JP2009507255A - Acrylic adhesive composition for polarizing plate - Google Patents
Acrylic adhesive composition for polarizing plate Download PDFInfo
- Publication number
- JP2009507255A JP2009507255A JP2008528937A JP2008528937A JP2009507255A JP 2009507255 A JP2009507255 A JP 2009507255A JP 2008528937 A JP2008528937 A JP 2008528937A JP 2008528937 A JP2008528937 A JP 2008528937A JP 2009507255 A JP2009507255 A JP 2009507255A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic
- meth
- acrylate
- sensitive adhesive
- adhesive composition
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 239000003522 acrylic cement Substances 0.000 title claims description 11
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 85
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 40
- -1 alkyl (meth) acrylic acid Chemical compound 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 26
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000853 adhesive Substances 0.000 claims description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 41
- 239000003431 cross linking reagent Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000004132 cross linking Methods 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 15
- 229920000058 polyacrylate Polymers 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 210000002858 crystal cell Anatomy 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000010556 emulsion polymerization method Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000010558 suspension polymerization method Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- UOMUPDCRXJLVGR-UHFFFAOYSA-N propane-1,2,2-triol Chemical compound CC(O)(O)CO UOMUPDCRXJLVGR-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000035882 stress Effects 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 23
- 125000000524 functional group Chemical group 0.000 description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
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- 239000011120 plywood Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 230000001681 protective effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
Abstract
本発明は、アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体を含有する（メタ）アクリル系共重合体を含み、ゲル分率が１０〜５５％であり、膨脹比が３０〜１１０であり、最終粘着剤からエチルアセテートで溶出されたゾルの重量平均分子量が８００，０００以上であり、及び分子量分布が２．０〜７．０であることを特徴とする偏光板用アクリル系粘着剤組成物であり、本発明に係る組成物を含む偏光板及びこれを含む液晶表示装置は高温・多湿条件下でも優れた粘着耐久信頼性を示し、高いモジュラス及び応力緩和特性を效果的に付与し、偏光板生産時、作業性に優れ、光漏れ現象を改善させる効果がある。 The present invention includes a (meth) acrylic copolymer containing an alkyl (meth) acrylic acid ester monomer having an alkyl carbon number of 1 to 12, a gel fraction of 10 to 55%, and an expansion ratio 30 to 110, the weight average molecular weight of the sol eluted with ethyl acetate from the final pressure-sensitive adhesive is 800,000 or more, and the molecular weight distribution is 2.0 to 7.0. A polarizing plate comprising the composition according to the present invention and a liquid crystal display comprising the same exhibit excellent adhesion durability reliability even under high temperature and high humidity conditions, and have high modulus and stress relaxation characteristics. Effectively imparts, has excellent workability during polarizing plate production, and has the effect of improving the light leakage phenomenon.
Description
本発明は、偏光板用アクリル系粘着剤組成物に関するものである。特に、高温及び／又は多湿条件下で、耐久信頼性及び低い光漏れ特性に優れ、偏光板作業性が大幅に向上することができる偏光板用粘着剤組成物、これを含む偏光板及び液晶表示装置に関するものである。 The present invention relates to an acrylic pressure-sensitive adhesive composition for polarizing plates. In particular, a pressure-sensitive adhesive composition for a polarizing plate, which is excellent in durability reliability and low light leakage characteristics under a high temperature and / or high humidity condition, and can greatly improve the workability of a polarizing plate, a polarizing plate containing the same, and a liquid crystal display It relates to the device.
一般に、液晶表示装置を製造するために 、基本的に液晶を含んでいる液晶セルと偏光板が必要とされ、これを接合するための適切な接着層または粘着層を使用しなければならない。さらに、液晶表示装置の機能を向上させるために、位相差板、広視野角補償板または輝度向上フィルムなどを付加的に偏光板に接着して使用することができる。 In general, in order to manufacture a liquid crystal display device, a liquid crystal cell containing a liquid crystal and a polarizing plate are basically required, and an appropriate adhesive layer or adhesive layer for bonding the liquid crystal cell must be used. Furthermore, in order to improve the function of the liquid crystal display device, a retardation plate, a wide viewing angle compensation plate, a brightness enhancement film, or the like can be additionally adhered to the polarizing plate.
液晶表示装置は、一定に配列されている液晶層；粘着層または接着層を含む多層構造の偏光板；位相差板；及び追加の機能性フィルム層などを含むのが一般的である。 The liquid crystal display device generally includes a liquid crystal layer that is regularly arranged; a polarizing plate having a multilayer structure including an adhesive layer or an adhesive layer; a retardation plate; and an additional functional film layer.
この時、偏光板は一定の方向に配列されたヨード系化合物または二色性偏光物質を含む構造であり、これらの偏光素子を保護するために両面にトリアセチルセルロース（ＴＡＣ）系等の保護フィルムを使用し、多層を構成する。また、偏光板は一方性分子配列を持つ形状の位相差フィルムや液晶型フィルムなどの広視野角補償フィルムを付加的に含むことができる。 At this time, the polarizing plate has a structure containing an iodo compound or a dichroic polarizing material arranged in a certain direction, and a protective film made of triacetyl cellulose (TAC) or the like on both sides in order to protect these polarizing elements. To configure multiple layers. Further, the polarizing plate may additionally include a wide viewing angle compensation film such as a retardation film having a unidirectional molecular arrangement and a liquid crystal film.
上記言及された各フィルムは互いに異なる分子構造及び組成を有する材料で作られるため、互いに異なる物理的特性を持っている。特に、高温・多湿条件下では、一方性分子配列を有する材料等の収縮または膨脹による寸法安定性が足りなくなる。従って、偏光板が粘着剤で固定されている場合に、高温・多湿条件下での偏光板の収縮または膨脹による変形応力が残留した状態で残り、これにより、応力が集中した部分から光漏れが発生される。 Each of the films mentioned above are made of materials having different molecular structures and compositions, and therefore have different physical properties. In particular, under high-temperature and high-humidity conditions, the dimensional stability due to shrinkage or expansion of a material having a unilateral molecular arrangement becomes insufficient. Therefore, when the polarizing plate is fixed with an adhesive, deformation stress due to contraction or expansion of the polarizing plate under a high temperature and high humidity condition remains, thereby causing light leakage from a portion where the stress is concentrated. Generated.
上記での光漏れ現象を改善させるための方法として、高温・多湿条件下で偏光板の収縮現象を低減することが求められるが、互いに異なる物理的特性を有する物質で構成された偏光板が付着された液晶パネルで発生される応力を除去することは非常に難しい。光漏れ現象を改善するさらに別の方法は偏光板を液晶パネルに固定する粘着剤層に優れた応力緩和機能を付与する方法である。一般に粘着剤はゴム系、アクリル系、及びシリコン系などがあるが、この中で、アクリル系粘着剤が接着特性、光学的特性、耐久性、または耐候性の面で有用であり、偏光板用粘着剤組成物の製造に最も広く使われている。 As a method for improving the light leakage phenomenon described above, it is required to reduce the shrinkage phenomenon of the polarizing plate under high temperature and high humidity conditions, but a polarizing plate composed of substances having different physical characteristics is attached. It is very difficult to remove the stress generated in the liquid crystal panel. Yet another method of improving the light leakage phenomenon is a method of imparting an excellent stress relaxation function to the pressure-sensitive adhesive layer that fixes the polarizing plate to the liquid crystal panel. Generally, there are rubber-based, acrylic-based, and silicon-based adhesives. Among them, acrylic adhesives are useful in terms of adhesive properties, optical properties, durability, or weather resistance. It is most widely used for the production of adhesive compositions.
上記の応力緩和機能を粘着層に付与するための通常的な粘着剤設計は、外部応力に対してずれ量が大きく、変形しやすいように設計することである。代表的な方法は多官能架橋剤と反応可能な架橋官能基を含む高分子量重合体に架橋可能官能基を少量含むか、含まない低分子量重合体を混合して粘着剤組成物に高温・多湿条件下で優れた耐久性及び応力緩和機能を付与する方法である。 The usual pressure-sensitive adhesive design for imparting the above-described stress relaxation function to the pressure-sensitive adhesive layer is to design so that the amount of deviation with respect to external stress is large and is easily deformed. A typical method is that a high molecular weight polymer containing a crosslinkable functional group capable of reacting with a polyfunctional crosslinker is mixed with a low molecular weight polymer containing a small amount of a crosslinkable functional group or a low molecular weight polymer not containing high molecular weight. It is a method of imparting excellent durability and stress relaxation function under the conditions.
例えば、特許文献１（大韓民国特許公開公報第１９９８−０７９２６６号）は、重量平均分子量が１００，０００以上である高分子量アクリル系共重合体１００重量部、重量平均分子量が３０，０００以下の低分子量アクリル系共重合体２０〜２００重量部及び多官能性架橋剤化合物０．００５〜５重量部からなる偏光板用粘着剤組成物を通じて応力緩和特性を付与することによって光漏れ現象を改善しようとした。 For example, Patent Document 1 (Korean Patent Publication No. 1998-079266) discloses that 100 parts by weight of a high molecular weight acrylic copolymer having a weight average molecular weight of 100,000 or more and a low molecular weight having a weight average molecular weight of 30,000 or less. An attempt was made to improve the light leakage phenomenon by imparting stress relaxation properties through a pressure-sensitive adhesive composition for a polarizing plate comprising 20 to 200 parts by weight of an acrylic copolymer and 0.005 to 5 parts by weight of a polyfunctional crosslinking agent compound. .
特許文献２（日本国特許公開公報第２００２−４７４６８号）は、重量平均分子量が８００，０００〜２，０００，０００の官能基を有する高分子量アクリル系共重合体１００重量部、重量平均分子量が５０，０００以下で、分散度が１．０〜２．５である官能基を持たない低分子量アクリル系共重合体５〜５０重量部、架橋剤及びシラン化合物からなる偏光板用粘着剤組成物を通じて応力緩和特性を付与しようとした。 Patent Document 2 (Japanese Patent Publication No. 2002-47468) discloses that 100 parts by weight of a high molecular weight acrylic copolymer having a functional group having a weight average molecular weight of 800,000 to 2,000,000, and a weight average molecular weight. A pressure-sensitive adhesive composition for a polarizing plate, comprising 50,000 or less and 5 to 50 parts by weight of a low molecular weight acrylic copolymer having no functional group with a dispersity of 1.0 to 2.5, a crosslinking agent and a silane compound I tried to give stress relaxation properties through.
また、特許文献３（日本国特許公開公報第２００３−４９１４１号）は、重量平均分子量１，０００，０００〜２，０００，０００の官能基を含む高分子量アクリル系共重合体、重量平均分子量が３０，０００〜３００，０００の官能基が２個未満含まれた中分子量アクリル系共重合体、重量平均分子量が１，０００〜２０，０００（分散度１．０〜２．５）である、官能基を持たない低分子量のアクリル系共重合体及び架橋剤からなる偏光板用粘着剤組成物を通じて応力緩和特性を付与することによって光漏れ現象を改善させようとした。 Patent Document 3 (Japanese Patent Publication No. 2003-49141) discloses a high molecular weight acrylic copolymer containing a functional group having a weight average molecular weight of 1,000,000 to 2,000,000, and a weight average molecular weight of A medium molecular weight acrylic copolymer containing less than 2 functional groups of 30,000 to 300,000, and a weight average molecular weight of 1,000 to 20,000 (dispersity of 1.0 to 2.5). An attempt was made to improve the light leakage phenomenon by imparting stress relaxation properties through a pressure-sensitive adhesive composition for a polarizing plate comprising a low molecular weight acrylic copolymer having no functional group and a crosslinking agent.
上記特許公報は、粘着剤の応力緩和性を改善させるために、最終粘着剤をソフトにする技術的思想を具現している。即ち、添加された低分子量体によって粘着剤のモジュラスが減少し、外部の応力に対してずれ量が大きくなり、変形しやくなり、偏光板の収縮または膨脹により発生される局部的な応力を緩和させるように設計している。しかし、低分子量体添加を通じてソフトな粘着剤を具現する場合、最終粘着剤層のモジュラスが低下し、偏光板製造工程で偏光板をロール形態に保管時、粘着剤のピット（Pit）不良が生じやすく、製造された偏光板を切断する場合、切断される偏光板の断面から粘着剤が突出（粘着剤はみ出し）するか、突出された粘着剤によって偏光板が容易に汚染されるという問題点がある。また、添加された低分子量が液晶パネルのガラスとＴＡＣの界面層への移動が容易に行われるため、高温・多湿条件で耐久性の低下が容易になる。 The above patent publication embodies the technical idea of softening the final pressure-sensitive adhesive in order to improve the stress relaxation property of the pressure-sensitive adhesive. That is, the added low molecular weight material reduces the modulus of the adhesive, increases the amount of displacement with respect to external stress, makes it easier to deform, and relieves local stress generated by contraction or expansion of the polarizing plate. Designed to let you. However, when a soft adhesive is implemented through the addition of a low molecular weight material, the modulus of the final adhesive layer is reduced, and when the polarizing plate is stored in a roll form during the manufacturing process of the polarizing plate, a pit failure of the adhesive occurs. When cutting the manufactured polarizing plate, the pressure-sensitive adhesive protrudes from the cross section of the polarizing plate to be cut (the pressure-sensitive adhesive protrudes), or the polarizing plate is easily contaminated by the protruding pressure-sensitive adhesive. is there. Moreover, since the added low molecular weight easily moves to the interface layer between the glass and TAC of the liquid crystal panel, the durability is easily lowered under high temperature and high humidity conditions.
応力緩和機能を粘着層に付加するためのまた別の方法は、架橋官能基を含む高分子量体で製造された最終粘着剤のゲル含量を、非常に少なく保持する方法である。このような方法は、粘着剤のモジュラスが大きく低下しない長所があるが、均一な低いゲル含量を保持するように再現することは非常に難しく、粘着剤架橋後、偏光板が切断可能な時点までの時間（熟成時間）が長い短所があり、高温・多湿下で耐久性が大きく低下される短所がある。 Another method for adding a stress relaxation function to the pressure-sensitive adhesive layer is to keep the gel content of the final pressure-sensitive adhesive made of a high molecular weight material containing a cross-linking functional group very low. Such a method has the advantage that the modulus of the pressure-sensitive adhesive is not greatly reduced, but it is very difficult to reproduce it so as to maintain a uniform low gel content, and until the polarizing plate can be cut after crosslinking of the pressure-sensitive adhesive. There is a disadvantage that the time (ripening time) is long and the durability is greatly reduced under high temperature and high humidity.
上記の高分子量体で構成された低いゲル含量を有する粘着剤を再現性よく製造する方法として、特許文献４（日本国特許公開公報昭６０−２０７１０１）を利用できる。この公報では、架橋可能な官能基を含むアクリル共重合体（Ａ）と架橋可能な官能基を含まないアクリル共重合体（Ｂ）と官能基２個以上の多官能性架橋剤とを混合し、上記Ａ／Ｂの重量比率が１／４〜４／１の領域で粘着剤を製造する発明を開示している。即ち、この公報は、架橋時、架橋可能な官能基の量に対し、対応する多官能架橋剤量を添加し、遊離された官能基を除去することで製造された偏光板の長期保管性に優れた技術的思想を示しているが、用いられるアクリル重合体の分子量に対する条件やその架橋構造に対する技術的思想は表現されておらず、特に光漏れ現象と関連した粘着剤の応力緩和特性に対する技術的思想は記載されていない。 Patent Document 4 (Japanese Patent Publication No. 60-207101) can be used as a method for producing an adhesive having a low gel content composed of the above-described high molecular weight substance with good reproducibility. In this publication, an acrylic copolymer (A) containing a crosslinkable functional group, an acrylic copolymer (B) containing no crosslinkable functional group, and a polyfunctional crosslinker having two or more functional groups are mixed. In the invention, the pressure-sensitive adhesive is produced in a region where the weight ratio of A / B is 1/4 to 4/1. That is, this publication describes the long-term storage property of a polarizing plate produced by adding a corresponding polyfunctional crosslinking agent amount to the amount of functional groups capable of crosslinking during crosslinking and removing the released functional groups. Although it shows an excellent technical idea, it does not express the conditions for the molecular weight of the acrylic polymer used and the technical idea for its cross-linking structure, especially the technique for stress relaxation characteristics of adhesives related to the light leakage phenomenon. The philosophy is not described.
従って、高温・多湿条件下だけでなく、長期間使用時、発生しうる耐久信頼性などの偏光板製品の主要特性をほとんど変化させることなく、最終粘着剤のモジュラス減少を最小化し、偏光板作業性低下を抑制しながら、光漏れ現象が改善された偏光板用粘着剤の開発及びこれを適用した偏光板が求められている実状にある。
上記のような従来の問題点を解決するために、本発明の目的は、高温・多湿条件下で発生しうる粘着耐久信頼性などの主要特性を変化させることなく、粘着剤のモジュラスを大きく減少せず、偏光板の作業性低下を抑制しながら、応力緩和特性向上を通じて光漏れ現象を改善した偏光板用アクリル系粘着剤組成物を提供することにある。
本発明の別の目的は、上記特性を有するアクリル系粘着剤組成物を用いた偏光板を提供することにある。
In order to solve the conventional problems as described above, the object of the present invention is to greatly reduce the modulus of an adhesive without changing main characteristics such as adhesive durability reliability that can occur under high temperature and high humidity conditions. The present invention also provides an acrylic pressure-sensitive adhesive composition for a polarizing plate that improves the light leakage phenomenon through an improvement in stress relaxation characteristics while suppressing a decrease in workability of the polarizing plate.
Another object of the present invention is to provide a polarizing plate using an acrylic pressure-sensitive adhesive composition having the above characteristics.
本発明のまた別の目的は、上記した特性を有するアクリル系粘着剤組成物から製造された偏光板を含む液晶表示装置を提供することにある。 Another object of the present invention is to provide a liquid crystal display device including a polarizing plate produced from an acrylic pressure-sensitive adhesive composition having the characteristics described above.
上記の目的を達成するために、本発明はアルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体を含有する（メタ）アクリル系共重合体を含み、下記数式（１）で示されるゲル分率が１０〜５５％であり、下記数式（２）で示される膨脹比が３０〜１１０であり、最終粘着剤からエチルアセテートで溶出されたゾルの重量平均分子量が８００，０００以上であり、及び分子量分布（重量平均分子量と数平均分子量の比率）が２．０〜７．０であることを特徴とするアクリル系粘着剤組成物を提供する：
ゲル分率（％）＝Ｂ／Ａ×１００ （１）
膨脹比＝Ｃ／Ｂ （２）
（上記式で、Ａはアクリル系粘着剤組成物の重量を示し、Ｂは常温で、エチルアセテートに４８時間、浸漬後のアクリル系粘着剤組成物の不溶解分の乾燥質量を示し、Ｃは常温で、エチルアセテートに４８時間、浸漬後のエチルアセテートによって膨脹された不溶解分の質量（アクリル粘着剤不溶解分質量＋浸透溶剤の質量）を示す。）。
In order to achieve the above object, the present invention includes a (meth) acrylic copolymer containing an alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms in alkyl, and the following formula (1) The gel fraction represented by the formula (10) is 10 to 55%, the expansion ratio represented by the following formula (2) is 30 to 110, and the weight average molecular weight of the sol eluted with ethyl acetate from the final adhesive is 800,000. The acrylic pressure-sensitive adhesive composition is characterized by having a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of 2.0 to 7.0.
Gel fraction (%) = B / A × 100 (1)
Expansion ratio = C / B (2)
(In the above formula, A indicates the weight of the acrylic pressure-sensitive adhesive composition, B indicates the dry mass of the insoluble content of the acrylic pressure-sensitive adhesive composition after immersion in ethyl acetate for 48 hours at normal temperature, and C indicates The mass of insoluble matter expanded by ethyl acetate after immersion in ethyl acetate at room temperature for 48 hours (the mass of acrylic adhesive insoluble matter plus the mass of penetrating solvent).
また、本発明は偏光フィルムの一面または両面に上記の偏光板用アクリル系粘着剤組成物で形成された粘着剤層を含むことを特徴とする粘着偏光板を提供する。 Moreover, this invention provides the adhesive polarizing plate characterized by including the adhesive layer formed with said acrylic adhesive composition for polarizing plates on the one or both surfaces of a polarizing film.
また、本発明は上記で製造された粘着偏光板を液晶セルの一面または両面に接合する液晶パネルを含むことを特徴とする液晶表示装置を提供する。 In addition, the present invention provides a liquid crystal display device including a liquid crystal panel that joins the adhesive polarizing plate manufactured as described above to one or both surfaces of a liquid crystal cell.
本発明は、最終粘着剤のゲル含量、膨脹比、溶剤によって溶出されたゾルの分子量及び分子量分布を調節することによって高温・多湿条件で耐久信頼性を保持し、最終粘着剤のモジュラスを偏光板作業性において問題のない水準に保持しながら、粘着剤の応力緩和特性を向上させ、光漏れを改善させたことを特徴とする。 The present invention maintains durability reliability under high temperature and high humidity conditions by adjusting the gel content of the final adhesive, the expansion ratio, the molecular weight and molecular weight distribution of the sol eluted by the solvent, and the modulus of the final adhesive is changed to a polarizing plate. It is characterized by improving the stress relaxation property of the pressure-sensitive adhesive and improving light leakage while maintaining a level with no problem in workability.
通常的に最終粘着剤を低いゲル含量で調節し、溶剤によって浸漬する場合、ゲルが溶剤によって膨脹された量（膨脹比または膨脹指数）は非常に大きく増大する。このような架橋構造を有する粘着剤の場合、非常に緩い架橋構造を形成する。従って、外部から応力が付加される場合、そのずれ量が大きく、容易に変形されるため、粘着剤の応力緩和特性が非常に優れ、且つ光漏れを改善させることができるが、高温・多湿下で耐久性が非常に悪くなる。 Usually, when the final adhesive is adjusted with a low gel content and soaked with a solvent, the amount that the gel is swollen by the solvent (expansion ratio or expansion index) increases very greatly. In the case of the pressure-sensitive adhesive having such a crosslinked structure, a very loose crosslinked structure is formed. Therefore, when stress is applied from the outside, the amount of deviation is large and it is easily deformed. Therefore, the stress relaxation property of the adhesive is very excellent and light leakage can be improved. The durability becomes very bad.
本発明者はこのような問題点を解決するために鋭意研究した結果、最終粘着剤のゲル含量が低く、且つ膨脹比が少ないように粘着剤を設計する場合、粘着剤は応力緩和特性に優れながら、さらに高温・多湿下で耐久性を保持することを見出し、本発明の完成に至った。理論的に制限されないが、ゲル含量が低く、且つ膨脹比が少ない粘着剤の場合、相対的に緻密な架橋構造を形成し、このような架橋構造を粘着剤のゾル（未架橋の自由高分子）を互いに連結し、耐久性と応力緩和特性を同時に満足させることができる。従って、本発明において架橋構造の調節は非常に重要である。類似なゲル含量でも架橋構造が非常に緻密になれば、未架橋高分子が架橋構造間を浸透し難くなるため、耐久信頼性が大きく低下される。反面に架橋構造が緩すぎると、未架橋高分子が架橋構造間で容易に浸透することができるが、粘着剤に力が加えられたとき、未架橋高分子が架橋構造間を容易に抜け出すようになり、やはり耐久信頼性が低下される。 As a result of diligent research to solve such problems, the present inventor has excellent stress relaxation characteristics when designing a pressure-sensitive adhesive so that the gel content of the final pressure-sensitive adhesive is low and the expansion ratio is small. However, the inventors have found that the durability is maintained under high temperature and high humidity, and have completed the present invention. Although not theoretically limited, in the case of a pressure-sensitive adhesive having a low gel content and a low expansion ratio, a relatively dense cross-linked structure is formed, and such a cross-linked structure is formed into a pressure-sensitive adhesive sol (uncrosslinked free polymer). ) Can be connected to each other to simultaneously satisfy the durability and stress relaxation characteristics. Therefore, in the present invention, the control of the crosslinked structure is very important. If the cross-linked structure becomes very dense even with a similar gel content, the uncrosslinked polymer will not easily penetrate between the cross-linked structures, and the durability reliability will be greatly reduced. On the other hand, if the crosslinked structure is too loose, the uncrosslinked polymer can easily penetrate between the crosslinked structures. However, when force is applied to the adhesive, the uncrosslinked polymer easily escapes between the crosslinked structures. As a result, the durability reliability is also lowered.
本発明の偏光板用粘着剤組成物は、種々の形態のアクリル系、シリコン系、ゴム系、ウレタン系、ポリエステル系、エポキシ系などの光学的に使われる諸般粘着、接着素材に制限なく、適用することができるが、その中でも、アクリル系粘着剤が好ましい。 The pressure-sensitive adhesive composition for polarizing plates of the present invention can be applied to various forms of acrylic, silicon, rubber, urethane, polyester, epoxy, and other optically used adhesives and adhesive materials in various forms. Among them, an acrylic pressure-sensitive adhesive is preferable.
以下、本発明をより具体的に説明する。
本発明は、アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体を含有する（メタ）アクリル系共重合体を含み、
下記数式（１）で示されるゲル分率が１０〜５５％であり、
下記数式（２）で示される膨脹比が３０〜１１０であり、
最終粘着剤からエチルアセテートで溶出されたゾルの重量平均分子量が８００，０００以上であり、及び
重量平均分子量と数平均分子量の比率（以下、‘分子量分布’）が２．０〜７．０であることを特徴とするアクリル系粘着剤組成物を提供する：
ゲル分率（％）＝Ｂ／Ａ×１００ （１）
膨脹比＝Ｃ／Ｂ （２）
（ここで、Ａ、Ｂ及びＣは上記同義である。）。
Hereinafter, the present invention will be described more specifically.
The present invention includes a (meth) acrylic copolymer containing an alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms in alkyl,
The gel fraction represented by the following formula (1) is 10 to 55%,
The expansion ratio shown by the following mathematical formula (2) is 30 to 110,
The sol eluted with ethyl acetate from the final adhesive has a weight average molecular weight of 800,000 or more, and the ratio of the weight average molecular weight to the number average molecular weight (hereinafter, “molecular weight distribution”) is 2.0 to 7.0. An acrylic pressure-sensitive adhesive composition is provided that is characterized by:
Gel fraction (%) = B / A × 100 (1)
Expansion ratio = C / B (2)
(Here, A, B and C are as defined above.)
本発明に係るアクリル系粘着剤組成物において、ゲル分率は１５〜４５％のものが好ましく、この場合、ゲル分率及び膨脹比が下記数式（３）を満足させることがより好ましい：
本発明によるアクリル系粘着剤組成物のゲル含量は、１０〜５５％、好ましくは１５〜４５％、より好ましくは１５〜３５％の範囲である。 The gel content of the acrylic pressure-sensitive adhesive composition according to the present invention is in the range of 10 to 55%, preferably 15 to 45%, more preferably 15 to 35%.
上記ゲル分率が５５％を超えると、粘着剤の応力緩和特性が大きく落ち、１０％未満であれば、高温・多湿条件下での耐久信頼性が非常に悪くなる。 If the gel fraction exceeds 55%, the stress relaxation property of the pressure-sensitive adhesive is greatly reduced, and if it is less than 10%, the durability reliability under high temperature and high humidity conditions becomes very poor.
同時にゲルによって測定される膨脹比が３０未満であれば、架橋構造が緻密になり過ぎて粘着剤の応力緩和特性が不充分となり、１１０を超えると、架橋構造が緩くなり過ぎ、耐久性が悪くなる。 At the same time, if the expansion ratio measured by the gel is less than 30, the crosslinked structure becomes too dense and the stress relaxation property of the pressure-sensitive adhesive becomes insufficient. If it exceeds 110, the crosslinked structure becomes too loose and the durability is poor. Become.
また、溶剤によって溶出されたゾルの分子量が８００，０００未満であれば、それぞれの架橋構造がゾル部分によって十分に連結されず、耐久性が悪くなる。 Moreover, if the molecular weight of the sol eluted by the solvent is less than 800,000, the respective crosslinked structures are not sufficiently connected by the sol part, and the durability is deteriorated.
一方、ゾルの分子量分布が２未満であれば、応力緩和特性が不足し、７を超えると、耐久性に問題が発生する。従って、上記ゾルの分子量分布は２．０〜７．０が好ましくて、３〜５．５の間に調節することが最も好ましい。 On the other hand, if the molecular weight distribution of the sol is less than 2, the stress relaxation characteristics are insufficient, and if it exceeds 7, a problem occurs in durability. Therefore, the molecular weight distribution of the sol is preferably 2.0 to 7.0, and most preferably adjusted between 3 and 5.5.
本発明に係る（メタ）アクリル系共重合体は、アルキル基が２〜１４のアルキル（メタ）アクリル酸エステル単量体８０〜９９．８重量部及び多官能性架橋剤と架橋可能なカルボキシル基又は水酸基を有するビニル系及び／又はアクリル系架橋性単量体 ０．０１〜５重量部を含むことが好ましい。 The (meth) acrylic copolymer according to the present invention comprises 80 to 99.8 parts by weight of an alkyl (meth) acrylate monomer having 2 to 14 alkyl groups and a carboxyl group capable of crosslinking with a polyfunctional crosslinking agent. Alternatively, it is preferable to contain 0.01 to 5 parts by weight of a vinyl-based and / or acrylic-based crosslinkable monomer having a hydroxyl group.
上記アルキルの炭素数が２〜１４のアルキル（メタ）アクリル酸エステル単量体は、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、t−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−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、またはテトラデシル（メタ）アクリレートなどが挙げられる。 アルキルの炭素数が上記範囲に属しないとき、粘着剤のガラス遷移温度（Ｔｇ）が高くなるか、粘着性の調節が難しいため、２〜１４の範囲に限定される。上記アルキル（メタ）アクリル酸エステルは単独で使われてもよく、２種類以上が併用されていてもよい。粘着力及び凝集力調節のために全体単量体成分中、上記アルキル基が２〜１４のアルキル（メタ）アクリル酸エステル単量体８０〜９９．８重量部の範囲内で使用することが好ましい。 The alkyl (meth) acrylate monomer having 2 to 14 carbon atoms is ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, Examples include lauryl (meth) acrylate and tetradecyl (meth) acrylate. When the carbon number of alkyl does not belong to the above range, the glass transition temperature (Tg) of the pressure-sensitive adhesive becomes high or it is difficult to adjust the pressure-sensitive adhesiveness. The said alkyl (meth) acrylic acid ester may be used independently and 2 or more types may be used together. It is preferable to use within the range of 80 to 99.8 parts by weight of the alkyl (meth) acrylate monomer having 2 to 14 alkyl groups in the whole monomer component in order to control adhesive force and cohesive force. .
本発明に係る（メタ）アクリル系共重合体は、粘着力及び凝集力を調節するために、多官能性架橋剤と架橋可能な水酸基またはカルボキシル基を含むビニル系及び／又はアクリル系架橋性単量体を共重合できる。 The (meth) acrylic copolymer according to the present invention is a vinyl-based and / or acrylic-based crosslinkable monomer containing a hydroxyl group or a carboxyl group capable of crosslinking with a polyfunctional crosslinking agent in order to adjust the adhesive force and cohesive force. A monomer can be copolymerized.
上記架橋性単量体の例は、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチレングリコール（メタ）アクリレート、２−ヒドロキシプロピレングリコール（メタ）アクリレート、アクリル酸、メタアクリル酸、アクリル酸二量体、イタコン酸、マレイン酸又はマレイン酸無水物の群から１種以上選択することができる。好ましくは、ビニル系及び／又はアクリル系架橋性単量体の量があまり多い場合、粘着性が低下され、剥離力が低下されるため、全体単量体成分中の０．０１〜５重量部の使用が好ましい。 Examples of the crosslinkable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxy One or more can be selected from the group of propylene glycol (meth) acrylate, acrylic acid, methacrylic acid, acrylic acid dimer, itaconic acid, maleic acid or maleic anhydride. Preferably, when the amount of the vinyl-based and / or acrylic-based crosslinkable monomer is too large, the tackiness is lowered and the peeling force is lowered, so that 0.01 to 5 parts by weight in the whole monomer component Is preferred.
本発明に係る（メタ）アクリル系共重合体は、粘着剤のガラス転移温度を調節するか、またはその他の機能性を付与するために、任意成分として総単量体重量対比０〜２０重量部の下記一般式（１）のビニル系単量体をさらに含むことが好ましい： In order to adjust the glass transition temperature of the pressure-sensitive adhesive or to impart other functionality, the (meth) acrylic copolymer according to the present invention is 0 to 20 parts by weight relative to the total monomer weight as an optional component. It is preferable to further contain a vinyl monomer represented by the following general formula (1):
好ましくは、Ｒ３〜Ｒ５の定義中のアルキルは、炭素数１〜６の低級アルキル、より好ましくはメチルまたはエチルを示す。 Preferably, alkyl in the definition of R 3 to R 5 represents lower alkyl having 1 to 6 carbon atoms, more preferably methyl or ethyl.
上記一般式（１）の化合物の例は、スチレン、アルファメチルスチレンのようなスチレン系単量体；酢酸ビニルのようなカルボン酸ビニルエステル；（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミドなどの窒素含有ビニル単量体などが挙げられる。上記アクリル系共重合体中の上記ビニル系単量体の量があまり多い場合、粘着剤組成物の柔軟性が低下され、剥離力が低下されるため、全体単量体成分中の２０重量部以下の使用が好ましい。 Examples of the compound of the general formula (1) include styrene monomers such as styrene and alphamethylstyrene; carboxylic acid vinyl esters such as vinyl acetate; (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and the like. And nitrogen-containing vinyl monomers. When the amount of the vinyl monomer in the acrylic copolymer is too large, the flexibility of the pressure-sensitive adhesive composition is lowered and the peeling force is lowered. Therefore, 20 parts by weight in the whole monomer component The following uses are preferred.
上記成分を含む本発明のアクリル系粘着剤組成物は架橋剤を、さらに含んでいてもよい。 The acrylic pressure-sensitive adhesive composition of the present invention containing the above components may further contain a crosslinking agent.
上記アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体を主成分とするアクリル系共重合体を架橋するのに使用される架橋剤は、アクリル系重合体のカルボキシル基及び水酸基などと反応することによって粘着剤の凝集力を高める機能を有する。上記架橋剤はイソシアネート系化合物、エポキシ系化合物、アジリジン系化合物、及び金属キレート系化合物よりなる群から選択され得る。 The crosslinking agent used to crosslink the acrylic copolymer based on the alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms as the alkyl is a carboxyl group of the acrylic polymer and It has a function of increasing the cohesive strength of the pressure-sensitive adhesive by reacting with a hydroxyl group or the like. The cross-linking agent may be selected from the group consisting of isocyanate compounds, epoxy compounds, aziridine compounds, and metal chelate compounds.
特に、上記イソシアネート系架橋剤としては、トリレンジイソシアネート、キシレ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、ヘキサメチレンジイソシアネート、アイソフォームジイソシアネート、テトラメチルキシレンジイソシアネート、ナフタレンジイソシアネート、またはこれらのトリメチロールプロパンのようなポリオールとの反応物などがある。また、エポキシ系架橋剤としては、エチレングリコールジグリシジルエーテル、トリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジルエチレンジアミン、またはグリセリンジグリシジルエーテルなどが上げられる。上記アジリジン系架橋剤は、Ｎ，Ｎ’−トルエン−２，４−ビス（１−アジリジンカルボキサイド）、Ｎ，Ｎ’−ジフェニルメタン-４，４’−ビス（１−アジリジンカルボキサイド）、トリエチレンメラミン、ビスイソプロタロイル−１−（２−メチルアジリジン）、またはトリ−１−アジリジニルホスフィンオキサイドなどがある。上記金属キレート系架橋剤は、アルミニウム、鉄、亜鉛、スズ、チタン、アンチモン、マグネシウム、またはバナジウムなどの多価金属がアセチルアセトンまたはアセト酢酸エチルに配位した化合物などが挙げられる。上記架橋剤の含量は（メタ）アクリル系共重合体１００重量部に対して０．０１〜１０重量部で使われることが好ましい。 In particular, the isocyanate-based crosslinking agent includes tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoform diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, or a reaction product thereof with a polyol such as trimethylolpropane. and so on. Examples of the epoxy-based crosslinking agent include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ′, N′-tetraglycidylethylenediamine, and glycerin diglycidyl ether. The above-mentioned aziridine-based crosslinking agents are N, N′-toluene-2,4-bis (1-aziridinecarboxide), N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxide), triethylene Examples include melamine, bisisoprotaloyl-1- (2-methylaziridine), or tri-1-aziridinylphosphine oxide. Examples of the metal chelate-based crosslinking agent include compounds in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, or vanadium is coordinated to acetylacetone or ethyl acetoacetate. The content of the crosslinking agent is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic copolymer.
また、本発明の粘着剤組成物は、シラン系カップリング剤をさらに含んでいてもよく、これはガラス板と接着する場合に接着安定性を向上させ、耐熱／耐湿特性を向上させることができる。上記シラン系カップリング剤は、特に高温と高湿下で、長時間放置された場合、接着信頼性を向上させる機能を持っている。その含量はアクリル共重合体１００重量部に対して０．００５〜５重量部で使用することができる。上記シラン系カップリング剤化合物は、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、γ−メタクリルオキシプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、３−イソシアネートプロピルトリエトキシシラン、またはγ−アセトアセテートプロピルトリメトキシシランである。これらは単独または混合して使用できる。 In addition, the pressure-sensitive adhesive composition of the present invention may further contain a silane coupling agent, which can improve the adhesion stability when adhering to a glass plate and can improve the heat / humidity resistance. . The silane coupling agent has a function of improving adhesion reliability particularly when left for a long time at high temperature and high humidity. The content can be 0.005-5 weight part with respect to 100 weight part of acrylic copolymers. The silane coupling agent compound is γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, Or γ-acetoacetate propyltrimethoxysilane. These can be used alone or in combination.
さらに、必要に応じて、本発明のアクリル系粘着剤組成物は粘着性能を調節するために粘着性付与樹脂をさらに含んでいてもよい。その含量はアクリル系共重合体１００重量部に対して１〜１００重量部の範囲で使用することができる。この時、上記粘着性付与樹脂が過量使われれば、粘着剤の相溶性または凝集力を減少する場合があるので、注意して適切に添加しなければならない。上記粘着性付与樹脂の例は、（水添）ハイドロカーボン系樹脂、（水添）ロジン樹脂、（水添）ロジンエステル樹脂、（水添）テルペン樹脂、（水添）テルペンフェノール樹脂、重合ロジン樹脂、または重合ロジンエステル樹脂などが上げられる。これらは単独または２種以上混合して使用することができる。 Furthermore, if necessary, the acrylic pressure-sensitive adhesive composition of the present invention may further contain a tackifier resin in order to adjust the pressure-sensitive adhesive performance. The content can be used in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the acrylic copolymer. At this time, if an excessive amount of the tackifying resin is used, the compatibility or cohesive force of the pressure-sensitive adhesive may be reduced, so it must be added appropriately with caution. Examples of the tackifying resin include (hydrogenated) hydrocarbon resin, (hydrogenated) rosin resin, (hydrogenated) rosin ester resin, (hydrogenated) terpene resin, (hydrogenated) terpene phenol resin, and polymerized rosin. Resin, polymerized rosin ester resin, etc. are raised. These can be used alone or in admixture of two or more.
また、本発明のアクリル系粘着剤組成物は、特定の目的のために可塑剤、エポキシ樹脂及び硬化剤などをさらに含んでいてもよい。また、紫外線安定剤、酸化防止剤、調色剤、補強剤、充填剤、消泡剤、界面活性剤などを適当に加えられる。 The acrylic pressure-sensitive adhesive composition of the present invention may further contain a plasticizer, an epoxy resin, a curing agent, and the like for a specific purpose. In addition, ultraviolet stabilizers, antioxidants, toning agents, reinforcing agents, fillers, antifoaming agents, surfactants, and the like can be appropriately added.
さらに、本発明は、アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体及び多官能性架橋剤と架橋可能なカルボキシル基又は水酸基を有するビニル系及び／又はアクリル系架橋性単量体を反応させて架橋用構造用アクリル系重合体を製造する段階；
アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体を反応させて未架橋構造用アクリル系重合体を製造する段階；及び
上記架橋構造用アクリル系重合体及び未架橋構造用アクリル系重合体を混合する段階；を含む本発明に係る偏光板用アクリル系粘着剤組成物の製造方法、または
アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体及び多官能性架橋剤と架橋可能なカルボキシル基又は水酸基を有するビニル系及び／又はアクリル系架橋性単量体を反応させて架橋用構造を含有するアクリル系重合体を製造する第１段階；及び
上記第１段階で得た架橋構造用アクリル系重合体の存在下で、アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体をさらに反応させ、未架橋用構造を提供する第２段階；を含む本発明に係る偏光板用アクリル系粘着剤組成物の製造方法に関するものである。
Furthermore, the present invention is a vinyl and / or acrylic crosslinkable having a carboxyl group or a hydroxyl group capable of crosslinking with an alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms and a polyfunctional crosslinking agent. Reacting the monomers to produce a structural acrylic polymer for crosslinking;
A step of producing an acrylic polymer for uncrosslinked structure by reacting an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms of alkyl; and the above-mentioned acrylic polymer for crosslinked structure and uncrosslinked structure A method for producing an acrylic pressure-sensitive adhesive composition for polarizing plates according to the present invention, or an alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms and many A first step of producing an acrylic polymer containing a crosslinking structure by reacting a functional crosslinking agent and a vinyl-based and / or acrylic-based crosslinking monomer having a crosslinkable carboxyl group or hydroxyl group; and In the presence of an acrylic polymer for a crosslinked structure obtained in one step, an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms is further reacted to form an uncrosslinked product. A process for producing a polarizing plate acrylic pressure-sensitive adhesive composition according to the present invention comprising: second providing a granulation.
上記のような本発明に係るアクリル系粘着剤組成物の製造方法は下記によって具体化される。 The manufacturing method of the acrylic adhesive composition according to the present invention as described above is embodied as follows.
上記アクリル系粘着剤は、本発明に好適な架橋構造を持つために、別途の２つのアクリル系重合体、即ち、架橋構造を形成する重合体と未架橋構造を形成する重合体を製造した後、一定の重量比率で混合するか、または反応器中で順次に２つのアクリル系重合体を製造した後、多官能架橋剤と反応させて製造することができる。上記架橋構造を形成する重合体は、架橋可能官能基を含有する必要がある。架橋官能基量が過度に多くなれば、架橋構造が緻密になり過ぎ、未架橋構造を形成する重合体が架橋構造間に浸透することが非常に難しくなり、耐久信頼性が大きく低下され、本発明のゲル分率と膨脹比を達成することができない。逆に、架橋構造を形成する重合体内に架橋官能基が一定含量以下の場合には、架橋構造が緩くなり過ぎ、未架橋構造を形成する重合体が架橋構造間への浸透は容易になるが、粘着剤に力が加えられた場合、未架橋構造形成重合体が架橋構造から容易に離脱され、耐久信頼性が低下される。一方、架橋構造を形成する重合体と未架橋構造を形成する重合体との組成が大きく異なれば、２つの重合体間の完全な混合が難しいため、可能なかぎり類似の組成が好ましい。また、２つ重合体の混合の側面で架橋官能基は、カルボキシル基より水酸基が有利である。未架橋構造を形成する重合体は架橋官能基（水酸基またはカルボキシル基）を含有しないことが好ましいが、架橋官能基を有していてもよい。 After the acrylic pressure-sensitive adhesive has a crosslinked structure suitable for the present invention, two separate acrylic polymers, that is, a polymer that forms a crosslinked structure and a polymer that forms an uncrosslinked structure are manufactured. The two acrylic polymers can be mixed in a constant weight ratio or sequentially prepared in a reactor and then reacted with a polyfunctional crosslinking agent. The polymer that forms the crosslinked structure needs to contain a crosslinkable functional group. If the amount of the cross-linking functional group is excessively large, the cross-linked structure becomes too dense, and it becomes very difficult for the polymer forming the uncross-linked structure to penetrate between the cross-linked structures, and the durability reliability is greatly reduced. The gel fraction and expansion ratio of the invention cannot be achieved. On the other hand, when the cross-linking functional group has a certain content or less in the polymer forming the cross-linked structure, the cross-linked structure becomes too loose, and the polymer forming the uncross-linked structure can easily penetrate between the cross-linked structures. When a force is applied to the pressure-sensitive adhesive, the uncrosslinked structure-forming polymer is easily detached from the crosslinked structure, and durability reliability is lowered. On the other hand, if the composition of the polymer that forms a crosslinked structure and the polymer that forms an uncrosslinked structure differ greatly, it is difficult to completely mix the two polymers. Further, in terms of mixing the two polymers, the cross-linking functional group is preferably a hydroxyl group rather than a carboxyl group. The polymer forming the uncrosslinked structure preferably does not contain a crosslinking functional group (hydroxyl group or carboxyl group), but may have a crosslinking functional group.
上記アクリル系共重合体の製造方法は、特に限定されず、溶液重合法、光重合法、バルク重合法、サスペンション重合法またはエマルジョン重合法によって製造することができる。好ましくは、アクリル系共重合体は溶液重合法を使用して製造し、重合温度は５０℃〜１４０℃が好ましく、単量体が均一に混合された状態で開始剤を添加することが好ましい。 The method for producing the acrylic copolymer is not particularly limited, and can be produced by a solution polymerization method, a photopolymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method. Preferably, the acrylic copolymer is produced using a solution polymerization method, the polymerization temperature is preferably 50 ° C. to 140 ° C., and the initiator is preferably added in a state where the monomers are uniformly mixed.
このような重合開始剤は、アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリルなどのアゾ系重合開始剤と過酸化ベンゾイル、過酸化アセチルなどの過酸化物を単独または混合して使用することが可能である。 As such a polymerization initiator, an azo polymerization initiator such as azobisisobutyronitrile or azobiscyclohexanecarbonitrile and a peroxide such as benzoyl peroxide or acetyl peroxide may be used alone or in combination. Is possible.
本発明の粘着剤組成物の製造方法は、特に限定されず、上記したアクリル系共重合体と架橋剤を常法で混合して得ることができる。 The method for producing the pressure-sensitive adhesive composition of the present invention is not particularly limited, and can be obtained by mixing the above-mentioned acrylic copolymer and a crosslinking agent by a conventional method.
この時、多官能性架橋剤は粘着層の形成のために実施する配合過程で、均一なコーティングのため、架橋剤の官能基架橋反応が起きるべきではない。上記コーティング作業が終了し、乾燥及び熟成過程を経ると、架橋構造が形成され、弾性があり、且つ凝集力の強い粘着層を得ることができる。 At this time, the functional cross-linking reaction of the cross-linking agent should not occur for the uniform coating in the compounding process performed for forming the adhesive layer. When the coating operation is completed and a drying and aging process is performed, a crosslinked structure is formed, and an adhesive layer having elasticity and strong cohesion can be obtained.
また、本発明は上記アクリル系粘着剤組成物を偏光フィルムの粘着層として含む偏光板を提供する。 Moreover, this invention provides the polarizing plate which contains the said acrylic adhesive composition as an adhesion layer of a polarizing film.
本発明の偏光板は、偏光フィルムの一方または両方面に上記粘着剤組成物から形成される粘着剤層を含み、偏光板を構成する偏光フィルムまたは偏光素子は特に制限されない。 The polarizing plate of this invention contains the adhesive layer formed from the said adhesive composition in the one or both surfaces of a polarizing film, and the polarizing film or polarizing element which comprises a polarizing plate in particular is not restrict | limited.
例えば、好ましい偏光フィルムは、ポリビニルアルコール系樹脂フィルムにヨウ素または二色性染料などの偏光成分を含有させ、延伸することによって得られた。これらの偏光フィルムの膜厚は特に制限されないので、通常的な膜厚を形成することができる。この時、上記ポリビニルアルコール系樹脂はポリビニルアルコール、ポリビニルホルマール、ポリビニルアセタール及びエチレン、酢酸ビニル共重合体のけん化物などが用いられる。 For example, a preferable polarizing film was obtained by allowing a polyvinyl alcohol-based resin film to contain a polarizing component such as iodine or a dichroic dye and stretching it. Since the film thickness of these polarizing films is not particularly limited, a normal film thickness can be formed. At this time, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, saponified ethylene, and vinyl acetate copolymer are used as the polyvinyl alcohol resin.
上記偏光フィルムの両面には、トリアセチルセルロースなどのセルロース系フィルム 、ポリカーボネートフィルム、ポリエチレンテレフタラートなどのポリエステル系フィルム、ポリエーテルスルホン系フィルム、ポリエチレン、ポリプロフィレン、シクロ系やノルボルネン構造を持つポリオレフィン系、エチレンプロピレン共重合体のようなポリオレフィン系などの保護フィルムが積層された多層フィルムなどを形成することができる。この時、これらの保護フィルムの膜厚は特に制限されず、通常的な膜厚を形成することができる。 On both sides of the polarizing film, a cellulose film such as triacetyl cellulose, a polycarbonate film, a polyester film such as polyethylene terephthalate, a polyethersulfone film, polyethylene, a polypropylene, a polyolefin film having a cyclo or norbornene structure, A multilayer film in which a protective film such as a polyolefin-based film such as an ethylene-propylene copolymer is laminated can be formed. At this time, the film thickness of these protective films is not particularly limited, and a normal film thickness can be formed.
本発明で偏光フィルムに粘着剤層を形成する方法は、特に制限がなく、この偏光フィルム表面に直接バーコーターなどを使用して上記粘着剤を塗布し、乾燥する方法、または上記粘着剤をまず剥離性基材表面に塗布し、乾燥した後、この剥離性基材表面に形成された粘着剤層を偏光フィルム表面に転写し、次いで熟成させる方法を用いることができる。 The method for forming the pressure-sensitive adhesive layer on the polarizing film in the present invention is not particularly limited, and the pressure-sensitive adhesive is directly applied to the surface of the polarizing film using a bar coater and dried. After applying to the surface of the peelable substrate and drying, the pressure-sensitive adhesive layer formed on the surface of the peelable substrate can be transferred to the surface of the polarizing film and then aged.
また、本発明の偏光板には保護層、反射層、防眩層、位相差板、広視野角補償フィルム、及び輝度向上フィルムなどの追加機能を提供する層が１種以上積層されていてもよい。 The polarizing plate of the present invention may be laminated with one or more layers providing additional functions such as a protective layer, a reflective layer, an antiglare layer, a retardation plate, a wide viewing angle compensation film, and a brightness enhancement film. Good.
本発明の粘着剤が適用された偏光板は、通常的な液晶表示装置に適用可能であり、その液晶パネルの種類は特に限定されない。好ましくは、本発明は上記粘着偏光板を液晶セルの一面または両面に接合した液晶パネルを含む液晶表示装置を構成することができる。 The polarizing plate to which the pressure-sensitive adhesive of the present invention is applied can be applied to an ordinary liquid crystal display device, and the type of the liquid crystal panel is not particularly limited. Preferably, the present invention can constitute a liquid crystal display device including a liquid crystal panel in which the above-mentioned adhesive polarizing plate is bonded to one surface or both surfaces of a liquid crystal cell.
以下、実施例及び比較例を通じて本発明をさらに詳細に説明するが、これは発明の具体的理解を助けるためにだけであって、本発明の範囲がこれらの実施例によって何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, this is only for the purpose of helping a specific understanding of the invention, and the scope of the present invention is not limited by these examples. Absent.
〔製造例１：アクリル系共重合体（Ａ−１）の製造〕
窒素ガスが還流及び温度調節が容易な冷却装置を備えた１Ｌ反応器に、下記表１に示した組成のように、ｎ−ブチルアクリレート（ＢＡ）９８重量部、ヒドロキシメタクリレート２．０重量部で構成される単量体の混合物を投入した。そして、溶剤として、エチルアセテート（ＥＡｃ）１２０重量部を投入した。酸素を除去するために、窒素ガスを６０分間パージ（purging）した後、温度は６０℃に保持し、反応開始剤であるアゾビスイソブチロニトリル（ＡＩＢＮ）０．０３重量部を投入し、８時間、反応した。反応後、エチルアセテート（ＥＡｃ）で希釈し、固形分１５重量％、重量平均分子量が１，６００，０００、分子量分布４．９のアクリル系共重合体（Ａ−１）を製造した。
[Production Example 1: Production of acrylic copolymer (A-1)]
In a 1 L reactor equipped with a cooling device in which nitrogen gas is easily refluxed and temperature controlled, as shown in Table 1 below, n-butyl acrylate (BA) 98 parts by weight and hydroxy methacrylate 2.0 parts by weight A mixture of composed monomers was charged. Then, 120 parts by weight of ethyl acetate (EAc) was added as a solvent. In order to remove oxygen, after purging with nitrogen gas for 60 minutes, the temperature was maintained at 60 ° C., and 0.03 part by weight of azobisisobutyronitrile (AIBN) as a reaction initiator was added, Reacted for 8 hours. After the reaction, it was diluted with ethyl acetate (EAc) to produce an acrylic copolymer (A-1) having a solid content of 15% by weight, a weight average molecular weight of 1,600,000 and a molecular weight distribution of 4.9.
〔製造例２、３：アクリル系共重合体Ａ−２、Ａ−３の製造〕
上記製造例１で、下記表１のように、 高分子量アクリル系共重合体（Ａ−１）の組成を基準に、各成分の一部を添加しないか、部分添加して高分子量アクリル系共重合体（Ａ−２とＡ−３）を製造した。これに対する結果値は表１に示した。
[Production Examples 2, 3: Production of acrylic copolymers A-2, A-3]
In Production Example 1, as shown in Table 1 below, on the basis of the composition of the high molecular weight acrylic copolymer (A-1), either a part of each component is not added or a partial addition is performed and the high molecular weight acrylic copolymer is added. Polymers (A-2 and A-3) were produced. The resulting values are shown in Table 1.
〔製造例４、５、６：アクリル系共重合体（Ｂ−１、Ｂ−２、Ｂ−３）の製造〕
上記製造例１で、下記表１のように、高分子量アクリル系共重合体（Ａ−１）の組成を基準に、各成分の一部を添加しないか、部分添加して高分子量アクリル系共重合体（Ｂ−１、Ｂ−２、Ｂ−３）を製造した。その結果は表１に示した。
[Production Examples 4, 5, 6: Production of acrylic copolymers (B-1, B-2, B-3)]
In Production Example 1, as shown in Table 1 below, on the basis of the composition of the high molecular weight acrylic copolymer (A-1), either a part of each component is not added, or a part of the high molecular weight acrylic copolymer is added. Polymers (B-1, B-2, B-3) were produced. The results are shown in Table 1.
〔製造例７：低分子量体アクリル系共重合体（Ｌ−１）の製造〕
上記製造例１で、下記表１のように、 高分子量アクリル系共重合体（Ａ−１）の組成を基準に、各成分の一部を添加しないか、部分添加して低分子量アクリル系共重合体（Ｌ−１）を製造した。これに対する結果値は、表１に示した。
[Production Example 7: Production of low molecular weight acrylic copolymer (L-1)]
In the production example 1, as shown in Table 1 below, on the basis of the composition of the high molecular weight acrylic copolymer (A-1), either a part of each component is not added, or a low molecular weight acrylic copolymer is partially added. A polymer (L-1) was produced. The resulting values are shown in Table 1.
〔製造例８、９：アクリル系共重合体（Ｉ−１、Ｉ−２）の製造〕
上記下記表２のように、第１段階反応で水酸基含有単量体が含まれる組成で、製造例１のような条件で、水酸基含有高分子量アクリル系共重合体を、まず製造した後、第１段階で製造した高分子の存在下で、第２段階組成で表２の組成のように投入し、同じ組件で反応した後、最終高分子量アクリル重合体を得た。
[Production Examples 8 and 9: Production of acrylic copolymer (I-1, I-2)]
As shown in Table 2 above, a hydroxyl group-containing high molecular weight acrylic copolymer was first produced under the conditions as in Production Example 1 with a composition containing a hydroxyl group-containing monomer in the first stage reaction. In the presence of the polymer produced in one stage, the second stage composition was charged as shown in Table 2 and reacted in the same composition to obtain the final high molecular weight acrylic polymer.
〔実施例１〕
＜配合＞
上記の準備段階で得られた高分子量アクリル系共重合体（Ａ−１）固形分２０重量部に対して高分子量アクリル系共重合体（Ｂ−１）を固形分８０重量部になるように混合した後、ここに、多官能性架橋剤としてイソシアネート系トリメチロールプロパンのトリレンジイソシアネート付加物（ＴＤＩ−１）０．１重量部を投入し、コーティング性を考慮して適正の濃度で希釈し、均一に混合した後、離型紙にコーティングして乾燥した後、３０ミクロンの均一な粘着層を得た。
＜合板過程＞
上記で製造された粘着層を、膜厚１８５ミクロンのヨード系偏光板に粘着加工した。得られた偏光板を適切なサイズで切断し、評価に用いた。上記粘着剤が適用された偏光板に関し、以下の評価の結果を下記の表３ａに示した。
[Example 1]
<Combination>
The high molecular weight acrylic copolymer (B-1) is 80 parts by weight of the solid content with respect to 20 parts by weight of the solid content of the high molecular weight acrylic copolymer (A-1) obtained in the preparation step. After mixing, 0.1 part by weight of an isocyanate-based trimethylolpropane tolylene diisocyanate adduct (TDI-1) is added as a polyfunctional crosslinking agent, and diluted with an appropriate concentration in consideration of coating properties. After mixing uniformly, the release paper was coated and dried, and a uniform adhesive layer of 30 microns was obtained.
<Plywood process>
The pressure-sensitive adhesive layer produced above was subjected to pressure-sensitive adhesive processing on an iodo-type polarizing plate having a film thickness of 185 microns. The obtained polarizing plate was cut at an appropriate size and used for evaluation. The following evaluation results are shown in Table 3a for the polarizing plate to which the pressure-sensitive adhesive was applied.
〔実施例２〜７〕
下記表３ａの配合比のように実施例１の配合を基準に一部を配合しないか、部分配合することによって上記実施例１と同様の方法でアクリル系共重合体を配合及び合板過程を実施した。以後、実施例１と同様の方法で耐久信頼性及び光透過均一性を評価し、その結果を表３ａに示した。
[Examples 2 to 7]
As shown in Table 3a below, the acrylic copolymer was blended and the plywood process was carried out in the same manner as in Example 1 above by not blending a part of the blend of Example 1 or by partially blending. did. Thereafter, durability reliability and light transmission uniformity were evaluated in the same manner as in Example 1, and the results are shown in Table 3a.
〔比較例１〜６〕
表３ｂで示されるように、下記表２の配合比のように実施例１の配合を基準に、一部を配合しないか、部分配合することによって上記実施例１と同様の方法でアクリル系共重合体を配合及び合板過程を実施した。以後、実施例１と同様の方法で耐久信頼性及び光透過均一性を評価し、その結果を表３ｂに示した。
[Comparative Examples 1-6]
As shown in Table 3b, the acrylic co-polymer is mixed in the same manner as in Example 1 above by not blending or partially blending with reference to the blending ratio of Example 1 as shown in Table 2 below. The polymer was blended and the plywood process was performed. Thereafter, durability reliability and light transmission uniformity were evaluated in the same manner as in Example 1, and the results are shown in Table 3b.
＜偏光板特性テスト＞
Ａ．耐久信頼性
上記実施例１で製造された粘着剤がコーディングされた偏光板（９０ｍｍ×１７０ｍｍ）をガラス基板（１１０ｍｍ×１９０ｍｍ×０．７ｍｍ）の両面に光学吸収軸がクロスされた状態で接着した。この時、加えられた圧力は約５ｋｇ／ｃｍ２であり、気泡や異物が生じないようにクリーンルーム作業を行った。この試片を、耐湿熱特性を把握するために、６０℃の温度及び９０％の相対湿度条件下で、１，０００時間放置した後、気泡や剥離の発生の有無を観察した。耐熱特性は８０℃の温度で１０００時間放置した後、気泡や剥離の発生の有無を観察した。試験片の状態を評価する直前に、常温で２４時間放置した後、実施した。また、上記で製造された粘着偏光板を５ケ月以上放置後、上記の方法で信頼性を評価した。信頼性に対する評価基準は次の通りである。
○：気泡や剥離現象無し
△：気泡や剥離現象若干発生
×：気泡や剥離現象多量発生
<Polarizing plate property test>
A. Durability Reliability The polarizing plate (90 mm × 170 mm) coded with the adhesive produced in Example 1 was bonded to both surfaces of the glass substrate (110 mm × 190 mm × 0.7 mm) with the optical absorption axis crossed. . At this time, the applied pressure was about 5 kg / cm 2 , and a clean room operation was performed so as not to generate bubbles and foreign matters. In order to grasp the moisture and heat resistance characteristics of this specimen, the specimen was allowed to stand for 1,000 hours at a temperature of 60 ° C. and a relative humidity of 90%, and then the presence or absence of bubbles or peeling was observed. As for the heat resistance, after leaving for 1000 hours at a temperature of 80 ° C., the presence or absence of bubbles and peeling was observed. Immediately before evaluating the state of the test piece, the test piece was left at room temperature for 24 hours, and then the test was performed. Moreover, after leaving the adhesive polarizing plate manufactured above for 5 months or more, reliability was evaluated by said method. The evaluation criteria for reliability are as follows.
○: No bubbles or exfoliation phenomenon △: Some bubbles or exfoliation phenomenon occurred ×: Large amount of bubbles or exfoliation
Ｂ．光透過均一性（光漏れ）
上記と同じ試片を用いて、光透過度の均一性を調べるために、バックライトを利用して暗室で光が漏れる部分があるかを観察した。光透過均一性を試験する方法としてはコーティングされた偏光板（２００ｍｍ×２００ｍｍ）をガラス基板（２１０ｍｍ×２１０ｍｍ×０．７ｍｍ）に９０度で交差して両面に接着し、観察する方法を採択した。光透過性の均一性は次のような基準で評価した。
◎：光透過性の不均一現象が肉眼で判断し難い
○：光透過性の不均一現象が若干ある
△：光透過性の不均一現象が多少ある
×：光透過性の不均一現象が多量ある
B. Light transmission uniformity (light leakage)
Using the same specimen as described above, in order to examine the uniformity of the light transmittance, the backlight was used to observe whether there was a portion where light leaked in the dark room. As a method for testing the light transmission uniformity, a method was adopted in which a coated polarizing plate (200 mm × 200 mm) was crossed at 90 degrees on a glass substrate (210 mm × 210 mm × 0.7 mm), adhered to both surfaces, and observed. . The uniformity of light transmission was evaluated according to the following criteria.
◎: Light transmission non-uniformity is difficult to judge with the naked eye ○: Light transmission non-uniformity is slightly △: Light transmission non-uniformity is somewhat ×: Light transmission non-uniformity is large is there
Ｃ．粘着剤ピット欠陥（貯蔵弾性率）
粘着剤ピット不良は、粘着剤の弾性率（貯蔵弾性率）が高いほど少ない。粘着剤の弾性率はレオメトリックス（Rheometrics）社のＲＭＳ−８００を利用して測定した。直径が８ｍｍの平行板フィクスチャー（Fixture）を用いて、温度３０℃で、粘着剤の膜厚１ｍｍ、変形率１０％、周波数１ｒａｄ／ｓｅｃ条件下で、貯蔵弾性率（storage modulus）を測定して粘着剤の弾性率を測定しており、測定された貯蔵弾性率を通じて下記の通りに判断した。
５点：粘着剤ピット不良が大変少ない（貯蔵弾性率＞１．８×１０４Ｐａ）
４点：粘着剤ピット不良が少しある（１．４×１０４Ｐａ＜貯蔵弾性率＜１．７×１０４Ｐａ）
３点：粘着剤ピット不良が多少ある（１．０×１０４Ｐａ＜貯蔵弾性率＜１．３×１０４Ｐａ）
２点：粘着剤ピット不良がたくさんある（０．８×１０４Ｐａ＜貯蔵弾性率＜１．０×１０４Ｐａ）
１点：粘着剤ピット不良が非常に多い（０．８×１０４Ｐａ＜貯蔵弾性率）
C. Adhesive pit defect (storage modulus)
The adhesive pit defect is smaller as the elastic modulus (storage elastic modulus) of the adhesive is higher. The elastic modulus of the adhesive was measured using RMS-800 manufactured by Rheometrics. Using a parallel plate fixture with a diameter of 8 mm, the storage modulus was measured at a temperature of 30 ° C. under the conditions of an adhesive film thickness of 1 mm, a deformation rate of 10%, and a frequency of 1 rad / sec. The elastic modulus of the pressure-sensitive adhesive was measured, and was judged as follows through the measured storage elastic modulus.
5 points: Very little adhesive pit failure (storage modulus> 1.8 × 10 4 Pa)
4 points: There is a little defective adhesive pit (1.4 × 10 4 Pa <storage elastic modulus <1.7 × 10 4 Pa)
3 points: There are some adhesive pit defects (1.0 × 10 4 Pa <storage modulus <1.3 × 10 4 Pa)
2 points: There are many adhesive pit defects (0.8 × 10 4 Pa <storage elastic modulus <1.0 × 10 4 Pa)
1 point: Very many adhesive pit defects (0.8 × 10 4 Pa <storage elastic modulus)
Ｄ．粘着剤はみ出しの測定
トムソン（Thompson）カッターを利用して上記合板後の偏光板を切断し、各偏光板の切断面を顕微鏡で観察し、次ぎのような基準で評価した。
３点：切断面の粘着剤のはみ出し程度が良好（０．２ｍｍ未満）
２点：切断面の粘着剤のはみ出し程度が多少不良（０．２〜０．５ｍｍ）
１点：切断面の粘着剤のはみ出し程度が激しい（０．５ｍｍ以上）
D. Measurement of protrusion of adhesive The polarizing plate after the plywood was cut using a Thompson cutter, the cut surface of each polarizing plate was observed with a microscope, and evaluated according to the following criteria.
3 points: Good extent of adhesive on the cut surface (less than 0.2 mm)
2 points: The degree of protrusion of the adhesive on the cut surface is somewhat poor (0.2 to 0.5 mm)
1 point: Excessive extent of adhesive on the cut surface (0.5 mm or more)
Ｅ．ゲル分率の測定
上記配合過程で乾燥された粘着剤を約１０日間、恒温恒湿室（２３℃、６０％ＲＨ）に放置した後、約０．３ｇの粘着剤を＃２００ステンレス金網に入れて１００ｍＬのエチルアセテートに浸漬し、常温、暗室で３日間保管後、不溶解分を分離後、不溶解分を７０℃オーブンで４時間、乾燥後、質量を測定した。
E. Measurement of gel fraction The pressure-sensitive adhesive dried in the above blending process is left in a constant temperature and humidity chamber (23 ° C., 60% RH) for about 10 days, and then about 0.3 g of the pressure-sensitive adhesive is put in a # 200 stainless steel wire mesh. The sample was immersed in 100 mL of ethyl acetate, stored at room temperature in a dark room for 3 days, the insoluble matter was separated, the insoluble matter was dried in a 70 ° C. oven for 4 hours, and the mass was measured.
Ｆ．膨脹比
上記ゲル含量測定時、不溶解分を分離した後、不溶解分と不溶解分に含まれていた（膨脹された）溶剤の重量を測定し、乾燥後、不溶解分の質量で割り、膨脹比を求めた。
F. Expansion ratio When measuring the gel content above, after separating the insoluble matter, weigh the insoluble matter and the solvent (expanded) contained in the insoluble matter, and after drying, divide by the mass of the insoluble matter. The expansion ratio was determined.
上記表１及び２で、略語は次の通りに定義される。
ｎ−ＢＡ：ｎ−ブチルアクリレート、
ＥＨＡ：エチルヘキシルアクリレート、
２−ＨＥＭＡ：２−ヒドロキシエチルメタアクリレート、
ＡＩＢＮ：アゾビスイソブチロニトリル、
ＥＡｃ：エチルアセテート。
In Tables 1 and 2 above, abbreviations are defined as follows.
n-BA: n-butyl acrylate,
EHA: ethylhexyl acrylate,
2-HEMA: 2-hydroxyethyl methacrylate,
AIBN: azobisisobutyronitrile,
EAc: ethyl acetate.
上記表３ａの結果より、本発明の実施例１〜７の場合、耐久信頼性、光漏れ特性に優れており、また粘着剤生産時、作業性と関連した粘着剤はみ出し、粘着剤ピット不良が少ない。反面、比較例１の場合、膨脹比が非常に高く、架橋構造が緩すぎて耐久性が不足しており、比較例２の場合には、ゲル含量が高く、膨脹比が低すぎて架橋構造が緻密過ぎ、応力緩和特性が不足して光漏れが改善されない場合である。比較例３の場合は、ゾルの分子量が低すぎて耐久性が不足した場合であり、比較例４は従来の技術である低分子量体を混合し、光漏れを改善した場合である。この場合には、モジュラスが急激に減少し、偏光板作業性が大きく劣る。比較例５の場合は、従来の技術のように多官能性架橋剤量を少量添加し、低いゲル含量を調節した場合や架橋構造が緩く、膨脹比が非常に大きく、これにより耐久性が大きく不足する場合であり、比較例６の場合は、一般的なゲル含量調節条件で粘着剤の応力緩和が大きく不足する場合である。 From the results of Table 3a above, in the case of Examples 1 to 7 of the present invention, the durability reliability and light leakage characteristics are excellent, and during the production of the pressure-sensitive adhesive, the pressure-sensitive adhesive protrudes and the pressure-sensitive adhesive pit is poor. Few. On the other hand, in the case of Comparative Example 1, the expansion ratio is very high and the crosslinked structure is too loose and the durability is insufficient, and in the case of Comparative Example 2, the gel content is high and the expansion ratio is too low to form a crosslinked structure. This is a case where the light leakage is not improved due to insufficient stress relaxation characteristics. The case of Comparative Example 3 is a case where the molecular weight of the sol is too low and the durability is insufficient, and the Comparative Example 4 is a case where light leakage is improved by mixing a low molecular weight body which is a conventional technique. In this case, the modulus rapidly decreases and the polarizing plate workability is greatly inferior. In the case of Comparative Example 5, when a small amount of polyfunctional crosslinking agent is added as in the prior art and the low gel content is adjusted, or the crosslinking structure is loose, the expansion ratio is very large, thereby increasing the durability. In the case of Comparative Example 6, the stress relaxation of the pressure-sensitive adhesive is largely insufficient under the general gel content adjustment conditions.
上記のように、本発明は粘着耐久性などの主要特性を変化させることなく、高温・多湿条件下で長期間使用時、偏光板の収縮により発生される応力を緩和させ、光漏れ改善に効果があり、最終粘着剤のモジュラスの高い偏光板用アクリル系粘着剤組成物を提供することができる。従って、本発明は上記粘着剤組成物を液晶表示装置の偏光板に適用し、長時間使用しても応力集中による光漏れ現象を防止することができ、高いモジュラスによって優れた作業性を得ることができる。 As described above, the present invention reduces the stress generated by the contraction of the polarizing plate when used for a long time under high temperature and high humidity conditions without changing main properties such as adhesion durability, and is effective in improving light leakage. There can be provided an acrylic pressure-sensitive adhesive composition for polarizing plates having a high modulus of the final pressure-sensitive adhesive. Therefore, the present invention applies the above-mentioned pressure-sensitive adhesive composition to a polarizing plate of a liquid crystal display device, can prevent light leakage due to stress concentration even when used for a long time, and obtains excellent workability with a high modulus. Can do.
Claims (17)
下記数式（１）で示されるゲル分率が１０〜５５％であり、
下記数式（２）で示される膨脹比が３０〜１１０であり、
粘着剤からエチルアセテートで溶出されたゾルの重量平均分子量が８００，０００以上であり、及び
分子量分布が２．０〜７．０であることを特徴とする偏光板用アクリル系粘着剤組成物：
ゲル分率（％）＝Ｂ／Ａ×１００ （１）
膨脹比＝Ｃ／Ｂ （２）
（上記式で、Ａはアクリル系粘着剤組成物の質量を示し、
Ｂは常温で、エチルアセテートに４８時間、浸漬後のアクリル系粘着剤組成物の不溶解分の乾燥質量を示し、
Ｃは常温で、エチルアセテートに４８時間、浸漬後のエチルアセテートによって膨脹された不溶解分の質量（アクリル粘着剤不溶解分の質量＋浸透溶剤の質量）を示す。）。 Including a (meth) acrylic copolymer containing an alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms of alkyl,
The gel fraction represented by the following formula (1) is 10 to 55%,
The expansion ratio shown by the following mathematical formula (2) is 30 to 110,
Acrylic pressure-sensitive adhesive composition for polarizing plate, characterized in that the sol eluted with ethyl acetate from the pressure-sensitive adhesive has a weight average molecular weight of 800,000 or more and a molecular weight distribution of 2.0 to 7.0:
Gel fraction (%) = B / A × 100 (1)
Expansion ratio = C / B (2)
(In the above formula, A represents the mass of the acrylic pressure-sensitive adhesive composition,
B shows the dry mass of the insoluble content of the acrylic pressure-sensitive adhesive composition after being immersed in ethyl acetate for 48 hours at room temperature,
C represents the mass of the insoluble matter expanded by the ethyl acetate after being immersed in ethyl acetate for 48 hours at room temperature (the mass of the acrylic pressure-sensitive adhesive insoluble + the mass of the penetrating solvent). ).
アルキル基が２〜１４のアルキル（メタ）アクリル酸エステル単量体８０〜９９．８重量部；
多官能性架橋剤０．０１〜１０重量部；及び
上記多官能性架橋剤と架橋可能なカルボキシル基又は水酸基を含むビニル系及び／又はアクリル系０．０１〜５重量部を含むことを特徴とする請求項１に記載の偏光板用アクリル系粘着剤組成物。 (Meth) acrylic copolymer
80 to 99.8 parts by weight of an alkyl (meth) acrylate monomer having an alkyl group of 2 to 14;
0.01 to 10 parts by weight of a polyfunctional crosslinking agent; and 0.01 to 5 parts by weight of a vinyl and / or acrylic series containing a carboxyl group or a hydroxyl group capable of crosslinking with the polyfunctional crosslinking agent. The acrylic pressure-sensitive adhesive composition for polarizing plates according to claim 1.
アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体を反応させて未架橋構造用アクリル系重合体を製造する段階；及び
上記架橋構造用アクリル系重合体及び未架橋構造用アクリル系重合体を混合する段階；
を含むことを特徴とする請求項１に係る偏光板用アクリル系粘着剤組成物の製造方法。 An alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms of alkyl and a polyfunctional crosslinking agent are reacted with a vinyl-based and / or acrylic-based crosslinking monomer containing a crosslinkable carboxyl group or hydroxyl group. Producing a structural acrylic polymer for cross-linking;
A step of producing an acrylic polymer for uncrosslinked structure by reacting an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms of alkyl; and the above-mentioned acrylic polymer for crosslinked structure and uncrosslinked structure Mixing an acrylic polymer;
The manufacturing method of the acrylic adhesive composition for polarizing plates concerning Claim 1 characterized by the above-mentioned.
上記第１段階で製造された架橋構造用アクリル系重合体の存在下で、アルキルの炭素数が１〜１２のアルキル（メタ）アクリル酸エステル単量体を、さらに反応させて未架橋用構造を提供する第２段階；
を含むことを特徴とする第１項に係る偏光板用アクリル系粘着剤組成物の製造方法。 A structure for crosslinking is obtained by reacting an alkyl (meth) acrylic acid ester monomer having 1 to 12 carbon atoms and a polyfunctional crosslinking agent with a vinyl group and / or an acrylic group containing a crosslinkable carboxyl group or hydroxyl group. An alkyl (meth) acrylic acid ester having 1 to 12 carbon atoms in the presence of the acrylic polymer for crosslinked structure produced in the first step; A second stage in which the monomer is further reacted to provide an uncrosslinked structure;
The manufacturing method of the acrylic adhesive composition for polarizing plates which concerns on 1st term | claim characterized by the above-mentioned.
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| KR10-2005-0082331 | 2005-09-05 | ||
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| KR1020060066537A KR100784995B1 (en) | 2005-09-05 | 2006-07-14 | Acrylic Pressure-Sensitive Adhesive Composition for the Polarizing Film |
| KR10-2006-0066537 | 2006-07-14 | ||
| PCT/KR2006/003404 WO2007029936A1 (en) | 2005-09-05 | 2006-08-29 | Acrylic pressure-sensitive adhesive composition for polarizing film |
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0312471A (en) * | 1989-06-10 | 1991-01-21 | Nitto Denko Corp | Pressure-adhesive layer and polarizing plate |
| JPH04178402A (en) * | 1990-11-09 | 1992-06-25 | Asahi Chem Ind Co Ltd | Production of strongly tacky emulsion type pressure-sensitive adhesive |
| JPH09145925A (en) * | 1995-09-22 | 1997-06-06 | Sekisui Chem Co Ltd | Self-adhesive polarizing plate |
| JP2002047468A (en) * | 2000-08-02 | 2002-02-12 | Saiden Chemical Industry Co Ltd | Self-adhesive-coated polarizing plate and self-adhesive composition used for the same |
| JP2002105415A (en) * | 2000-09-29 | 2002-04-10 | Nippon Shokubai Co Ltd | Adhesive product and pressure-sensitive adhesive |
| JP2002241707A (en) * | 2001-02-19 | 2002-08-28 | Soken Chem & Eng Co Ltd | Method for producing pressure-sensitive adhesive sheet for optical member |
| JP2002341141A (en) * | 2001-05-15 | 2002-11-27 | Nitto Denko Corp | Adhesion type optical film and liquid crystal display device |
| JP2003034781A (en) * | 2001-05-15 | 2003-02-07 | Soken Chem & Eng Co Ltd | Pressure sensitive adhesive for optical member and optical member provided with the adhesive |
| JP2003049143A (en) * | 2001-05-31 | 2003-02-21 | Soken Chem & Eng Co Ltd | Adhesive for optical film and optical film using the adhesive |
| JP2003064336A (en) * | 2001-08-23 | 2003-03-05 | Nitto Denko Corp | Adhesive composition for medical application and adhesive tape or sheet using the same composition |
| JP2004059893A (en) * | 2002-06-04 | 2004-02-26 | Sekisui Chem Co Ltd | Acrylic adhesive composition and adhesive tape |
| JP2004091500A (en) * | 2002-08-29 | 2004-03-25 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive for optical member and optical member using the same pressure-sensitive adhesive |
| JP2005179467A (en) * | 2003-12-18 | 2005-07-07 | Nitto Denko Corp | Adhesive composition for optical film, adhesive layer for optical film, adherent type optical film and image display device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100446664B1 (en) * | 2002-02-20 | 2004-09-04 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive composition for the polarizing firm |
| US7285313B2 (en) * | 2004-01-20 | 2007-10-23 | Lg Chem Ltd. | Acrylic pressure-sensitive adhesive composition for polarizing film |
| KR100668943B1 (en) * | 2004-04-23 | 2007-01-12 | 주식회사 엘지화학 | Acrylic Pressure-Sensitive Adhesive Composition for the Polarizing Film |
| JP3916638B2 (en) * | 2004-12-02 | 2007-05-16 | 日東電工株式会社 | Adhesive optical film and image display device |
-
2006
- 2006-07-14 KR KR1020060066537A patent/KR100784995B1/en active IP Right Grant
- 2006-08-29 CN CN2006800325026A patent/CN101258214B/en active Active
- 2006-08-29 JP JP2008528937A patent/JP5128478B2/en active Active
- 2006-09-01 TW TW095132311A patent/TWI335932B/en active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0312471A (en) * | 1989-06-10 | 1991-01-21 | Nitto Denko Corp | Pressure-adhesive layer and polarizing plate |
| JPH04178402A (en) * | 1990-11-09 | 1992-06-25 | Asahi Chem Ind Co Ltd | Production of strongly tacky emulsion type pressure-sensitive adhesive |
| JPH09145925A (en) * | 1995-09-22 | 1997-06-06 | Sekisui Chem Co Ltd | Self-adhesive polarizing plate |
| JP2002047468A (en) * | 2000-08-02 | 2002-02-12 | Saiden Chemical Industry Co Ltd | Self-adhesive-coated polarizing plate and self-adhesive composition used for the same |
| JP2002105415A (en) * | 2000-09-29 | 2002-04-10 | Nippon Shokubai Co Ltd | Adhesive product and pressure-sensitive adhesive |
| JP2002241707A (en) * | 2001-02-19 | 2002-08-28 | Soken Chem & Eng Co Ltd | Method for producing pressure-sensitive adhesive sheet for optical member |
| JP2002341141A (en) * | 2001-05-15 | 2002-11-27 | Nitto Denko Corp | Adhesion type optical film and liquid crystal display device |
| JP2003034781A (en) * | 2001-05-15 | 2003-02-07 | Soken Chem & Eng Co Ltd | Pressure sensitive adhesive for optical member and optical member provided with the adhesive |
| JP2003049143A (en) * | 2001-05-31 | 2003-02-21 | Soken Chem & Eng Co Ltd | Adhesive for optical film and optical film using the adhesive |
| JP2003064336A (en) * | 2001-08-23 | 2003-03-05 | Nitto Denko Corp | Adhesive composition for medical application and adhesive tape or sheet using the same composition |
| JP2004059893A (en) * | 2002-06-04 | 2004-02-26 | Sekisui Chem Co Ltd | Acrylic adhesive composition and adhesive tape |
| JP2004091500A (en) * | 2002-08-29 | 2004-03-25 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive for optical member and optical member using the same pressure-sensitive adhesive |
| JP2005179467A (en) * | 2003-12-18 | 2005-07-07 | Nitto Denko Corp | Adhesive composition for optical film, adhesive layer for optical film, adherent type optical film and image display device |
| WO2005061648A1 (en) * | 2003-12-18 | 2005-07-07 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive type optical film, and image display |
Cited By (13)
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| JP2011528447A (en) * | 2008-07-18 | 2011-11-17 | エルジー・ケム・リミテッド | Polarizing plate and liquid crystal display device |
| JP2014160246A (en) * | 2008-07-18 | 2014-09-04 | Lg Chem Ltd | Polarizing plate and liquid crystal display device |
| US9394465B2 (en) | 2008-10-15 | 2016-07-19 | Mitsubishi Plastics, Inc. | Transparent adhesive sheet and image display device |
| JPWO2010044229A1 (en) * | 2008-10-15 | 2012-03-15 | 三菱樹脂株式会社 | Transparent adhesive sheet and image display device |
| US9109141B2 (en) | 2008-10-15 | 2015-08-18 | Mitsubishi Plastics, Inc. | Transparent adhesive sheet and image display device |
| JP2011122104A (en) * | 2009-12-11 | 2011-06-23 | Saiden Chemical Industry Co Ltd | Adhesive composition for polarizing plate |
| JP2013523940A (en) * | 2010-04-05 | 2013-06-17 | エルジー・ハウシス・リミテッド | Adhesive composition for touch panel, adhesive film and touch panel |
| JP2012208247A (en) * | 2011-03-29 | 2012-10-25 | Sumitomo Chemical Co Ltd | Liquid crystal display device |
| KR20170032313A (en) | 2014-07-18 | 2017-03-22 | 닛폰고세이가가쿠고교 가부시키가이샤 | Adhesive composition and adhesive using same, and adhesive for polarizing plate |
| JP2016084433A (en) * | 2014-10-28 | 2016-05-19 | フジコピアン株式会社 | Double-sided adhesive film and protective member for information display screen using the same |
| US11214721B2 (en) | 2016-10-14 | 2022-01-04 | Shin-Etsu Chemical Co., Ltd. | Thermally conductive composite silicone rubber sheet and method for manufacturing same |
| JP2018077480A (en) * | 2017-11-30 | 2018-05-17 | 住友化学株式会社 | Liquid crystal display device |
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| CN101258214B (en) | 2010-12-15 |
| KR100784995B1 (en) | 2007-12-11 |
| TWI335932B (en) | 2011-01-11 |
| KR20070025980A (en) | 2007-03-08 |
| JP5128478B2 (en) | 2013-01-23 |
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| TW200720387A (en) | 2007-06-01 |
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