness is small on a small display screen, white spots and color unevenness increase as the display screen becomes large. Even if the occurrence of missing or uneven color is small, there is a problem that the occurrence of white missing or uneven color increases as the display screen becomes small, and the above test was performed. As a result, those using the pressure-sensitive adhesive composition of the present invention were able to effectively prevent the occurrence of white spots and color unevenness without depending on the size of the display screen.
・評価基準
○：偏光板に白抜けが観察されなかった。
△：偏光板に白抜けが僅かに観察された。
×：偏光板に白抜けが観察された。
-Evaluation criteria ○: No white spots were observed on the polarizing plate.
Δ: Slight white spots were observed on the polarizing plate.
X: White spots were observed on the polarizing plate.
本発明によれば、本発明の粘着剤組成物を液晶表示装置の液晶セルを構成するガラス基板と偏光板、特にディスコティック液晶がコートされている偏光板、および延伸フィルム、例えば、延伸トリアセチルセルロース系フィルム、延伸ポリシクロオレフィン系フィルムまたは延伸セルロースアセテートプロピオネートフィルムを基材とする偏光板との間の粘着剤層の形成に用いることにより、液晶表示装置において特有の額縁型或いは対角型の色むら・白抜け現象の発生を効果的に防止することができる。本発明の粘着剤組成物は、上記偏光板の伸縮によって発生する応力を緩和するだけでなく、同時にその応力によって上記偏光板に発生した光学的な歪を、装置のサイズに依存することなくバランスよく補正すると思われる。 According to the present invention, the pressure-sensitive adhesive composition of the present invention comprises a glass substrate constituting a liquid crystal cell of a liquid crystal display device and a polarizing plate, in particular, a polarizing plate coated with a discotic liquid crystal, and a stretched film such as stretched triacetyl. By using it to form a pressure-sensitive adhesive layer between a cellulose-based film, a stretched polycycloolefin-based film, or a stretched cellulose acetate propionate film as a base material, a frame type or diagonal characteristic unique to a liquid crystal display device It is possible to effectively prevent the occurrence of uneven color and white spots in the mold. The pressure-sensitive adhesive composition of the present invention not only relieves the stress generated by the expansion and contraction of the polarizing plate, but also balances the optical distortion generated in the polarizing plate by the stress without depending on the size of the apparatus. It seems to correct well.
Claims (5)
上記共重合体Ａにおける単量体の使用割合が、単量体ａ〜ｄの合計を１００質量％としたときに、単量体ｂが０．５〜８質量％、単量体ｃが０．５〜５質量％、単量体ｄが１〜１０質量％、および残りが単量体ａであり、
硬化後のゲル分率８０〜９９％であり、かつ粘着剤層を形成した場合の２０℃におけるその貯蔵弾性率が１．０×１０5Ｐａ以上であり、ガラス転移点温度（Ｔｇ）が−５０℃以上であることを特徴とする偏光板用粘着剤組成物。 From a copolymer A and a curing agent B of a (meth) acrylic acid ester monomer a, a carboxyl group-containing monomer b, an acetoacetyl group-containing monomer c, and a dialkyl-substituted acrylamide monomer d Become
The proportion of monomers used in the copolymer A is such that when the total of the monomers a to d is 100 mass%, the monomer b is 0.5 to 8 mass% and the monomer c is 0. 5 to 5 mass%, monomer d is 1 to 10 mass%, and the remainder is monomer a,
The gel fraction after curing is 80 to 99%, the storage elastic modulus at 20 ° C. when the pressure-sensitive adhesive layer is formed is 1.0 × 10 5 Pa or more, and the glass transition temperature (Tg) is − It is 50 degreeC or more, The adhesive composition for polarizing plates characterized by the above-mentioned.
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| JP5936538B2 (en) * | 2010-03-10 | 2016-06-22 | 日東電工株式会社 | Optical adhesive sheet |
| JP5758088B2 (en) * | 2010-06-28 | 2015-08-05 | 日東電工株式会社 | Optical film adhesive composition, optical film adhesive layer, adhesive optical film, and image display device |
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