JP6530376B2 - Pressure-sensitive adhesive composition for polarizing plate, pressure-sensitive adhesive sheet and polarizing plate with pressure-sensitive adhesive layer - Google Patents
Pressure-sensitive adhesive composition for polarizing plate, pressure-sensitive adhesive sheet and polarizing plate with pressure-sensitive adhesive layerInfo
- Publication number
- JP6530376B2 JP6530376B2 JP2016508612A JP2016508612A JP6530376B2 JP 6530376 B2 JP6530376 B2 JP 6530376B2 JP 2016508612 A JP2016508612 A JP 2016508612A JP 2016508612 A JP2016508612 A JP 2016508612A JP 6530376 B2 JP6530376 B2 JP 6530376B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- pressure
- sensitive adhesive
- polarizing plate
- 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.)
- Active
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 141
- 239000010410 layer Substances 0.000 title claims description 79
- 239000000203 mixture Substances 0.000 title claims description 76
- -1 isocyanate compound Chemical class 0.000 claims description 101
- 239000000178 monomer Substances 0.000 claims description 78
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- 230000001070 adhesive effect Effects 0.000 claims description 37
- 239000000853 adhesive Substances 0.000 claims description 34
- 239000012948 isocyanate Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 32
- 150000002978 peroxides Chemical class 0.000 claims description 31
- 239000003505 polymerization initiator Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000013522 chelant Substances 0.000 claims description 25
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- 238000000034 method Methods 0.000 claims description 21
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 238000005227 gel permeation chromatography Methods 0.000 claims description 14
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- 125000002704 decyl 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])* 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
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- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 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 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
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- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical group C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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Description
本発明は、偏光板用粘着剤組成物に関する。 The present invention relates to a pressure-sensitive adhesive composition for a polarizing plate.
液晶セルは、液晶層が2枚の基板(例:ガラス板)間に挟まれた構造を有しており、前記基板の表面には粘着剤層を介して偏光板が貼付されている。偏光板は、高温・高湿熱環境下において、熱収縮しやすいことから寸法安定性に欠け、液晶セルに反りが発生することがある。近年、液晶セルの薄型化(例:液晶セルを構成する基板の薄型化)および偏光板の薄型化に伴い、高温・高湿熱環境下での液晶セルの反りがより大きな問題となっている。液晶セルの反りの原因としては、例えば、偏光板の熱収縮(寸法変化)に粘着剤層が追従することができないこと、粘着剤層の応力緩和特性が低いことが挙げられる。 The liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates (eg, a glass plate), and a polarizing plate is attached to the surface of the substrate via an adhesive layer. Since the polarizing plate is easily thermally shrunk in a high temperature and high humidity and heat environment, it may lack dimensional stability and may cause warpage in the liquid crystal cell. In recent years, with the reduction in thickness of liquid crystal cells (eg, reduction in thickness of substrates constituting liquid crystal cells) and the reduction in thickness of polarizing plates, warpage of liquid crystal cells under high-temperature, high-humidity heat environment has become a serious problem. The causes of the warpage of the liquid crystal cell include, for example, the inability of the pressure-sensitive adhesive layer to follow the thermal contraction (dimension change) of the polarizing plate and the low stress relaxation property of the pressure-sensitive adhesive layer.
また、高温・高湿熱環境下では、偏光板と基板との界面での発泡や、粘着剤層の断裂、偏光板の剥がれ等の不具合も生じやすい。したがって、偏光板用粘着剤には、高い耐久性が要求される。 In addition, in a high temperature and high humidity and heat environment, defects such as foaming at the interface between the polarizing plate and the substrate, tearing of the pressure-sensitive adhesive layer, peeling of the polarizing plate, and the like easily occur. Therefore, high durability is required for the polarizing plate adhesive.
一般的に、液晶セルの反りを抑制する手段として、偏光板の寸法変化に対応することができる柔軟性の高い粘着剤層を使用する方法が挙げられる。しかしながら、このような粘着剤層では凝集力が不足し、耐久性の悪化および加工性の悪化等の問題が生じる。 In general, as a means for suppressing the warpage of the liquid crystal cell, there is mentioned a method using a highly flexible pressure-sensitive adhesive layer which can cope with the dimensional change of the polarizing plate. However, such an adhesive layer lacks cohesion and causes problems such as deterioration in durability and deterioration in processability.
例えば特許文献1には、耐久性や光学部材の寸法変化に起因する応力緩和特性(ガラスの反り)、再剥離性を課題として、特定の(メタ)アクリル系ポリマーとイソシアネート系架橋剤とを含有する光学部材用粘着剤組成物が開示されており、特許文献2には、リワーク性や耐久性を課題として、特定の共重合体と、金属キレート系硬化剤と、イソシアネート系硬化剤とを含有する粘着剤組成物が開示されている。 For example, Patent Document 1 contains a specific (meth) acrylic polymer and an isocyanate-based crosslinking agent with durability, stress relaxation characteristics (warpage of glass) due to dimensional changes of optical members, and removability as subjects. Patent Document 2 discloses a pressure-sensitive adhesive composition for an optical member, which contains a specific copolymer, a metal chelate-based curing agent, and an isocyanate-based curing agent, with reworkability and durability as issues. An adhesive composition is disclosed.
本発明の課題は、液晶セルの反り(ベンディング)を抑制でき、かつ耐久性に優れた粘着剤層を形成することが可能な偏光板用粘着剤組成物、前記組成物から形成された粘着剤層を有する偏光板用粘着シート、および前記粘着剤層を有する粘着剤層付き偏光板を提供することにある。 The object of the present invention is to provide a pressure-sensitive adhesive composition for a polarizing plate capable of suppressing a bending (bending) of a liquid crystal cell and capable of forming a pressure-sensitive adhesive layer excellent in durability, and a pressure-sensitive adhesive formed from the composition It is providing the adhesive sheet for polarizing plates which has a layer, and the polarizing plate with an adhesive layer which has the said adhesive layer.
本発明者らは上記課題を解決すべく鋭意検討した。その結果、分岐度が特定の範囲にある(メタ)アクリル系共重合体を用い、かつ架橋剤としてイソシアネート化合物および金属キレート化合物を併用した場合に、液晶セルの反り(ベンディング)を抑制でき、かつ耐久性に優れた粘着剤層を形成することができることを見出した。上述の特許文献1〜2には、このような分岐度に関して何ら言及されていない。すなわち、本発明者らは、以下の特定の構成を有する偏光板用粘着剤組成物を用いることにより上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors diligently studied to solve the above problems. As a result, when a (meth) acrylic copolymer having a branching degree in a specific range is used and an isocyanate compound and a metal chelate compound are used in combination as a crosslinking agent, warpage (bending) of the liquid crystal cell can be suppressed and It has been found that a pressure-sensitive adhesive layer excellent in durability can be formed. The above-mentioned Patent Documents 1 and 2 do not mention at all such a degree of branching. That is, the present inventors have found that the above-mentioned problems can be solved by using the pressure-sensitive adhesive composition for a polarizing plate having the following specific constitution, and have completed the present invention.
本発明は、例えば以下の[1]〜[9]である。
[1](A)アルキル基の炭素数が4〜18の(メタ)アクリル酸アルキルエステルおよびカルボキシル基含有モノマーを含むモノマー成分を共重合して得られ、かつゲルパーミエーションクロマトグラフィー法/多角度レーザー光散乱検出器(GPC−MALS)により測定される分岐度が0.55以下である(メタ)アクリル系共重合体と、(B1)イソシアネート化合物と、(B2)金属キレート化合物とを含有することを特徴とする偏光板用粘着剤組成物。The present invention is, for example, the following [1] to [9].
[1] (A) obtained by copolymerizing a monomer component containing a (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms of an alkyl group and a carboxyl group-containing monomer, and gel permeation chromatography method / multiple angle Contains a (meth) acrylic copolymer having a degree of branching measured by a laser light scattering detector (GPC-MALS) of 0.55 or less, (B1) an isocyanate compound, and (B2) a metal chelate compound The adhesive composition for polarizing plates characterized by the above-mentioned.
[2]前記(メタ)アクリル系共重合体(A)が、過酸化物系重合開始剤の存在下で前記共重合により得られた共重合体である、前記[1]記載の偏光板用粘着剤組成物。 [2] The polarizing plate according to [1], wherein the (meth) acrylic copolymer (A) is a copolymer obtained by the copolymerization in the presence of a peroxide polymerization initiator. Adhesive composition.
[3]前記(メタ)アクリル系共重合体(A)のゲルパーミエーションクロマトグラフィー法(GPC法)により測定される重量平均分子量(Mw)が、20万〜150万である、前記[1]または[2]記載の偏光板用粘着剤組成物。 [3] The above-mentioned [1], wherein the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC method) of the (meth) acrylic copolymer (A) is 200,000 to 1,500,000. Or the adhesive composition for polarizing plates as described in [2].
[4]前記(メタ)アクリル系共重合体(A)のGPC−MALSにより測定される分岐度が、0.10〜0.54である、前記[1]〜[3]のいずれか1項記載の偏光板用粘着剤組成物。 [4] Any one of the above [1] to [3], wherein the degree of branching measured by GPC-MALS of the (meth) acrylic copolymer (A) is 0.10 to 0.54. The adhesive composition for polarizing plates as described.
[5]前記(メタ)アクリル系共重合体(A)が、さらにカルボキシル基含有モノマー以外の極性基含有モノマーを共重合して得られた共重合体である、前記[1]〜[4]のいずれか1項記載の偏光板用粘着剤組成物。 [5] The above [1] to [4], wherein the (meth) acrylic copolymer (A) is a copolymer obtained by further copolymerizing a polar group-containing monomer other than a carboxyl group-containing monomer The pressure-sensitive adhesive composition for a polarizing plate according to any one of the above.
[6]過酸化物の含有量が、(メタ)アクリル系共重合体(A)100質量部に対して、0.1質量部以下である、前記[1]〜[5]のいずれか1項記載の偏光板用粘着剤組成物。 [6] Any one of the above [1] to [5], wherein the content of the peroxide is 0.1 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic copolymer (A) The adhesive composition for polarizing plates as described in a term.
[7]前記偏光板用粘着剤組成物より形成された粘着剤のゲル分率が、20〜70質量%である、前記[1]〜[6]のいずれか1項記載の偏光板用粘着剤組成物。 [7] The adhesive for polarizing plate according to any one of the above [1] to [6], wherein the gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition for polarizing plate is 20 to 70% by mass. Agent composition.
[8]前記[1]〜[7]のいずれか1項記載の偏光板用粘着剤組成物より形成された粘着剤層を有することを特徴とする偏光板用粘着シート。 [8] A pressure-sensitive adhesive sheet for a polarizing plate comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition for a polarizing plate according to any one of the above [1] to [7].
[9]偏光板と、前記偏光板の少なくとも一方の面に、前記[1]〜[7]のいずれか1項記載の偏光板用粘着剤組成物より形成された粘着剤層とを有することを特徴とする粘着剤層付き偏光板。 [9] A polarizing plate, and a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition for a polarizing plate according to any one of the above [1] to [7] on at least one surface of the polarizing plate. A polarizing plate with a pressure-sensitive adhesive layer characterized by
本発明によれば、液晶セルの反り(ベンディング)を抑制でき、かつ耐久性に優れた粘着剤層を形成することが可能な偏光板用粘着剤組成物、前記組成物から形成された粘着剤層を有する偏光板用粘着シート、および前記粘着剤層を有する粘着剤層付き偏光板を提供することができる。 According to the present invention, it is possible to suppress the bending (bending) of a liquid crystal cell, and to form a pressure-sensitive adhesive composition for a polarizing plate capable of forming a pressure-sensitive adhesive layer excellent in durability, and a pressure-sensitive adhesive formed from the composition The adhesive sheet for polarizing plates which has a layer, and the polarizing plate with an adhesive layer which has the said adhesive layer can be provided.
以下、本発明の偏光板用粘着剤組成物、偏光板用粘着シートおよび粘着剤層付き偏光板を説明する。以下では、本発明の偏光板用粘着剤組成物を単に「粘着剤組成物」ともいい、本発明の偏光板用粘着シートを単に「粘着シート」ともいう。 Hereinafter, the pressure-sensitive adhesive composition for a polarizing plate, the pressure-sensitive adhesive sheet for a polarizing plate, and the polarizing plate with a pressure-sensitive adhesive layer of the present invention will be described. Hereinafter, the pressure-sensitive adhesive composition for polarizing plate of the present invention is simply referred to as "pressure-sensitive adhesive composition", and the pressure-sensitive adhesive sheet for polarizing plate of the present invention is also simply referred to as "pressure-sensitive adhesive sheet".
〔偏光板用粘着剤組成物〕
本発明の偏光板用粘着剤組成物は、(メタ)アクリル系共重合体(A)とイソシアネート化合物(B1)と金属キレート化合物(B2)とを含有する。前記粘着剤組成物は、必要に応じて、シランカップリング剤(C)、帯電防止剤(D)および有機溶媒(E)から選択される少なくとも1種を含有してもよい。 [Pressure-sensitive adhesive composition for polarizing plate]
The pressure-sensitive adhesive composition for a polarizing plate of the present invention contains a (meth) acrylic copolymer (A), an isocyanate compound (B1) and a metal chelate compound (B2). The pressure-sensitive adhesive composition may optionally contain at least one selected from a silane coupling agent (C), an antistatic agent (D) and an organic solvent (E).
以下では、イソシアネート化合物(B1)と金属キレート化合物(B2)とを総称して、「架橋剤(B)」ともいう。本発明では、(メタ)アクリル系共重合体(A)を、これらの架橋剤を併用して架橋することで、粘着剤層を形成する。 Hereinafter, the isocyanate compound (B1) and the metal chelate compound (B2) are collectively referred to as "crosslinking agent (B)". In the present invention, the pressure-sensitive adhesive layer is formed by crosslinking the (meth) acrylic copolymer (A) in combination with these crosslinking agents.
[(メタ)アクリル系共重合体(A)]
(メタ)アクリル系共重合体(A)は、アルキル基の炭素数が4〜18の(メタ)アクリル酸アルキルエステルおよびカルボキシル基含有モノマーを含むモノマー成分を共重合して得られた共重合体である。共重合体(A)のモノマー成分としては、その他、カルボキシル基含有モノマー以外の極性基含有モノマー、これら以外のその他のモノマーが挙げられる。 [(Meth) acrylic copolymer (A)]
The (meth) acrylic copolymer (A) is a copolymer obtained by copolymerizing a monomer component containing an alkyl group having a carbon number of 4 to 18 (meth) acrylic acid alkyl ester and a carboxyl group-containing monomer It is. Other examples of the monomer component of the copolymer (A) include polar group-containing monomers other than carboxyl group-containing monomers, and other monomers other than these.
本明細書において、アクリルおよびメタクリルを総称して「(メタ)アクリル」とも記載する。また、重合体に含まれる、あるモノマーaに由来する構成単位を「モノマーa単位」とも記載する。 In the present specification, acrylic and methacrylic are also collectively referred to as "(meth) acrylic". Moreover, the structural unit derived from a certain monomer a contained in a polymer is also described as a "monomer a unit."
(メタ)アクリル系共重合体(A)は、ゲルパーミエーションクロマトグラフィー法/多角度レーザー光散乱検出器(GPC−MALS)により測定される分岐度が、0.55以下であり、好ましくは0.10〜0.54、より好ましくは0.20〜0.53、特に好ましくは0.30〜0.53である。分岐度の測定条件の詳細は、実施例に記載する。 The (meth) acrylic copolymer (A) has a branching degree of 0.55 or less, preferably 0, as measured by gel permeation chromatography / multiangle laser light scattering detector (GPC-MALS). And more preferably 0.20 to 0.53, and particularly preferably 0.30 to 0.53. Details of the measurement conditions of the degree of branching are described in the examples.
分岐度は、0.55以下の場合に分岐状ポリマーであり、0.55を超える場合に直線状ポリマーであることを示す指標である。また、分岐状ポリマーにおいて、分岐度の値が小さい場合はポリマー分子の枝分かれが多く、高分岐鎖を有することを示し、分岐度の値が大きい場合はポリマー分子の枝分かれが少なく、低分岐鎖を有することを示す。 The degree of branching is an index showing that it is a branched polymer when it is 0.55 or less and it is a linear polymer when it exceeds 0.55. Moreover, in the branched polymer, when the value of the degree of branching is small, it indicates that the polymer molecule is highly branched and has a highly branched chain, and when the value of degree of branching is large, the polymer molecule is less branched and the low branched chain Indicates having.
分岐度が上記範囲にある(メタ)アクリル系共重合体(A)は、(1)室温程度ではポリマー分子相互の分岐鎖に起因する絡み合いが多く発生し、結果として、ポリマーの分子量および粘着剤層のゲル分率が低い設計においても、ポリマーの凝集性が維持され、粘着特性、粘着剤層を打ち抜く等の加工性、粘着剤層の変形およびはみ出しが少ない等の保管性に優れる粘着剤層が得られ;(2)高温(例:60℃)ではポリマー分子相互の前記絡み合いが一部緩むため、粘着剤層が優れた柔軟性を示し、偏光板の反り(ベンディング)抑制に優れるとともに、一部残存している前記絡み合いに起因して、粘着剤層が優れた耐久性を示す。 In the (meth) acrylic copolymer (A) having a degree of branching in the above range, (1) many entanglements due to branching between polymer molecules occur around room temperature, and as a result, the molecular weight of the polymer and the pressure-sensitive adhesive Even in the design where the gel fraction of the layer is low, the cohesiveness of the polymer is maintained, and the adhesive property is excellent, the adhesive property, the processability such as punching the adhesive layer, and the storage properties such as the deformation of the adhesive layer and little storage (2) The adhesive layer exhibits excellent flexibility because the entanglement of polymer molecules is partially loosened at high temperature (eg, 60 ° C.), and it is excellent in suppression of bending (bending) of the polarizing plate, The pressure-sensitive adhesive layer exhibits excellent durability due to the entanglement which is partially remaining.
上記(1)および(2)に関して、本発明では、架橋剤の一部に金属キレート化合物(B2)を使用しており、(メタ)アクリル系共重合体(A)/金属キレート化合物(B2)間で配位結合により架橋が形成される(疑似架橋)。このため、上記室温時には前記架橋が維持され、ポリマーが凝集性を発揮するのに対して、上記高温時には前記架橋が一部解かれ、粘着剤層がより優れた柔軟性を示す。 Regarding the above (1) and (2), in the present invention, the metal chelate compound (B2) is used as a part of the crosslinking agent, and (meth) acrylic copolymer (A) / metal chelate compound (B2) Crosslinks are formed between one another by coordination (pseudocrosslinking). Therefore, the crosslinking is maintained at the room temperature and the polymer exhibits cohesiveness, whereas the crosslinking is partially solved at the high temperature, and the pressure-sensitive adhesive layer exhibits more excellent flexibility.
偏光板の反りが抑制される点については、以下の理由によるものと推測される。例えば偏光板/粘着剤層/被着体という構成において、被着体としてガラス板を使用する場合を例にとって説明する。偏光板およびガラス板はそれぞれ熱収縮率が異なり、偏光板はガラス板に比べて熱収縮率(寸法変化)が通常大きい。粘着剤層が高温・高湿熱環境下での柔軟性に欠ける場合、偏光板の寸法変化に対して粘着剤層が追従することができず、粘着剤層で応力を緩和することが出来ず、応力がガラス板に集中し、これによってガラス板に反りが発生する。一方本発明の粘着剤組成物を用いて形成される粘着剤層は高分岐鎖ポリマーを含有し、架橋剤の一部に金属キレート化合物を用いているため、高温・高湿熱環境下において上記絡み合いが一部緩み、また上記架橋が一部解かれるため、偏光板の寸法変化に対して粘着剤層が追従することができるため、応力が発生せず、ガラス板に応力が集中することがない。また、偏光板も異方性なく均一に熱収縮することができ、偏光板の複屈折を誘発することがない。以上のように、本発明では、偏光板の寸法変化に伴う応力を粘着剤層が吸収・緩和することができ、よってガラス板に対して過度の応力(負荷)がかかることがないため、ガラス板の反り抑制へとつながると推測される。 About the point by which the curvature of a polarizing plate is suppressed, it is estimated by the following reasons. For example, in the configuration of polarizing plate / pressure-sensitive adhesive layer / adherend, the case of using a glass plate as an adherend will be described as an example. The polarizing plate and the glass plate have different thermal contraction rates, and the polarizing plate usually has a thermal contraction rate (dimension change) larger than that of the glass plate. When the pressure-sensitive adhesive layer lacks flexibility under high temperature and high humidity heat environment, the pressure-sensitive adhesive layer can not follow the dimensional change of the polarizing plate, and the stress can not be relieved by the pressure-sensitive adhesive layer. The stress is concentrated on the glass plate, which causes the glass plate to warp. On the other hand, the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition of the present invention contains a highly branched polymer, and a metal chelate compound is used as a part of the crosslinking agent. Since the pressure-sensitive adhesive layer can follow the dimensional change of the polarizing plate because stress is partially loosened and the above-mentioned crosslinking is partially solved, stress is not generated and stress is not concentrated on the glass plate . In addition, the polarizing plate can also be thermally shrunk uniformly without anisotropy, and the birefringence of the polarizing plate is not induced. As described above, in the present invention, the pressure-sensitive adhesive layer can absorb and relieve the stress caused by the dimensional change of the polarizing plate, and therefore, the glass plate is not subjected to an excessive stress (load). It is presumed that it leads to the board curb curbing.
本発明の粘着剤組成物は、以上の特性を有することから、液晶セルを構成する基板と偏光板との貼り合わせ用途に好適である。特に、薄型化された液晶セルを構成するガラス板の厚さが0.1〜1.0mm程度と小さい場合においても、当該基板と偏光板との貼り合わせ用途に好適である。 The pressure-sensitive adhesive composition of the present invention has the above-described properties, and thus is suitable for use in laminating a substrate constituting a liquid crystal cell and a polarizing plate. In particular, even in the case where the thickness of the glass plate constituting the thinned liquid crystal cell is as small as about 0.1 to 1.0 mm, it is suitable for use for bonding the substrate and the polarizing plate.
《(メタ)アクリル酸アルキルエステル》
(メタ)アクリル酸アルキルエステルとしては、アルキル基の炭素数が4〜18の(メタ)アクリル酸アルキルエステル(CH2=CR1−COOR2;R1は水素原子またはメチル基であり、R2は炭素数4〜18のアルキル基である)が用いられ、ここで前記アルキル基の炭素数は4〜12がより好ましい。 << (meth) acrylic acid alkyl ester >>
As the (meth) acrylic acid alkyl ester, an alkyl group having 4 to 18 carbon atoms (meth) acrylic acid alkyl ester (CH 2 = CR 1 -COOR 2 ; R 1 is a hydrogen atom or a methyl group, R 2 Is an alkyl group having 4 to 18 carbon atoms, and the alkyl group preferably has 4 to 12 carbon atoms.
アルキル基の炭素数が4〜18の(メタ)アクリル酸アルキルエステルとしては、例えば、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert−ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、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、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ウンデカ(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレートが挙げられる。これらは1種単独で用いてもよく、2種以上を用いてもよい。 Examples of (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms of alkyl group include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undeca (meth) acrylate, Examples include lauryl (meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate. These may be used singly or in combination of two or more.
(メタ)アクリル系共重合体(A)を形成するモノマー成分100質量%中、アルキル基の炭素数が4〜18の(メタ)アクリル酸アルキルエステルの合計量は、良好な粘着力および耐久性発現の観点から、好ましくは99.8〜20質量%、より好ましくは99.5〜30質量%、さらに好ましくは99〜50質量%である。 The total amount of (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms in the alkyl group in 100% by mass of the monomer component forming the (meth) acrylic copolymer (A) has good adhesion and durability. From the viewpoint of expression, it is preferably 99.8 to 20% by mass, more preferably 99.5 to 30% by mass, and still more preferably 99 to 50% by mass.
(メタ)アクリル系共重合体(A)のモノマー成分として、アルキル基の炭素数が1〜3の(メタ)アクリル酸アルキルエステル(CH2=CR3−COOR4;R3は水素原子またはメチル基であり、R4は炭素数1〜3のアルキル基である)を使用することも可能である。As a monomer component of the (meth) acrylic copolymer (A), an alkyl group having 1 to 3 carbon atoms (meth) acrylic acid alkyl ester (CH 2 3CR 3 -COOR 4 ; R 3 is a hydrogen atom or methyl And R 4 is an alkyl group having 1 to 3 carbon atoms.
アルキル基の炭素数が1〜3の(メタ)アクリル酸アルキルエステルとしては、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、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレートが挙げられる。これらは1種単独で用いてもよく、2種以上を用いてもよい。 Examples of (meth) acrylic acid alkyl ester having 1 to 3 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and isopropyl (meth) acrylate . These may be used singly or in combination of two or more.
アルキル基の炭素数が1〜3の(メタ)アクリル酸アルキルエステルの使用量は、応力緩和特性の観点から、モノマー成分100質量%中、60質量%以下が好ましく、より好ましくは50質量%以下であり、さらに好ましくは40質量%以下である。 The amount of the (meth) acrylic acid alkyl ester having 1 to 3 carbon atoms in the alkyl group is preferably 60% by mass or less, more preferably 50% by mass or less in 100% by mass of the monomer component, from the viewpoint of stress relaxation properties. More preferably, it is 40 mass% or less.
《カルボキシル基含有モノマー》
カルボキシル基含有モノマーとしては、例えば、(メタ)アクリル酸β−カルボキシエチル、(メタ)アクリル酸5−カルボキシペンチル、コハク酸モノ(メタ)アクリロイルオキシエチルエステル、ω−カルボキシポリカプロラクトンモノ(メタ)アクリレート等のカルボキシル基含有(メタ)アクリレート;アクリル酸、メタクリル酸、イタコン酸、クロトン酸、フマル酸、マレイン酸が挙げられる。 << Carboxyl group-containing monomer >>
As a carboxyl group-containing monomer, for example, (meth) acrylic acid β-carboxyethyl, (meth) acrylic acid 5-carboxypentyl, succinic acid mono (meth) acryloyl oxyethyl ester, ω-carboxy polycaprolactone mono (meth) acrylate Etc .; and acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid.
本明細書においてカルボキシル基含有モノマーには、2つのカルボキシル基が脱水縮合してなる酸無水物基を含有するモノマーも含まれ、例えば、無水マレイン酸、無水イタコン酸等のカルボン酸無水物が挙げられる。 In the present specification, the carboxyl group-containing monomer also includes a monomer containing an acid anhydride group formed by dehydration condensation of two carboxyl groups, and examples thereof include carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. Be
カルボキシル基含有モノマーは1種単独で用いてもよく、2種以上を用いてもよい。
カルボキシル基含有モノマーに含まれる当該カルボキシル基は、イソシアネート化合物(B1)や金属キレート化合物(B2)との架橋性官能基として機能する。カルボキシル基含有モノマーの使用量は、モノマー成分100質量%中、好ましくは0.01〜15質量%、より好ましくは0.05〜10質量%、さらに好ましくは0.1〜5質量%である。例えば、(メタ)アクリル系共重合体(A)の酸価は、好ましくは0.1〜117mgKOH/g、より好ましくは0.4〜78mgKOH/gである。The carboxyl group-containing monomer may be used alone or in combination of two or more.
The said carboxyl group contained in a carboxyl group-containing monomer functions as a crosslinkable functional group with an isocyanate compound (B1) and a metal chelate compound (B2). The amount of the carboxyl group-containing monomer to be used is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 5% by mass in 100% by mass of the monomer component. For example, the acid value of the (meth) acrylic copolymer (A) is preferably 0.1 to 117 mg KOH / g, more preferably 0.4 to 78 mg KOH / g.
カルボキシル基含有モノマーの使用量が前記上限値以下であると、(メタ)アクリル系共重合体(A)と架橋剤(B)とにより形成される架橋密度が高くなりすぎず、応力緩和特性に優れる粘着剤層が得られる。カルボキシル基含有モノマーの使用量が前記下限値以上であると、架橋構造が有効に形成され、常温において適切な強度を有する粘着剤層が得られる。 When the amount of use of the carboxyl group-containing monomer is less than or equal to the above upper limit, the crosslink density formed by the (meth) acrylic copolymer (A) and the crosslinking agent (B) does not become too high. An excellent pressure-sensitive adhesive layer is obtained. A crosslinked structure is effectively formed as the usage-amount of a carboxyl group-containing monomer is more than the said lower limit, and the adhesive layer which has appropriate intensity | strength at normal temperature is obtained.
《極性基含有モノマー》
極性基含有モノマーとしては、例えば、水酸基含有モノマー、カルボキシル基含有モノマー以外の酸基含有モノマー、アミノ基含有モノマー、アミド基含有モノマー、窒素系複素環含有モノマー、シアノ基含有モノマーが挙げられる。極性基含有モノマーとしては、架橋剤(B)が有する架橋性官能基と反応することが可能な極性基(架橋性官能基)を有するモノマーを用いることが好ましい。 << Polar group-containing monomer >>
Examples of polar group-containing monomers include hydroxyl group-containing monomers, acid group-containing monomers other than carboxyl group-containing monomers, amino group-containing monomers, amide group-containing monomers, nitrogen-based heterocycle-containing monomers, and cyano group-containing monomers. As the polar group-containing monomer, it is preferable to use a monomer having a polar group (crosslinkable functional group) capable of reacting with the crosslinkable functional group possessed by the crosslinking agent (B).
(メタ)アクリル系共重合体(A)は、カルボキシル基含有モノマーとともに、当該モノマー以外の極性基含有モノマーを共重合して得られた共重合体であることが好ましい。これらの中でも、偏光板等の光学フィルムとの基材密着性向上の観点から、カルボキシル基含有モノマーとともに、水酸基含有モノマーを用いることが好ましい。 The (meth) acrylic copolymer (A) is preferably a copolymer obtained by copolymerizing a polar group-containing monomer other than the carboxyl group-containing monomer with the carboxyl group-containing monomer. Among these, it is preferable to use a hydroxyl group-containing monomer together with the carboxyl group-containing monomer from the viewpoint of improving the adhesion to a substrate with an optical film such as a polarizing plate.
水酸基含有モノマーとしては、例えば、水酸基含有(メタ)アクリレートが挙げられ、具体的には、2−ヒドロキシエチル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロシキブチル(メタ)アクリレート、6−ヒドロキシヘキシル(メタ)アクリレート、8−ヒドロキシオクチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレートが挙げられる。ヒドロキシアルキル(メタ)アクリレートでのヒドロキシアルキル基の炭素数は、通常2〜8、好ましくは2〜6である。 Examples of the hydroxyl group-containing monomer include a hydroxyl group-containing (meth) acrylate, and specifically, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate. The carbon number of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate is generally 2-8, preferably 2-6.
水酸基含有モノマーに含まれる当該水酸基は、イソシアネート化合物(B1)に含まれるイソシアネート基との架橋性官能基として機能する。水酸基含有モノマーの使用量は、モノマー成分100質量%中、好ましくは0〜15質量%、より好ましくは0.05〜10質量%、さらに好ましくは0.1〜7質量%である。水酸基含有モノマーの使用量が前記上限値以下であると、(メタ)アクリル系共重合体(A)とイソシアネート化合物(B1)とにより形成される架橋密度が高くなりすぎず、応力緩和特性に優れる粘着剤層が得られる。水酸基含有モノマーの使用量が前記下限値以上であると、架橋構造が有効に形成され、常温において適切な強度を有する粘着剤層が得られる。 The said hydroxyl group contained in a hydroxyl-containing monomer functions as a crosslinkable functional group with the isocyanate group contained in an isocyanate compound (B1). The amount of the hydroxyl group-containing monomer used is preferably 0 to 15% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 7% by mass in 100% by mass of the monomer component. The crosslinking density formed by the (meth) acrylic copolymer (A) and the isocyanate compound (B1) does not become too high when the amount of the hydroxyl group-containing monomer used is not more than the above upper limit, and the stress relaxation characteristics are excellent. An adhesive layer is obtained. A crosslinked structure is effectively formed as the usage-amount of a hydroxyl-containing monomer is more than the said lower limit, and the adhesive layer which has appropriate intensity | strength at normal temperature is obtained.
本明細書において酸基としては、例えば、リン酸基、硫酸基が挙げられる。リン酸基含有モノマーとしては、側鎖にリン酸基を有する(メタ)アクリル系モノマーが挙げられ、硫酸基含有モノマーとしては、側鎖に硫酸基を有する(メタ)アクリル系モノマーが挙げられる。 In the present specification, examples of the acid group include a phosphate group and a sulfate group. As a phosphoric acid group containing monomer, the (meth) acrylic-type monomer which has a phosphoric acid group in a side chain is mentioned, As a sulfuric acid group containing monomer, the (meth) acrylic-type monomer which has a sulfate group in a side chain is mentioned.
アミノ基含有モノマーとしては、例えば、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート等のアミノ基含有(メタ)アクリレートが挙げられる。アミド基含有モノマーとしては、例えば、(メタ)アクリルアミド、N−メチル(メタ)アクリルアミド、N−エチル(メタ)アクリルアミド、N−プロピル(メタ)アクリルアミド、N−ヘキシル(メタ)アクリルアミドが挙げられる。窒素系複素環含有モノマーとしては、例えば、ビニルピロリドン、アクリロイルモルホリン、ビニルカプロラクタムが挙げられる。シアノ基含有モノマーとしては、例えば、シアノ(メタ)アクリレート、(メタ)アクリロニトリルが挙げられる。
極性基含有モノマーは1種単独で用いてもよく、2種以上を用いてもよい。Examples of the amino group-containing monomer include amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. Examples of the amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-hexyl (meth) acrylamide. Examples of nitrogen-based heterocycle-containing monomers include vinyl pyrrolidone, acryloyl morpholine and vinyl caprolactam. Examples of cyano group-containing monomers include cyano (meth) acrylate and (meth) acrylonitrile.
The polar group-containing monomer may be used alone or in combination of two or more.
《その他のモノマー》
(メタ)アクリル系共重合体(A)を形成するモノマー成分は、(メタ)アクリル系共重合体(A)の物性を損なわない範囲で、例えば、アルコキシアルキル(メタ)アクリレート、アルコキシポリアルキレングリコールモノ(メタ)アクリレート、脂環式基または芳香環含有(メタ)アクリレートなどの、その他の(メタ)アクリル酸エステルを含むことができる。 << Other monomer >>
The monomer component for forming the (meth) acrylic copolymer (A) is, for example, alkoxyalkyl (meth) acrylate or alkoxypolyalkylene glycol, as long as the physical properties of the (meth) acrylic copolymer (A) are not impaired. Other (meth) acrylic esters may be included, such as mono (meth) acrylates, alicyclic groups or aromatic ring-containing (meth) acrylates.
アルコキシアルキル(メタ)アクリレートとしては、例えば、メトキシメチル(メタ)アクリレート、2−メトキシエチル(メタ)アクリレート、2−エトキシエチル(メタ)アクリレート、3−メトキシプロピル(メタ)アクリレート、3−エトキシプロピル(メタ)アクリレート、4−メトキシブチル(メタ)アクリレート、4−エトキシブチル(メタ)アクリレートが挙げられる。 Examples of alkoxyalkyl (meth) acrylates include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (3-ethoxypropyl (meth) acrylate Examples include meta) acrylate, 4-methoxybutyl (meth) acrylate and 4-ethoxybutyl (meth) acrylate.
アルコキシポリアルキレングリコールモノ(メタ)アクリレートとしては、例えば、メトキシジエチレングリコールモノ(メタ)アクリレート、メトキシジプロピレングリコールモノ(メタ)アクリレート、エトキシトリエチレングリコールモノ(メタ)アクリレート、エトキシジエチレングリコールモノ(メタ)アクリレート、メトキシトリエチレングリコールモノ(メタ)アクリレートが挙げられる。 As alkoxypolyalkylene glycol mono (meth) acrylate, for example, methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, Methoxy triethylene glycol mono (meth) acrylate is mentioned.
脂環式基または芳香環含有(メタ)アクリレートとしては、例えば、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェニル(メタ)アクリレートが挙げられる。 As an alicyclic group or aromatic ring containing (meth) acrylate, a cyclohexyl (meth) acrylate, a benzyl (meth) acrylate, phenyl (meth) acrylate is mentioned, for example.
上記共重合における、上記その他の(メタ)アクリル酸エステルの全使用量は、モノマー成分100質量%中、60質量%以下であることが好ましく、より好ましくは40質量%以下である。 The total amount of the other (meth) acrylic acid ester used in the copolymerization is preferably 60% by mass or less, more preferably 40% by mass or less, in 100% by mass of the monomer component.
また、(メタ)アクリル系共重合体(A)の物性を損わない範囲で、例えば、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、プロピルスチレン、ブチルスチレン、へキシルスチレン、ヘプチルスチレンおよびオクチルスチレン等のアルキルスチレン、フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨウ化スチレン、ニトロスチレン、アセチルスチレンおよびメトキシスチレン等のスチレン系単量体;酢酸ビニルなどの、共重合性モノマーを用いることもできる。 In addition, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene, as long as the physical properties of the (meth) acrylic copolymer (A) are not impaired. Styrene-based monomers such as alkylstyrenes, fluorostyrenes, chlorostyrenes, bromostyrenes, dibromostyrenes, iodostyrenes, nitrostyrenes, nitrostyrenes, acetylstyrenes and methoxystyrenes; copolymerizable monomers such as vinyl acetate it can.
上記共重合における、上記共重合性モノマーの全使用量は、モノマー成分100質量%中、40質量%以下であることが好ましく、より好ましくは20質量%以下である。
その他のモノマーは1種単独で用いてもよく、2種以上を用いてもよい。The total amount of the copolymerizable monomer used in the copolymerization is preferably 40% by mass or less, and more preferably 20% by mass or less in 100% by mass of the monomer component.
The other monomers may be used alone or in combination of two or more.
《(メタ)アクリル系共重合体(A)の製造条件》
(メタ)アクリル系共重合体(A)は、過酸化物系重合開始剤の存在下で前記共重合により得られた共重合体であることが好ましい。すなわち、重合開始剤として、過酸化物系重合開始剤を用いることで、分岐度が上記範囲にある共重合体が得られる傾向にある。 << Production conditions of (meth) acrylic copolymer (A) >>
The (meth) acrylic copolymer (A) is preferably a copolymer obtained by the copolymerization in the presence of a peroxide polymerization initiator. That is, by using a peroxide-based polymerization initiator as the polymerization initiator, a copolymer having a degree of branching in the above range tends to be obtained.
(メタ)アクリル系共重合体(A)は、例えば、溶液重合法、塊状重合法、乳化重合法、懸濁重合法等の従来公知の重合法により製造することができ、これらの中でも溶液重合法が好ましい。具体的には、反応容器内に重合溶媒およびモノマー成分を仕込み、窒素ガス等の不活性ガス雰囲気下で重合開始剤を添加し、反応開始温度を通常40〜100℃、好ましくは50〜80℃に設定し、通常50〜90℃、好ましくは70〜90℃の温度に反応系を維持して、4〜20時間反応させる。 The (meth) acrylic copolymer (A) can be produced, for example, by a conventionally known polymerization method such as solution polymerization method, bulk polymerization method, emulsion polymerization method, suspension polymerization method, etc. Legal is preferred. Specifically, a polymerization solvent and a monomer component are charged in a reaction vessel, a polymerization initiator is added under an inert gas atmosphere such as nitrogen gas, and the reaction initiation temperature is usually 40 to 100 ° C., preferably 50 to 80 ° C. The reaction is carried out for 4 to 20 hours while maintaining the reaction system at a temperature of usually 50 to 90.degree. C., preferably 70 to 90.degree.
過酸化物系重合開始剤としては、例えば、
ジ(2−tert−ブチルパーオキシイソプロピル)ベンゼン、ジクミルパーオキサイド、2,5−ジメチル−2,5−ジ(tert−ブチルパーオキシ)ヘキサン、tert−ブチルクミルパーオキサイド、ジ−tert−ヘキシルパーオキサイド、ジ−tert−ブチルパーオキサイド等のジアルキルパーオキサイド類(例:R−O−O−Rで表される化合物、式中のRはそれぞれ独立にアルキル基またはアリール基置換アルキル基である;R−O−O−A−O−O−Rで表される化合物、式中のRはそれぞれ独立にアルキル基またはアリール基置換アルキル基であり、Aは2価の炭化水素基である);
ジイソブチリルパーオキサイド、ジ(3,5,5−トリメチルヘキサノイル)パーオキサイド、ジラウロイルパーオキサイド、ジベンゾイルパーオキサイド、ベンゾイル(3−メチルベンゾイル)パーオキサイド、ジ(3−メチルベンゾイル)パーオキサイド、ジ(4−メチルベンゾイル)パーオキサイド等のジアシルパーオキサイド類(例:R−COO−OCO−Rで表される化合物、式中のRはそれぞれ独立にアルキル基またはアリール基である);
ジ−n−プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジ(4−tert−ブチルシクロヘキシル)パーオキシジカーボネート、ジ(2−エチルヘキシル)パーオキシジカーボネート、ジ−sec−ブチルパーオキシジカーボネート等のパーオキシジカーボネート(例:R−OCO−O−O−COO−Rで表される化合物、式中のRはそれぞれ独立にアルキル基またはシクロアルキル基である);
クミルパーオキシネオデカノエート、1,1,3,3−テトラメチルブチルパーオキシネオデカノエート、tert−ヘキシルパーオキシネオデカノエート、tert−ブチルパーオキシネオデカノエート、tert−ブチルパーオキシネオヘプタノエート、tert−ヘキシルパーオキシピバレート、tert−ブチルパーオキシピバレート、1,1,3,3−テトラメチルブチルパーオキシ−2−エチルヘキサノエート、2,5−ジメチル−2,5−ジ(2−エチルヘキサノイルパーオキシ)ヘキサン、tert−ヘキシルパーオキシ−2−エチルヘキサノエート、tert−ブチルパーオキシ−2−エチルヘキサノエート、tert−ブチルパーオキシ−3,5,5−トリメチルヘキサノエート、tert−ブチルパーオキシラウレート、tert−ヘキシルパーオキシベンゾエート、2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン、tert−ブチルパーオキシアセテート、tert−ブチルパーオキシ−3−メチルベンゾエート、tert−ブチルパーオキシベンゾエート等のパーオキシエステル類(例:R1−O−O−CO−R2で表される化合物、式中のR1はアルキル基またはアリール基置換アルキル基であり、R2はアルキル基、アリール基またはアリール基置換アルキル基である;R−CO−O−O−A−O−O−CO−Rで表される化合物、式中のRはそれぞれ独立にアルキル基またはアリール基であり、Aは2価の炭化水素基である);
tert−ヘキシルパーオキシイソプロピルモノカーボネート、tert−ブチルパーオキシイソプロピルモノカーボネート、tert−ブチルパーオキシ−2−エチルヘキシルモノカーボネート等のパーオキシモノカーボネート類(例:R−O−O−COO−Rで表される化合物、式中のRはそれぞれ独立にアルキル基である);
が挙げられる。As a peroxide type polymerization initiator, for example,
Di (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-hexyl Dialkyl peroxides such as peroxides and di-tert-butyl peroxides (eg compounds represented by R—O—O—R, wherein R in the formula is each independently an alkyl group or an aryl group-substituted alkyl group A compound represented by R-O-O-A-O-O-R, wherein R is each independently an alkyl group or an aryl group-substituted alkyl group, and A is a divalent hydrocarbon group) ;
Diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, dibenzoyl peroxide, benzoyl (3-methylbenzoyl) peroxide, di (3-methylbenzoyl) peroxide, Diacyl peroxides such as di (4-methylbenzoyl) peroxide (eg, a compound represented by R-COO-OCO-R, wherein R is each independently an alkyl group or an aryl group);
Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate Peroxydicarbonates (eg, compounds represented by R-OCO-O-O-COO-R, wherein R is each independently an alkyl group or a cycloalkyl group);
Kumylperoxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, tert-hexylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperone Oxyneoheptanoate, tert-hexylperoxypivalate, tert-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2 5-di (2-ethylhexanoylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5 3,5-trimethylhexanoate, tert-butyl peroxy laurate, tert-hexyl peroxybenzoate, 2,5- Peroxy esters such as dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyacetate, tert-butylperoxy-3-methylbenzoate, tert-butylperoxybenzoate and the like (example: R 1- O-O-CO-R compounds represented by 2, R 1 in the formula is an alkyl group or an aryl group-substituted alkyl group, R 2 is an alkyl group, an aryl group or an aryl group-substituted alkyl group; R- A compound represented by CO-O-O-A-O-O-CO-R, wherein R is each independently an alkyl group or an aryl group, and A is a divalent hydrocarbon group);
Peroxy monocarbonates such as tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate etc. (example: R-O-O-COO-R Compounds wherein R in the formula is each independently an alkyl group);
Can be mentioned.
過酸化物系重合開始剤の中でも、高分岐鎖の(メタ)アクリル系共重合体が得られることから、パーオキシエステル類が好ましく、下記式(1)で表される過酸化物系重合開始剤がより好ましい。 Among the peroxide type polymerization initiators, peroxy esters are preferable because a highly branched (meth) acrylic copolymer can be obtained, and the peroxide type polymerization initiation represented by the following formula (1) Agents are more preferred.
式(1)で表される過酸化物系重合開始剤の中でも、tert−ブチルパーオキシピバレート、tert−ヘキシルパーオキシピバレート、tert−ブチルパーオキシネオデカノエート、tert−ブチルパーオキシネオヘプタノエート、tert−ブチルパーオキシ−2−エチルヘキサノエート、クミルパーオキシネオデカノエートが好ましく、高分岐鎖の共重合体が得られることから、tert−ブチルパーオキシピバレート、tert−ヘキシルパーオキシピバレート、tert−ブチルパーオキシネオデカノエート、tert−ブチルパーオキシネオヘプタノエート、tert−ブチルパーオキシ−2−エチルヘキサノエートが特に好ましい。 Among the peroxide type polymerization initiators represented by the formula (1), tert-butyl peroxypivalate, tert-hexyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyneo Preferably, heptanoate, tert-butylperoxy-2-ethylhexanoate, and cumylperoxyneodecanoate are preferred, and a highly branched copolymer is obtained. Particularly preferred are hexyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxy neoheptanoate, tert-butyl peroxy-2-ethylhexanoate.
過酸化物系重合開始剤は1種単独で用いてもよく、2種以上を用いてもよい。また、重合中に、過酸化物系重合開始剤を複数回添加することも制限されない。
重合開始剤として、分岐度が上記範囲にある限り、過酸化物系開始剤とともにアゾ系開始剤を用いることもできる。アゾ系開始剤としては、例えば、2,2'−アゾビスイソブチロニトリル、2,2'−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、2,2'−アゾビス(2−シクロプロピルプロピオニトリル)、2,2'−アゾビス(2,4−ジメチルバレロニトリル)、2,2'−アゾビス(2−メチルブチロニトリル)、1,1'−アゾビス(シクロヘキサン−1−カルボニトリル)、2−(カルバモイルアゾ)イソブチロニトリル、2−フェニルアゾ−4−メトキシ−2,4−ジメチルバレロニトリル、2,2'−アゾビス(2−アミジノプロパン)ジヒドロクロリド、2,2'−アゾビス(N,N'−ジメチレンイソブチルアミジン)、2,2'−アゾビス〔2−メチル−N−(2−ヒドロキシエチル)−プロピオンアミド〕、2,2'−アゾビス(イソブチルアミド)ジヒドレート、4,4'−アゾビス(4−シアノペンタン酸)、2,2'−アゾビス(2−シアノプロパノール)、ジメチル−2,2'−アゾビス(2−メチルプロピオネート)、2,2'−アゾビス[2−メチル−N−(2−ヒドロキシエチル)プロピオンアミド]等のアゾ化合物が挙げられる。これらの重合開始剤は1種単独で用いてもよく、2種以上を用いてもよい。A peroxide type polymerization initiator may be used individually by 1 type, and may use 2 or more types. In addition, the addition of the peroxide-based polymerization initiator multiple times during the polymerization is also not limited.
As the polymerization initiator, an azo initiator may be used together with the peroxide initiator as long as the degree of branching is in the above range. As an azo initiator, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-) Cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbo) Nitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'- Azobis (N, N′-dimethylene isobutyl amidine), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azo Di (isobutylamido) dihydrate, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-cyanopropanol), dimethyl-2,2'-azobis (2-methyl propionate) And azo compounds such as 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]. One of these polymerization initiators may be used alone, or two or more thereof may be used.
過酸化物系重合開始剤は、(メタ)アクリル系共重合体(A)を形成するモノマー成分100質量部に対して、通常0.001〜5質量部、好ましくは0.005〜3質量部の範囲内の量で使用される。また、アゾ系開始剤は使用しないことが好ましく、その使用量は、過酸化物系重合開始剤100質量部に対して、好ましくは0.5質量部以下、より好ましくは0.2質量部以下、さらに好ましくは0質量部である。ただし、反応後半に残存モノマーを減少させる目的で用いることは制限されない。また、上記重合反応中に、重合開始剤、連鎖移動剤、モノマー成分、重合溶媒を適宜追加添加してもよい。 The peroxide-based polymerization initiator is usually 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass, per 100 parts by mass of the monomer component forming the (meth) acrylic copolymer (A). Used in amounts in the range of Moreover, it is preferable not to use an azo initiator, and the amount thereof used is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, with respect to 100 parts by mass of a peroxide type polymerization initiator. And more preferably 0 parts by mass. However, use for the purpose of reducing residual monomers in the latter half of the reaction is not limited. In addition, during the polymerization reaction, a polymerization initiator, a chain transfer agent, a monomer component, and a polymerization solvent may be added as appropriate.
溶液重合に用いる重合溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素類;n−ペンタン、n−ヘキサン、n−ヘプタン、n−オクタン等の脂肪族炭化水素類;シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン等の脂環式炭化水素類;ジエチルエーテル、ジイソプロピルエーテル、1,2−ジメトキシエタン、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール、フェニルエチルエーテル、ジフェニルエーテル等のエーテル類;クロロホルム、四塩化炭素、1,2−ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類;酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル等のエステル類;アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類;N,N−ジメチルホルムアミド、N,N−ジメチルアセタミド、N−メチルピロリドン等のアミド類;アセトニトリル、ベンゾニトリル等のニトリル類;ジメチルスルホキシド、スルホラン等のスルホキシド類等が挙げられる。これらの重合溶媒は1種単独で用いてもよく、2種以上を用いてもよい。 As a polymerization solvent used for solution polymerization, for example, aromatic hydrocarbons such as benzene, toluene, xylene and the like; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane and the like; cyclopentane, Alicyclic hydrocarbons such as cyclohexane, cycloheptane and cyclooctane; diethylether, diisopropylether, 1,2-dimethoxyethane, dibutylether, tetrahydrofuran, dioxane, anisole, phenylethylether, ethers such as diphenylether; chloroform, Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone And ketones such as cyclohexanone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide and sulfolane Etc. One of these polymerization solvents may be used alone, or two or more thereof may be used.
本発明の粘着剤組成物において、(メタ)アクリル系共重合体(A)を製造する際に重合開始剤として好ましく用いられる過酸化物系重合開始剤のt時間反応後の残存率(%)は、以下の式により求めることができる。
残存率(%)=exp(−kdt)×100(%)
式中、kdは熱分解速度定数であり、アレニウスの式:kd=A×exp(−ΔE/RT)で表され、ここでAは頻度因子であり、ΔEは重合開始剤の熱分解反応における活性化エネルギーであり、Rは気体定数(8.314J/mol・K)であり、Tは絶対温度(K)であり;tは反応時間である。In the pressure-sensitive adhesive composition of the present invention, the residual ratio (%) after reaction for t time of the peroxide-based polymerization initiator preferably used as a polymerization initiator when producing the (meth) acrylic copolymer (A) Can be obtained by the following equation.
Residual rate (%) = exp (-k d t) x 100 (%)
Where k d is the thermal decomposition rate constant and is represented by the Arrhenius equation: k d = A × exp (−ΔE / RT), where A is a frequency factor and ΔE is the thermal decomposition of the polymerization initiator Activation energy in the reaction, R is a gas constant (8.314 J / mol · K), T is an absolute temperature (K); t is a reaction time.
上記過酸化物系重合開始剤について、頻度因子(A)および活性化エネルギー(ΔE)は求められており、例えば日油株式会社 有機過酸化物カタログ(第10版)に記載されている値を使用することができる。例えば、tert−ブチルパーオキシピバレートではΔE=119.1kJ/mol、A=6.93×1017hr-1であり、tert−ヘキシルパーオキシピバレートではΔE=118.5kJ/mol、A=6.45×1017hr-1であり、クミルパーオキシネオデカノエートではΔE=105.3kJ/mol、A=3.94×1016hr-1である。The frequency factor (A) and the activation energy (ΔE) of the peroxide-based polymerization initiator are determined, for example, the values described in NOF Corporation organic peroxide catalog (10th edition). It can be used. For example, ΔE = 119.1 kJ / mol, A = 6.93 × 10 17 hr −1 for tert-butyl peroxypivalate, ΔE = 118.5 kJ / mol for tert-hexyl peroxypivalate, A = 6.45 × 10 17 hr −1 , and for cumyl peroxy neodecanoate, ΔE = 105.3 kJ / mol, A = 3.94 × 10 16 hr −1 .
したがって、所定温度でのkdを算出できることから、所定温度でt時間反応後の過酸化物系重合開始剤の残存率(%)を上記式に従って算出することができる。よって、粘着剤組成物に含まれる過酸化物系重合開始剤の残存量は、上記共重合で使用した過酸化物系重合開始剤の量×残存率(%)により、算出することができる。Therefore, since the k d at a predetermined temperature can be calculated, the residual ratio (%) of the peroxide-based polymerization initiator after reaction for a predetermined time t can be calculated according to the above equation. Therefore, the remaining amount of the peroxide-based polymerization initiator contained in the pressure-sensitive adhesive composition can be calculated by the amount of the peroxide-based polymerization initiator used in the above copolymerization and the remaining rate (%).
《(メタ)アクリル系共重合体(A)の物性および含有量》
(メタ)アクリル系共重合体(A)のGPC法により測定される重量平均分子量(Mw)は、ポリスチレン換算値で、通常20万〜150万であり、好ましくは40万〜130万、より好ましくは50万〜110万である。共重合体(A)は、Mwが前記範囲にあっても高分岐鎖を有しているので、共重合体(A)鎖同士が相互に適度に絡み合うことができ、粘着剤層の耐久性や加工性が悪化することがない。特にMwが40万以上であると、凝集性の高い粘着剤層が得られる。 << Physical properties and content of (meth) acrylic copolymer (A) >>
The weight average molecular weight (Mw) of the (meth) acrylic copolymer (A) measured by the GPC method is, in terms of polystyrene, usually from 200,000 to 1,500,000, preferably from 400,000 to 1,300,000, more preferably Is 500,000 to 1,100,000. The copolymer (A) has hyperbranched chains even if Mw is in the above range, so that the copolymer (A) chains can be appropriately intertwined with each other, and the durability of the pressure-sensitive adhesive layer And processability does not deteriorate. In particular, when the Mw is 400,000 or more, a highly cohesive pressure-sensitive adhesive layer can be obtained.
(メタ)アクリル系共重合体(A)のGPC法により測定される分子量分布(Mw/Mn)は、通常50以下であり、好ましくは30以下、より好ましくは20以下である。
(メタ)アクリル系共重合体(A)のガラス転移温度(Tg)は、例えば、当該重合体を構成するモノマー単位およびその含有割合から、Foxの式により算定することができる。例えば、Foxの式により求めたガラス転移温度(Tg)が通常−70〜0℃、好ましくは−60〜−30℃となるように、(メタ)アクリル系共重合体(A)を合成することができる。このようなガラス転移温度(Tg)を有する(メタ)アクリル系共重合体(A)を用いることにより、常温で粘着性に優れた粘着剤組成物を得ることができる。
Foxの式:1/Tg=(W1/Tg1)+(W2/Tg2)+…+(Wm/Tgm)
W1+W2+…+Wm=1
式中、Tgは(メタ)アクリル系共重合体(A)のガラス転移温度であり、Tg1,Tg2,…,Tgmは各モノマーからなるホモポリマーのガラス転移温度であり、W1,W2,…,Wmは各モノマー由来の構成単位の前記共重合体(A)における重量分率である。The molecular weight distribution (Mw / Mn) of the (meth) acrylic copolymer (A) measured by the GPC method is usually 50 or less, preferably 30 or less, more preferably 20 or less.
The glass transition temperature (Tg) of the (meth) acrylic copolymer (A) can be calculated, for example, from the monomer units constituting the polymer and the content ratio thereof by the Fox equation. For example, the (meth) acrylic copolymer (A) is synthesized such that the glass transition temperature (Tg) determined by the Fox equation is usually −70 to 0 ° C., preferably −60 to −30 ° C. Can. By using the (meth) acrylic copolymer (A) having such a glass transition temperature (Tg), a pressure-sensitive adhesive composition having excellent adhesiveness at normal temperature can be obtained.
Fox's formula: 1 / Tg = (W 1 / Tg 1 ) + (W 2 / Tg 2 ) +... + (W m / Tg m )
W 1 + W 2 + ... + W m = 1
In the formula, Tg is the glass transition temperature of the (meth) acrylic copolymer (A), Tg 1 , Tg 2 ,..., Tg m is the glass transition temperature of the homopolymer comprising each monomer, W 1 , W 2 ,..., W m are weight fractions of the constituent units derived from the respective monomers in the copolymer (A).
前記Foxの式における各単量体からなるホモポリマーのガラス転移温度は、例えば、Polymer Handbook Fourth Edition(Wiley−Interscience 1999)記載の値を用いることができる。 The glass transition temperature of the homopolymer comprising each monomer in the Fox formula can be, for example, the value described in Polymer Handbook Fourth Edition (Wiley-Interscience 1999).
本発明の粘着剤組成物中の(メタ)アクリル系共重合体(A)の含有量は、当該組成物中の有機溶媒(E)を除く固形分100質量%中、通常50〜99.99質量%、より好ましくは60〜99.95質量%、特に好ましくは80〜99.90質量%である。(メタ)アクリル系共重合体(A)の含有量が前記範囲にあると、粘着剤としての性能のバランスがとれ、粘着特性に優れる。 The content of the (meth) acrylic copolymer (A) in the pressure-sensitive adhesive composition of the present invention is usually 50 to 99.99 in 100% by mass of the solid content excluding the organic solvent (E) in the composition. % By mass, more preferably 60 to 99.95% by mass, particularly preferably 80 to 99.90% by mass. When the content of the (meth) acrylic copolymer (A) is in the above range, the performance as an adhesive can be balanced, and the adhesive properties are excellent.
[イソシアネート化合物(B1)]
イソシアネート化合物(B1)としては、1分子中のイソシアネート基数が2以上のイソシアネート化合物が通常用いられる。イソシアネート化合物(B1)により(メタ)アクリル系共重合体(A)を架橋することで、架橋体(ネットワークポリマー)を形成することができる。 [Isocyanate Compound (B1)]
As the isocyanate compound (B1), an isocyanate compound having two or more isocyanate groups in one molecule is usually used. A crosslinked body (network polymer) can be formed by crosslinking the (meth) acrylic copolymer (A) with the isocyanate compound (B1).
イソシアネート化合物(B1)のイソシアネート基数は、通常2以上であり、好ましくは2〜8であり、より好ましくは3〜6である。イソシアネート基数が前記範囲にあると、(メタ)アクリル系共重合体(A)とイソシアネート化合物(B1)との架橋反応効率の点、および粘着剤層の柔軟性を保つ点で好ましい。 The number of isocyanate groups of the isocyanate compound (B1) is usually 2 or more, preferably 2 to 8, and more preferably 3 to 6. When the number of isocyanate groups is in the above range, it is preferable in terms of the crosslinking reaction efficiency of the (meth) acrylic copolymer (A) and the isocyanate compound (B1) and in terms of maintaining the flexibility of the pressure-sensitive adhesive layer.
1分子中のイソシアネート基数が2のジイソシアネート化合物としては、例えば、脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香族ジイソシアネートが挙げられる。脂肪族ジイソシアネートとしては、エチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、2−メチル−1,5−ペンタンジイソシアネート、3−メチル−1,5−ペンタンジイソシアネート、2,2,4−トリメチル−1,6−ヘキサメチレンジイソシアネート等の炭素数4〜30の脂肪族ジイソシアネートが挙げられる。脂環族ジイソシアネートとしては、イソホロンジイソシアネート、シクロペンチルジイソシアネート、シクロヘキシルジイソシアネート、水素添加キシリレンジイソシアネート、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加テトラメチルキシリレンジイソシアネート等の炭素数7〜30の脂環族ジイソシアネートが挙げられる。芳香族ジイソシアネートとしては、例えば、フェニレンジイソシアネート、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、ナフチレンジイソシアネート、ジフェニルエーテルジイソシアネート、ジフェニルメタンジイソシアネート、ジフェニルプロパンジイソシアネート等の炭素数8〜30の芳香族ジイソシアネートが挙げられる。 Examples of the diisocyanate compound having 2 isocyanate groups per molecule include aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates. As aliphatic diisocyanates, ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl isocyanate Aliphatic diisocyanates having 4 to 30 carbon atoms such as 1,6-hexamethylene diisocyanate can be mentioned. Examples of alicyclic diisocyanates include isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and the like. Family diisocyanates. Examples of the aromatic diisocyanate include aromatic diisocyanates having 8 to 30 carbon atoms, such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthyl diisocyanate, diphenyl ether diisocyanate, diphenyl methane diisocyanate, diphenyl propane diisocyanate, and the like.
1分子中のイソシアネート基数が3以上のイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環族ポリイソシアネートが挙げられる。具体的には、2,4,6−トリイソシアネートトルエン、1,3,5−トリイソシアネートベンゼン、4,4',4"−トリフェニルメタントリイソシアネートが挙げられる。 Examples of the isocyanate compound having 3 or more isocyanate groups in one molecule include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specifically, 2,4,6- triisocyanate toluene, 1,3,5-triisocyanate benzene, 4,4 ', 4 "-triphenylmethane triisocyanate is mentioned.
また、イソシアネート化合物(B1)としては、例えば、イソシアネート基数が2または3以上の上記イソシアネート化合物の、多量体(例えば2量体または3量体、ビウレット体、イソシアヌレート体)、誘導体(例えば、多価アルコールと2分子以上のジイソシアネート化合物との付加反応生成物)、重合物が挙げられる。前記誘導体における多価アルコールとしては、低分子量多価アルコールとして、例えば、トリメチロールプロパン、グリセリン、ペンタエリトリトール等の3価以上のアルコールが挙げられ;高分子量多価アルコールとして、例えば、ポリエーテルポリオール、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が挙げられる。 In addition, as the isocyanate compound (B1), for example, a multimer (for example, dimer or trimer, biuret body, isocyanurate body), a derivative (for example, many polymers) of the above-mentioned isocyanate compound having two or more isocyanate groups The addition reaction product of a dihydric alcohol and a diisocyanate compound of two or more molecules), and a polymer. Examples of the polyhydric alcohol in the derivative include low molecular weight polyhydric alcohols such as tri- or higher alcohols such as trimethylolpropane, glycerin and pentaerythritol; and high molecular weight polyhydric alcohols such as polyether polyols, Polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols are mentioned.
このようなイソシアネート化合物としては、例えば、ジフェニルメタンジイソシアネートの3量体、ポリメチレンポリフェニルポリイソシアネート、ヘキサメチレンジイソシアネートまたはトリレンジイソシアネートのビウレット体またはイソシアヌレート体、トリメチロールプロパンとトリレンジイソシアネートまたはキシリレンジイソシアネートとの反応生成物(例えばトリレンジイソシアネートまたはキシリレンジイソシアネートの3分子付加物)、トリメチロールプロパンとヘキサメチレンジイソシアネートとの反応生成物(例えばヘキサメチレンジイソシアネートの3分子付加物)、ポリエーテルポリイソシアネート、ポリエステルポリイソシアネートが挙げられる。 As such an isocyanate compound, for example, trimer of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, biuret or isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate (For example, trimolecular adduct of tolylene diisocyanate or xylylene diisocyanate), reaction product of trimethylolpropane with hexamethylene diisocyanate (for example, trimolecular adduct of hexamethylene diisocyanate), polyether polyisocyanate, Polyester polyisocyanate is mentioned.
イソシアネート化合物(B1)の中でも、エージング性および光漏れ性能を向上させることができる点で、トリメチロールプロパンとトリレンジイソシアネートまたはキシリレンジイソシアネートとの反応生成物(綜研化学社製L−45、綜研化学社製TD−75等)、ヘキサメチレンジイソシアネートまたはトリレンジイソシアネートのイソシアヌレート体(旭化成工業社製TSE−100、日本ポリウレタン社製2050等)が好ましい。
イソシアネート化合物(B1)は1種単独で用いてもよく、2種以上を用いてもよい。Among isocyanate compounds (B1), the reaction product of trimethylolpropane with tolylene diisocyanate or xylylene diisocyanate in that it can improve the aging property and the light leakage performance (L-45 manufactured by Soken Chemical Co., Ltd., Soken Chemical Inc. TD-75 etc.), isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate (TSE-100 manufactured by Asahi Kasei Kogyo Co., Ltd., 2050 manufactured by Nippon Polyurethane Industry Co., Ltd.) is preferable.
The isocyanate compound (B1) may be used singly or in combination of two or more.
[金属キレート化合物(B2)]
本発明では、架橋剤(B)の一部に金属キレート化合物(B2)を用いる。金属キレート化合物(B2)は、配位結合により(メタ)アクリル系共重合体(A)を架橋する。このため、高温時には前記架橋が一部解かれ、粘着剤層がより優れた柔軟性を示す。 [Metal chelate compound (B2)]
In the present invention, the metal chelate compound (B2) is used as a part of the crosslinking agent (B). The metal chelate compound (B2) crosslinks the (meth) acrylic copolymer (A) by coordination bond. Therefore, when the temperature is high, the crosslinking is partially solved, and the pressure-sensitive adhesive layer exhibits more excellent flexibility.
金属キレート化合物(B2)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、ジルコニウム等の多価金属に、アルコキシド、アセチルアセトン、アセト酢酸エチル等が配位した化合物が挙げられる。これらの中でも、特にアルミキレート化合物(綜研化学社製 M−12AT等)が好ましい。具体的には、アルミニウムイソプロピレート、アルミニウムセカンダリーブチレート、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムトリスエチルアセトアセテート、アルミニウムトリスアセチルアセトネートが挙げられる。 Examples of the metal chelate compound (B2) include alkoxides, acetylacetone, ethyl acetoacetate and the like with polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. The compound which coordinated is mentioned. Among these, aluminum chelate compounds (M-12AT manufactured by Soken Chemical Co., Ltd.) are particularly preferable. Specific examples thereof include aluminum isopropylate, aluminum secondary butyrate, aluminum ethylacetoacetate / diisopropylate, aluminum trisethylacetoacetate and aluminum trisacetylacetonate.
金属キレート化合物(B2)は1種単独で用いてもよく、2種以上を用いてもよい。
本発明の粘着剤組成物において、イソシアネート化合物(B1)と金属キレート化合物(B2)との合計含有量は、(メタ)アクリル系共重合体(A)100質量部に対して、通常0.01〜5質量部、より好ましくは0.05〜2.5質量部、さらに好ましくは0.1〜1質量部である。この含有量が前記範囲にあると、耐久性と応力緩和特性のバランスが取りやすい点で好ましい。The metal chelate compound (B2) may be used alone or in combination of two or more.
In the pressure-sensitive adhesive composition of the present invention, the total content of the isocyanate compound (B1) and the metal chelate compound (B2) is usually 0.01 relative to 100 parts by mass of the (meth) acrylic copolymer (A). The amount is 5 to 5 parts by mass, more preferably 0.05 to 2.5 parts by mass, and still more preferably 0.1 to 1 parts by mass. When the content is in the above range, it is preferable from the viewpoint that balance between durability and stress relaxation characteristics can be easily achieved.
本発明の粘着剤組成物において、金属キレート化合物(B2)の含有量は、イソシアネート化合物(B1)100質量部に対して、通常10〜1000質量部、より好ましくは50〜600質量部、さらに好ましくは100〜400質量部である。この含有量が前記範囲にあると、ベンディング量抑制および偏光板等の光学フィルムとの基材密着性向上の点で好ましい。 In the pressure-sensitive adhesive composition of the present invention, the content of the metal chelate compound (B2) is usually 10 to 1000 parts by mass, preferably 50 to 600 parts by mass, more preferably 100 parts by mass of the isocyanate compound (B1). Is 100 to 400 parts by mass. When this content is in the above-mentioned range, it is preferable in terms of suppression of bending amount and improvement of adhesion to a substrate with an optical film such as a polarizing plate.
[シランカップリング剤(C)]
本発明の偏光板用粘着剤組成物は、さらにシランカップリング剤(C)を含有することが好ましい。シランカップリング剤(C)は、粘着剤層をガラス板等の被着体に対して強固に接着させ、高湿熱環境下で剥がれを防止する点に寄与する。 [Silane coupling agent (C)]
The pressure-sensitive adhesive composition for a polarizing plate of the present invention preferably further contains a silane coupling agent (C). A silane coupling agent (C) adheres an adhesive layer firmly to adherends, such as a glass plate, and contributes to the point which prevents peeling in a high humidity and heat environment.
シランカップリング剤(C)としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン等の重合性不飽和基含有シランカップリング剤;3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有シランカップリング剤;3−アミノプロピルトリメトキシシラン,N−(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルメチルジメトキシシラン等のアミノ基含有シランカップリング剤;3−クロロプロピルトリメトキシシラン等のハロゲン含有シランカップリング剤が挙げられる。 Examples of the silane coupling agent (C) include polymerizable unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane Epoxy groups such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Containing silane coupling agents; amino such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Group containing silane coupling Agents; halogen-containing silane coupling agents such as 3-chloropropyl trimethoxysilane.
本発明の偏光板用粘着剤組成物におけるシランカップリング剤(C)の含有量は、(メタ)アクリル系共重合体(A)100質量部に対して、通常1質量部以下、好ましくは0.01〜1質量部、より好ましくは0.05〜0.5質量部である。含有量が前記範囲にあると、高湿熱環境下における偏光板の剥がれや、高温環境下におけるシランカップリング剤(C)のブリードが防止される傾向にある。 The content of the silane coupling agent (C) in the pressure-sensitive adhesive composition for a polarizing plate of the present invention is usually 1 part by mass or less, preferably 0 based on 100 parts by mass of the (meth) acrylic copolymer (A). 0.01 to 1 part by mass, more preferably 0.05 to 0.5 parts by mass. If the content is in the above range, peeling of the polarizing plate in a high humidity and heat environment and bleeding of the silane coupling agent (C) in a high temperature environment tend to be prevented.
[帯電防止剤(D)]
帯電防止剤(D)は、例えば、本発明の偏光板用粘着剤組成物の表面抵抗値を低下させるために使用することができる。帯電防止剤(D)としては、例えば、界面活性剤、イオン性化合物、導電性ポリマーが挙げられる。 [Antistatic agent (D)]
The antistatic agent (D) can be used, for example, to reduce the surface resistance of the pressure-sensitive adhesive composition for a polarizing plate of the present invention. As an antistatic agent (D), surfactant, an ionic compound, a conductive polymer is mentioned, for example.
界面活性剤としては、例えば、4級アンモニウム塩類、アミド4級アンモニウム塩類、ピリジウム塩類、第1級〜第3級アミノ基等のカチオン性基を有するカチオン性界面活性剤;スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基等のアニオン性基を有するアニオン性界面活性剤;アルキルベタイン類、アルキルイミダゾリニウムベタイン類、アルキルアミンオキサイド類、アミノ酸硫酸エステル類等の両性界面活性剤、グリセリン脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシエチレンアルキルアミン類、ポリオキシエチレンアルキルアミン脂肪酸エステル類、N−ヒドロキシエチル−N−2−ヒドロキシアルキルアミン類、アルキルジエタノールアミド類等の非イオン性界面活性剤が挙げられる。 As the surfactant, for example, cationic surfactants having cationic groups such as quaternary ammonium salts, amide quaternary ammonium salts, pyridinium salts, primary to tertiary amino groups, etc .; sulfonic acid groups, sulfuric acid esters Anionic surfactants having an anionic group such as a base or a phosphate ester base; Amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfates etc., glycerin fatty acid esters And nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines and alkyl diethanolamides Be
また、界面活性剤として重合性基を有する反応型乳化剤も挙げられ、上記の界面活性剤または反応性乳化剤を含むモノマー成分を高分子量化したポリマー系界面活性剤を用いることもできる。 Moreover, the reaction type emulsifier which has a polymeric group as surfactant is also mentioned, The polymer type surfactant which polymerized the monomer component containing said surfactant or a reactive emulsifier can also be used.
イオン性化合物は、カチオン部とアニオン部とから構成され、室温下(23℃/50%RH)では固体状でも液体状のいずれであってもよい。
イオン性化合物を構成するカチオン部としては、無機系カチオンまたは有機系カチオンのいずれか一方であっても双方であってもよい。無機系カチオンとしては、アルカリ金属イオンおよびアルカリ土類金属イオンが好ましく、帯電防止性が優れたLi+、Na+およびK+がより好ましい。有機系カチオンとしては、例えば、ピリジニウムカチオン、ピペリジニウムカチオン、ピロリジニウム系カチオン、ピロリンカチオン、ピロールカチオン、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオンおよびこれらの誘導体が挙げられる。The ionic compound is composed of a cation moiety and an anion moiety, and may be solid or liquid at room temperature (23 ° C./50% RH).
The cation moiety constituting the ionic compound may be either an inorganic cation or an organic cation or both. As an inorganic type cation, an alkali metal ion and an alkaline earth metal ion are preferable, and Li + , Na + and K + having an excellent antistatic property are more preferable. Examples of organic cations include pyridinium cation, piperidinium cation, pyrrolidinium cation, pyrroline cation, pyrrole cation, pyrrole cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, pyrazolinium There may be mentioned cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations and their derivatives.
イオン性化合物を構成するアニオン部としては、カチオン部とイオン結合してイオン性化合物を形成し得るものであれば特に制限されない。具体的には、F-、Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、SCN-、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(F2SO2)2N-、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、F(HF)n -、(CN)2N-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-および(CF3SO2)(CF3CO)N-が挙げられる。これらの中では、フッ素原子を含むアニオンは、低融点のイオン性化合物を与えるので好ましく、(F2SO2)2N-および(CF3SO2)2N-がとりわけ好ましい。The anion moiety constituting the ionic compound is not particularly limited as long as it can form an ionic compound by ionic bonding with the cation moiety. Specifically, F -, Cl -, Br -, I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, SCN -, ClO 4 -, NO 3 -, CH 3 COO - , CF 3 COO − , CH 3 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , (F 2 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , AsF 6 − , SbF 6 − , NbF 6 − , TaF 6 − , F (HF) n − , (CN) 2 N − , C 4 F 9 SO 3 − , (C 2 F 5 SO 2 ) 2 N − , C 3 F 7 COO − and (CF 3 SO 2 ) (CF 3 CO) N − can be mentioned. Among these, anions containing a fluorine atom are preferable because they give low melting point ionic compounds, and (F 2 SO 2 ) 2 N − and (CF 3 SO 2 ) 2 N − are particularly preferable.
イオン性化合物としては、リチウムビス(トリフルオロメタンスルホニル)イミド、リチウムビス(ジフルオロスルホニル)イミド、リチウムトリス(トリフルオロメタンスルホニル)メタン、カリウムビス(トリフルオロメタンスルホニル)イミド、カリウムビス(ジフルオロスルホニル)イミド、1−エチルピリジニウムヘキサフルオロホスフェート、1−ブチルピリジニウムヘキサフルオロホスフェート、1−ヘキシル−4−メチルピリジニウムヘキサフルオロホスフェート、1−オクチル−4−メチルピリジニウムヘキサフルオロホスフェート、1−オクチル−4−メチルピリジニウムビス(フルオロスルホニル)イミド、1−オクチル−4−メチルピリジニウムビス(トリフルオロメタンスルホニル)イミド、(N,N−ジエチル−N−メチル−N−(2−メトキシエチル)アンモニウムテトラフルオロボレート、N,N−ジエチル−N−メチル−N−(2−メトキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)イミド、1−オクチルピリジニウムフルオロスホニウムイミド、1−オクチル−3−メチルピリジニウム、トリフルオロスルホニウムイミドが好ましい。 As the ionic compound, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (difluorosulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methane, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (difluorosulfonyl) imide, 1 -Ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (fluoro) Sulfonyl) imide, 1-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide, (N, N-diethyl) N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, 1-octyl pyridinium fluorosulfonyl Preferred are aluminum imide, 1-octyl-3-methylpyridinium and trifluorosulfonium imide.
導電性ポリマーとしては、例えば、ポリチオフェン、ポリアニリン、ポリピロールおよびこれらの誘導体が挙げられる。
本発明の偏光板用粘着剤組成物における帯電防止剤(D)の含有量は、(メタ)アクリル系共重合体(A)100質量部に対して、通常3質量部以下、好ましくは0.01〜3質量部、より好ましくは0.05〜2.5質量部である。As the conductive polymer, for example, polythiophene, polyaniline, polypyrrole and derivatives thereof can be mentioned.
The content of the antistatic agent (D) in the pressure-sensitive adhesive composition for a polarizing plate of the present invention is usually 3 parts by mass or less, preferably 0. 0 to 100 parts by mass of the (meth) acrylic copolymer (A). It is 0.1 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass.
[有機溶媒(E)]
本発明の粘着剤組成物は、その塗布性を調製するため、有機溶媒(E)を含有することが好ましい。有機溶媒としては、(メタ)アクリル系共重合体(A)の欄で説明した重合溶媒が挙げられる。例えば、上記共重合で得られた、(メタ)アクリル系共重合体(A)および重合溶媒を含むポリマー溶液と、イソシアネート化合物(B1)および金属キレート化合物(B2)とを混合して、粘着剤組成物を調製することができる。本発明の粘着剤組成物において、有機溶媒の含有量は、通常50〜90質量%、好ましくは60〜85質量%である。 [Organic solvent (E)]
The pressure-sensitive adhesive composition of the present invention preferably contains an organic solvent (E) in order to adjust its coatability. As an organic solvent, the polymerization solvent demonstrated by the column of the (meth) acrylic-type copolymer (A) is mentioned. For example, a polymer solution containing a (meth) acrylic copolymer (A) and a polymerization solvent obtained by the above copolymerization, and an isocyanate compound (B1) and a metal chelate compound (B2) are mixed to obtain an adhesive. The composition can be prepared. In the pressure-sensitive adhesive composition of the present invention, the content of the organic solvent is usually 50 to 90% by mass, preferably 60 to 85% by mass.
なお、本明細書において「固形分」とは、粘着剤組成物中の含有成分のうち上記有機溶媒(E)を除いた全成分をいい、「固形分濃度」とは、粘着剤組成物100質量%に対する前記固形分の割合をいう。 In addition, in this specification, "solid content" means all the components except the said organic solvent (E) among the components in an adhesive composition, and "solid content concentration" means the adhesive composition 100. The ratio of said solid content to mass% is said.
[過酸化物]
本発明の粘着剤組成物には、架橋剤としての過酸化物(過酸化物系架橋剤)を配合しないことが好ましい。(メタ)アクリル系共重合体(A)の合成時に使用した過酸化物系重合開始剤の残存量も含めて、過酸化物の含有量は、(メタ)アクリル系共重合体(A)100質量部に対して、好ましくは0.1質量部以下であり、より好ましくは0.05質量部以下、さらに好ましくは0.01質量部以下である。架橋剤としてイソシアネート化合物(B1)および金属キレート化合物(B2)を用い、過酸化物系架橋剤を用いないことで、残留した過酸化物に基づく粘着剤層の経時劣化を抑制することができる。 [Peroxide]
It is preferable not to mix | blend the peroxide (peroxide system crosslinking agent) as a crosslinking agent with the adhesive composition of this invention. The content of the peroxide, including the residual amount of the peroxide-based polymerization initiator used at the time of synthesis of the (meth) acrylic copolymer (A), is (meth) acrylic copolymer (A) 100. Preferably it is 0.1 mass part or less with respect to mass part, More preferably, it is 0.05 mass part or less, More preferably, it is 0.01 mass part or less. By using an isocyanate compound (B1) and a metal chelate compound (B2) as a crosslinking agent and not using a peroxide crosslinking agent, it is possible to suppress the temporal deterioration of the pressure-sensitive adhesive layer based on the remaining peroxide.
[添加剤]
本発明の粘着剤組成物は、上記成分のほか、本発明の効果を損なわない範囲で、酸化防止剤、光安定剤、金属腐蝕防止剤、粘着付与剤、可塑剤、架橋促進剤、前記(A)以外の(メタ)アクリル系重合体およびリワーク剤から選択される1種または2種以上を含有してもよい。 [Additive]
The pressure-sensitive adhesive composition of the present invention may contain, in addition to the above components, an antioxidant, a light stabilizer, a metal corrosion inhibitor, a tackifier, a plasticizer, a crosslinking accelerator, as long as the effects of the present invention are not impaired. You may contain 1 type, or 2 or more types selected from (meth) acrylic-type polymers and rework agents other than A).
[偏光板用粘着剤組成物の調製]
本発明の偏光板用粘着剤組成物は、(メタ)アクリル系共重合体(A)とイソシアネート化合物(B1)と金属キレート化合物(B2)と、必要に応じて他の成分とを、従来公知の方法により混合することで調製することができる。例えば、(メタ)アクリル系共重合体(A)を合成する際に得られた、当該ポリマーを含むポリマー溶液に、イソシアネート化合物(B1)と金属キレート化合物(B2)と必要に応じて他の成分とを配合することが挙げられる。 [Preparation of pressure-sensitive adhesive composition for polarizing plate]
The pressure-sensitive adhesive composition for a polarizing plate of the present invention comprises a (meth) acrylic copolymer (A), an isocyanate compound (B1), a metal chelate compound (B2), and, if necessary, other components, It can be prepared by mixing according to the method of For example, in the polymer solution containing the polymer obtained when synthesizing the (meth) acrylic copolymer (A), the isocyanate compound (B1) and the metal chelate compound (B2) and other components as needed And compounding.
本発明の粘着剤組成物より形成された粘着剤のゲル分率は、好ましくは20〜70質量%、より好ましくは24〜60質量%、さらに好ましくは30〜55質量%である。前記ゲル分率は、例えば実施例記載の条件により採取された粘着剤について測定される値である。 The gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition of the present invention is preferably 20 to 70% by mass, more preferably 24 to 60% by mass, and still more preferably 30 to 55% by mass. The gel fraction is, for example, a value measured for a pressure-sensitive adhesive collected under the conditions described in the examples.
〔粘着剤層〕
本発明の粘着剤層は、例えば、上述の粘着剤組成物中の架橋反応を進めることにより、具体的には(メタ)アクリル系共重合体(A)をイソシアネート化合物(B1)および金属キレート化合物(B2)で架橋することにより得られる。 [Adhesive layer]
In the pressure-sensitive adhesive layer of the present invention, for example, the crosslinking reaction in the above-mentioned pressure-sensitive adhesive composition is advanced, and specifically, the (meth) acrylic copolymer (A) is an isocyanate compound (B1) and a metal chelate compound It is obtained by crosslinking with (B2).
粘着剤層の形成条件は、例えば以下のとおりである。本発明の粘着剤組成物を支持体上に塗布し、溶媒の種類によっても異なるが、通常50〜150℃、好ましくは60〜100℃で、通常1〜10分間、好ましくは2〜7分間乾燥して溶媒を除去し、塗膜を形成する。乾燥塗膜の膜厚は、通常5〜75μm、好ましくは10〜50μmである。 The conditions for forming the pressure-sensitive adhesive layer are, for example, as follows. The pressure-sensitive adhesive composition of the present invention is coated on a support, and usually dried at 50 to 150 ° C., preferably 60 to 100 ° C., usually 1 to 10 minutes, preferably 2 to 7 minutes. The solvent is removed to form a coating. The thickness of the dried coating is usually 5 to 75 μm, preferably 10 to 50 μm.
粘着剤層は、以下の条件で形成することが好ましい。本発明の粘着剤組成物を支持体上に塗布し、上記条件で形成された塗膜上にカバーフィルムを貼付した後、通常3日以上、好ましくは7〜10日間、通常5〜60℃、好ましくは15〜40℃、通常30〜70%RH、好ましくは40〜70%RHの環境下で養生する。上記のような熟成条件で架橋を行うと、効率よく架橋体(ネットワークポリマー)の形成が可能である。 The pressure-sensitive adhesive layer is preferably formed under the following conditions. The pressure-sensitive adhesive composition of the present invention is coated on a support, and a cover film is attached on a coating film formed under the above conditions, usually 3 days or more, preferably 7 to 10 days, usually 5 to 60 ° C. Preferably, curing is performed in an environment of 15 to 40 ° C., usually 30 to 70% RH, preferably 40 to 70% RH. When crosslinking is performed under the above-described aging conditions, formation of a crosslinked product (network polymer) can be efficiently performed.
粘着剤組成物の塗布方法としては、公知の方法、例えばスピンコート法、ナイフコート法、ロールコート法、バーコート法、ブレードコート法、ダイコート法、グラビアコート法などにより、所定の厚さになるように塗布・乾燥する方法を用いることができる。 As a method of applying the pressure-sensitive adhesive composition, a predetermined thickness can be obtained by a known method such as spin coating, knife coating, roll coating, bar coating, blade coating, die coating, gravure coating, etc. Thus, a method of coating and drying can be used.
支持体およびカバーフィルムとしては、例えば、ポリエチレンテレフタレート(PET)等のポリエステルフィルム;ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体等のポリオレフィンフィルムなどのプラスチックフィルムが挙げられる。 Examples of the support and the cover film include plastic films such as polyester films such as polyethylene terephthalate (PET); and polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
本発明の粘着剤組成物より形成された粘着剤層は、偏光板の歪み抑制、凝集力、接着力、再剥離性の観点から、ゲル分率が、好ましくは20〜70質量%、より好ましくは24〜60質量%、さらに好ましくは30〜55質量%である。ゲル分率が前記範囲にあっても(メタ)アクリル系共重合体(A)が高分岐鎖を有しているので、共重合体(A)の分岐鎖同士が相互に適度に絡み合うことができ、粘着剤層の耐久性や加工性が悪化することがない。特にゲル分率が30質量%以上であると、凝集性の高い粘着剤層が得られる。ゲル分率が前記範囲を超えると、高温・高湿熱環境下での偏光板の寸法変化に起因する応力を、粘着剤層が充分に吸収・緩和できないことがある。 The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention preferably has a gel fraction of 20 to 70% by mass, more preferably from the viewpoint of distortion suppression of a polarizing plate, cohesion, adhesion and removability. Is 24 to 60% by mass, more preferably 30 to 55% by mass. Since the (meth) acrylic copolymer (A) has highly branched chains even when the gel fraction is in the above range, the branched chains of the copolymer (A) may be appropriately intertwined with each other There is no deterioration in the durability and processability of the pressure-sensitive adhesive layer. In particular, when the gel fraction is 30% by mass or more, a highly cohesive pressure-sensitive adhesive layer is obtained. When the gel fraction exceeds the above range, the pressure-sensitive adhesive layer may not be able to sufficiently absorb and relieve the stress caused by the dimensional change of the polarizing plate under high temperature and high humidity and heat environment.
〔偏光板用粘着シート〕
本発明の偏光板用粘着シートは、上述の偏光板用粘着剤組成物より形成された粘着剤層を有する。粘着シートとしては、例えば、上記粘着剤層のみを有する両面粘着シート、基材と、基材の両面に形成された上記粘着剤層とを有する両面粘着シート、基材と、基材の一方の面に形成された上記粘着剤層を有する片面粘着シート、およびそれら粘着シートの粘着剤層の基材と接していない面に剥離処理されたカバーフィルムが貼付された粘着シートが挙げられる。 [Adhesive sheet for polarizing plate]
The pressure-sensitive adhesive sheet for a polarizing plate of the present invention has a pressure-sensitive adhesive layer formed of the above-described pressure-sensitive adhesive composition for a polarizing plate. As the pressure-sensitive adhesive sheet, for example, a double-sided pressure-sensitive adhesive sheet having only the pressure-sensitive adhesive layer, a double-sided pressure-sensitive adhesive sheet having the substrate and the pressure-sensitive adhesive layer formed on both sides of the substrate, a substrate, and one of the substrates The adhesive sheet in which the single-sided adhesive sheet which has the said adhesive layer formed in the surface and the cover film by which the peeling process was carried out on the surface which is not in contact with the base material of the adhesive layer of these adhesive sheets is mentioned.
基材およびカバーフィルムとしては、例えば、ポリエチレンテレフタレート(PET)等のポリエステルフィルム;ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体等のポリオレフィンフィルムなどのプラスチックフィルムが挙げられる。 As a base material and a cover film, For example, Polyester film, such as a polyethylene terephthalate (PET); Plastic film, such as polyolefin films, such as polyethylene, a polypropylene, an ethylene-vinyl acetate copolymer, etc. are mentioned.
粘着剤層の形成条件は、〔粘着剤層〕の欄に記載した条件と同様である。
粘着剤層の膜厚は、粘着性能維持の観点から、通常5〜75μm、好ましくは10〜50μmである。基材およびカバーフィルムの膜厚は、特に限定されないが、通常10〜125μm、好ましくは25〜75μmである。The formation conditions of the pressure-sensitive adhesive layer are the same as the conditions described in the section of [pressure-sensitive adhesive layer].
The thickness of the pressure-sensitive adhesive layer is usually 5 to 75 μm, preferably 10 to 50 μm, from the viewpoint of maintaining the adhesion performance. Although the film thickness of a base material and a cover film is not specifically limited, Usually, 10-125 micrometers, Preferably it is 25-75 micrometers.
〔粘着剤層付き偏光板〕
本発明の粘着剤層付き偏光板は、偏光板と、前記偏光板の少なくとも一方の面に、本発明の偏光板用粘着剤組成物より形成された粘着剤層とを有することを特徴とする。なお、本明細書では、「偏光板」は「偏光フィルム」を包含する意味で用いる。 [Polarizer with adhesive layer]
The polarizing plate with a pressure-sensitive adhesive layer of the present invention is characterized by having a polarizing plate and a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition for a polarizing plate of the present invention on at least one surface of the polarizing plate. . In the present specification, “polarizing plate” is used to mean including “polarizing film”.
偏光板としては、従来公知の偏光フィルムを使用することができる。例えば、ポリビニルアルコール系樹脂からなるフィルムに偏光成分を含有させて延伸することにより得られる延伸フィルムと、前記延伸フィルム上に配置された保護フィルムとを有する多層フィルムが挙げられる。ポリビニルアルコール系樹脂としては、例えば、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、エチレン・酢酸ビニル共重合体の鹸化物が挙げられる。偏光成分としては、例えば、ヨウ素または二色性染料が挙げられる。保護フィルムとしては、例えば、トリアセチルセルロース等のセルロースフィルム、ポリカーボネートフィルム、ポリエーテルスルホンフィルムが挙げられる。 A conventionally known polarizing film can be used as the polarizing plate. For example, a multilayer film having a stretched film obtained by adding a polarizing component to a film made of a polyvinyl alcohol resin and stretching the film, and a protective film disposed on the stretched film can be mentioned. Examples of polyvinyl alcohol resins include polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, and saponified ethylene-vinyl acetate copolymer. The polarization component includes, for example, iodine or a dichroic dye. As a protective film, cellulose films, such as a triacetyl cellulose, a polycarbonate film, a polyether sulfone film is mentioned, for example.
偏光板の厚さは、通常30〜250μm、好ましくは50〜200μmである。
偏光板表面に粘着剤層を形成する方法に特に制限はなく、偏光板表面に直接バーコーター等を用いて上記粘着剤組成物を塗布し乾燥させる方法、本発明の偏光板用粘着シートが有する粘着剤層を偏光板表面に転写し熟成させる方法が挙げられる。乾燥および熟成の条件やゲル分率の範囲等は、〔粘着剤層〕の欄に記載した条件と同様である。The thickness of the polarizing plate is usually 30 to 250 μm, preferably 50 to 200 μm.
There is no particular limitation on the method of forming the pressure-sensitive adhesive layer on the surface of the polarizing plate, and a method of applying and drying the above-mentioned pressure-sensitive adhesive composition directly on the surface of the polarizing plate using a bar coater etc. There is a method of transferring the pressure-sensitive adhesive layer to the surface of the polarizing plate and aging it. The conditions for drying and aging, the range of the gel fraction, and the like are the same as the conditions described in the section of [adhesive layer].
偏光板上に形成される粘着剤層の厚さは、乾燥膜厚で通常5〜75μm、好ましくは10〜50μmである。なお、粘着剤層は、偏光板の少なくとも一方の面に形成されていればよく、偏光板の片面のみに粘着剤層が形成される態様、偏光板の両面に粘着剤層が形成される態様が挙げられる。 The thickness of the pressure-sensitive adhesive layer formed on the polarizing plate is usually 5 to 75 μm, preferably 10 to 50 μm, in dry thickness. The pressure-sensitive adhesive layer may be formed on at least one surface of the polarizing plate, and the pressure-sensitive adhesive layer may be formed on only one side of the polarizing plate, or the pressure-sensitive adhesive layer may be formed on both sides of the polarizing plate. Can be mentioned.
また、上記偏光板には、例えば保護層、防眩層、位相差層、視野角向上層等の他の機能を有する層が積層されていてもよい。
上記のようにして得られる本発明の粘着剤層付き偏光板を液晶セルの基板表面に設けることにより液晶素子が製造される。ここで液晶セルは、液晶層が2枚の基板間に挟まれた構造を有している。In addition, layers having other functions such as a protective layer, an antiglare layer, a retardation layer, and a viewing angle improvement layer may be stacked on the polarizing plate.
A liquid crystal element is manufactured by providing the adhesive layer-attached polarizing plate of the present invention obtained as described above on the substrate surface of a liquid crystal cell. Here, the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates.
液晶セルが有する基板としては、例えばガラス板が挙げられる。基板の厚さとしては、通常0.1〜1mm、好ましくは0.15〜0.8mmである。特に本発明では、上記粘着剤組成物を用いることで偏光板および基板の反りを抑制することができる。このため、基板の厚さが小さい場合(例:0.8mm以下、好ましくは0.15〜0.7mm)にも、偏光板と基板との貼り合わせに、上記粘着剤組成物は好適に用いることができる。 As a substrate which a liquid crystal cell has, a glass plate is mentioned, for example. The thickness of the substrate is usually 0.1 to 1 mm, preferably 0.15 to 0.8 mm. In the present invention, in particular, warpage of the polarizing plate and the substrate can be suppressed by using the pressure-sensitive adhesive composition. Therefore, even when the thickness of the substrate is small (e.g., 0.8 mm or less, preferably 0.15 to 0.7 mm), the above-mentioned pressure-sensitive adhesive composition is suitably used for bonding the polarizing plate and the substrate. be able to.
以下、本発明を実施例に基づいてさらに具体的に説明するが、本発明はこれら実施例に限定されない。以下の実施例等の記載において、特に言及しない限り、「部」は「質量部」を示す。 Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In the description of the following examples etc., unless otherwise stated, "part" shows a "mass part".
〔GPCおよびGPC−MALS〕
(メタ)アクリル系共重合体について、ゲルパーミエーションクロマトグラフィー法(GPC法)により、下記条件で、重量平均分子量(Mw)および数平均分子量(Mn)を、ゲルパーミエーションクロマトグラフィー法/多角度レーザー光散乱検出器(GPC−MALS)により、下記条件で、分岐度を求めた。
・測定装置:HLC−8320GPC(東ソー(株)製)
・GPCカラム構成:以下の4連カラム(すべて東ソー(株)製)
(1)TSKgel HxL−H(ガードカラム)
(2)TSKgel GMHxL
(3)TSKgel GMHxL
(4)TSKgel G2500HxL
・流速:1.0mL/min
・カラム温度:40℃
・サンプル濃度:1.5%(w/v)(テトラヒドロフランで希釈)
・移動相溶媒:テトラヒドロフラン
・検出器:DAWN HELEOS(MALS検出器)+Optilab rEX(RI検出器)
・標準ポリスチレン換算(MwおよびMnを測定する場合) [GPC and GPC-MALS]
For the (meth) acrylic copolymer, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (multi-angle method) by gel permeation chromatography (GPC method) under the following conditions. The degree of branching was determined by a laser light scattering detector (GPC-MALS) under the following conditions.
-Measuring device: HLC-8320GPC (made by Tosoh Corp.)
・ GPC column configuration: the following 4 columns (all manufactured by Tosoh Corporation)
(1) TSKgel HxL-H (guard column)
(2) TSKgel GMHxL
(3) TSKgel GMHxL
(4) TSKgel G2500HxL
・ Flow rate: 1.0 mL / min
・ Column temperature: 40 ° C
Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran)
Mobile phase solvent: Tetrahydrofuran Detector: DAWN HELEOS (MALS detector) + Optilab rEX (RI detector)
· Standard polystyrene equivalent (when measuring Mw and Mn)
[合成例1]
撹拌機、還流冷却器、温度計および窒素導入管を備えた反応装置に、n−ブチルアクリレート98.8部、4−ヒドロキシブチルアクリレート1部、アクリル酸0.2部、および酢酸エチル溶媒100部を仕込み、窒素ガスを導入しながら80℃に昇温した。次いで、tert−ブチルパーオキシピバレート0.1部を加え、窒素ガス雰囲気下、80℃で6時間重合反応を行った。反応終了後、酢酸エチルにて希釈し、固形分濃度30質量%のポリマー溶液を調製した。得られた(メタ)アクリル系共重合体Aの重量平均分子量(Mw)は70万であり、分子量分布(Mw/Mn)は7.1であり、分岐度は0.51であり、酸価は1.6mgKOH/gであった。 Synthesis Example 1
98.8 parts of n-butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 0.2 parts of acrylic acid, and 100 parts of ethyl acetate solvent in a reaction apparatus equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube The temperature was raised to 80.degree. C. while introducing nitrogen gas. Next, 0.1 part of tert-butyl peroxypivalate was added, and a polymerization reaction was performed at 80 ° C. for 6 hours in a nitrogen gas atmosphere. After completion of the reaction, the reaction solution was diluted with ethyl acetate to prepare a polymer solution having a solid concentration of 30% by mass. The weight average molecular weight (Mw) of the obtained (meth) acrylic copolymer A is 700,000, the molecular weight distribution (Mw / Mn) is 7.1, the degree of branching is 0.51, and the acid value is Was 1.6 mg KOH / g.
[合成例2〜12]
重合反応に用いたモノマー成分および重合開始剤を表1に記載したとおりに変更したこと以外は合成例1と同様に行い、固形分濃度30質量%のポリマー溶液を調製した。結果を表1に示す。 Synthesis Examples 2 to 12
A polymer solution with a solid concentration of 30% by mass was prepared in the same manner as in Synthesis Example 1 except that the monomer components and the polymerization initiator used for the polymerization reaction were changed as described in Table 1. The results are shown in Table 1.
[実施例1]
(1)粘着剤組成物の調製
合成例1で得られた(メタ)アクリル系ポリマー溶液(固形分濃度30質量%)と、当該溶液に含まれる(メタ)アクリル系ポリマー100部(固形分量)に対して、イソシアネート化合物として綜研化学(株)製「TD−75」(固形分75質量%、酢酸エチル溶液)0.05部(固形分量)と、金属キレート化合物として綜研化学(株)製「M−12AT」(固形分10質量%、トルエン、アセチルアセトン溶液)0.14部(固形分量)と、シランカップリング剤として信越化学工業(株)製「KBM−403」(固形分100%)0.2部と、帯電防止剤として第一工業製薬(株)製「AS−804」(固形分100%)1部とを混合して、粘着剤組成物を得た。 Example 1
(1) Preparation of adhesive composition The (meth) acrylic polymer solution (solid content concentration: 30% by mass) obtained in Synthesis Example 1 and 100 parts (solid content) of the (meth) acrylic polymer contained in the solution And 0.05 parts (solid content) of “TD-75” (solid content 75% by mass, ethyl acetate solution) manufactured by Soken Chemical Co., Ltd. as an isocyanate compound, and “K-Kanken Co. M-12AT "(solid content: 10% by mass, toluene, acetylacetone solution) 0.14 parts (solid content), and as a silane coupling agent, Shin-Etsu Chemical Co., Ltd." KBM-403 "(solid content: 100%) 0 .2 parts and 1 part of "AS-804" (solid content 100%) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. as an antistatic agent were mixed to obtain a pressure-sensitive adhesive composition.
(2)粘着シートの作製
泡抜け後、剥離処理されたポリエチレンテレフタレートフィルム(PETフィルム)上に、上記(1)で得られた粘着剤組成物をドクターブレードを用いて塗布し、90℃で3分間乾燥して、乾燥膜厚20μmの塗膜を形成した。塗膜の前記PETフィルムの貼付面とは反対面に、剥離処理されたPETフィルムをさらに貼り合わせ、23℃/50%RH環境下で7日間静置して熟成させて、2枚のPETフィルムに挟まれた厚さ20μmの粘着剤層を有する粘着シートを得た。 (2) Preparation of Pressure-Sensitive Adhesive Sheet After foaming, the pressure-sensitive adhesive composition obtained in the above (1) is applied onto a release-treated polyethylene terephthalate film (PET film) using a doctor blade, and 3 It was dried for a minute to form a coating having a dry film thickness of 20 μm. On the opposite side of the coated surface of the PET film to which the PET film is attached, a peeling-treated PET film is further attached, allowed to stand for 7 days in a 23 ° C./50% RH environment, and aged to obtain two PET films. A pressure-sensitive adhesive sheet having a 20 μm-thick pressure-sensitive adhesive layer sandwiched therebetween was obtained.
(3)粘着剤層付き偏光板の作製
泡抜け後、剥離処理されたポリエチレンテレフタレートフィルム(PETフィルム)上に、上記(1)で得られた粘着剤組成物をドクターブレードを用いて塗布し、90℃で3分間乾燥して、乾燥膜厚20μmの塗膜を有するシートを得た。前記シートと偏光板(厚さ:110μm、層構成:トリアセチルセルロースフィルム/ポリビニルアルコールフィルム/トリアセチルセルロースフィルム)とを、前記塗膜と偏光板とが接するように貼り合わせ、23℃/50%RHの条件で7日間静置して熟成させて、PETフィルムと厚さ20μmの粘着剤層と偏光板とを有する粘着剤層付き偏光板を得た。 (3) Preparation of Polarizing Plate with Pressure-Sensitive Adhesive Layer After foaming, the pressure-sensitive adhesive composition obtained in the above (1) is applied onto a release-treated polyethylene terephthalate film (PET film) using a doctor blade, It dried at 90 degreeC for 3 minutes, and obtained the sheet | seat which has a coating film with a dry film thickness of 20 micrometers. The sheet and a polarizing plate (thickness: 110 μm, layer structure: triacetyl cellulose film / polyvinyl alcohol film / triacetyl cellulose film) are laminated so that the coating film and the polarizing plate are in contact with each other, and 23 ° C./50% The mixture was allowed to stand for 7 days under the conditions of RH for aging to obtain a polarizing plate with a pressure-sensitive adhesive layer having a PET film, a pressure-sensitive adhesive layer with a thickness of 20 μm, and a polarizing plate.
[実施例2〜11、比較例1〜2]
実施例1において、(メタ)アクリル系ポリマー溶液を合成例2〜12で得られたポリマー溶液に変更し、配合組成を表2に記載したとおりに変更したこと以外は実施例1と同様にして、粘着剤組成物、粘着シートおよび粘着剤層付き偏光板を得た。 [Examples 2-11, Comparative Examples 1-2]
In the same manner as in Example 1 except that the (meth) acrylic polymer solution is changed to the polymer solution obtained in Synthesis Example 2 to 12 and the composition is changed as described in Table 2 in Example 1. A pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive layer were obtained.
[評価]
〔ゲル分率〕
実施例・比較例で得られた粘着シートから、粘着剤約0.1gをサンプリング瓶に採取し、酢酸エチル30mLを加えて4時間振盪した後、このサンプル瓶の内容物を200メッシュのステンレス製金網で濾過し、金網上の残留物を100℃で2時間乾燥して乾燥重量を測定した。次式により、粘着剤のゲル分率を求めた。
・ゲル分率(%)=(乾燥重量/粘着剤採取重量)×100(%) [Evaluation]
[Gel fraction]
About 0.1 g of a pressure-sensitive adhesive is taken from a pressure-sensitive adhesive sheet obtained in Example and Comparative Example in a sampling bottle, and 30 mL of ethyl acetate is added thereto and shaken for 4 hours. The resultant was filtered through a wire mesh, and the residue on the wire mesh was dried at 100 ° C. for 2 hours to determine the dry weight. The gel fraction of the adhesive was determined by the following equation.
・ Gel fraction (%) = (dry weight / adhesive collected weight) x 100 (%)
〔Creep値〕
実施例・比較例で得られた粘着剤層付き偏光板(PETフィルム/粘着剤層/偏光板からなる積層体)を幅10mm×長さ100mmにカットし、前記剥離処理されたPETフィルムを剥がして、アルカリ処理ガラス板上に、前記粘着剤層が前記ガラス板に接するように、かつ10mm×10mmの貼り合わせ面積になるように貼り合わせて、評価用粘着加工偏光板試験片を得た。 [Creep value]
The polarizing plate with a pressure-sensitive adhesive layer (laminate consisting of PET film / pressure-sensitive adhesive layer / polarizing plate) obtained in Examples and Comparative Examples is cut into a width of 10 mm × length 100 mm, and the release-treated PET film is peeled off Then, on an alkali-treated glass plate, the pressure-sensitive adhesive layer was bonded so that the pressure-sensitive adhesive layer was in contact with the glass plate, and a bonding area of 10 mm × 10 mm was obtained, to obtain a tackified polarizing plate test piece for evaluation.
評価用粘着加工偏光板試験片について、オートクレーブ処理(50℃、5atm)を行い、23℃/50%RH雰囲気下で24時間静置した。次に前記試験片を、微少クリープ測定機のチャンバーBOX内に固定用チャック部分の長さ15mmにてセットした。引張荷重800g、引張時間1000秒にて、前記試験片における前記評価用粘着加工偏光板を、当該偏光板と前記ガラスとの接着面に平行にかつ前記偏光板の長さ方向に引っ張り、前記試験片における前記ガラス板と偏光板との貼り合わせ部分のズレの距離(μm)をクリープ値として測定した。 The adhesion-processed polarizing plate test pieces for evaluation were subjected to an autoclave treatment (50 ° C., 5 atm), and left to stand under an atmosphere of 23 ° C./50% RH for 24 hours. Next, the test piece was set in the chamber BOX of the micro creep measuring machine with a length of 15 mm of the fixing chuck portion. The adhesion-processed polarizing plate for evaluation in the test piece is pulled parallel to the bonding surface of the polarizing plate and the glass in the longitudinal direction of the polarizing plate at a tensile load of 800 g and a tensile time of 1000 seconds, and the test is performed. The distance (μm) of the displacement of the bonded portion of the glass plate and the polarizing plate in the piece was measured as a creep value.
〔粘着力の測定〕
実施例・比較例で得られた粘着剤層付き偏光板(PETフィルム/粘着剤層/偏光板からなる積層体)を70mm×25mmの大きさに裁断して試験片を作成した。試験片からPETフィルムを剥離し、ラミネーターロールを用いて、粘着剤層/偏光板からなる積層体を厚さ2mmのガラス板の片面に、粘着剤層とガラス板とが接するように貼着した。得られた積層体を、50℃/5気圧に調整されたオートクレーブ中に20分間保持した。次いで23℃/50%RH環境下に1時間放置した後、ガラス板面に対して90°方向に300mm/minの速度で偏光板端部を引っ張り、粘着力(剥離強度)を測定した。 [Measurement of adhesive force]
A polarizing plate with a pressure-sensitive adhesive layer (a laminate comprising a PET film / pressure-sensitive adhesive layer / a polarizing plate) obtained in Examples and Comparative Examples was cut into a size of 70 mm × 25 mm to prepare a test piece. The PET film was peeled off from the test piece, and the laminate consisting of the pressure-sensitive adhesive layer / polarizing plate was attached using a laminator roll so that the pressure-sensitive adhesive layer and the glass plate were in contact with one side of a 2 mm-thick glass plate. . The resulting laminate was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes. Subsequently, after leaving it to stand in a 23 ° C./50% RH environment for 1 hour, the end of the polarizing plate was pulled at a speed of 300 mm / min in the direction of 90 ° with respect to the surface of the glass plate to measure adhesive strength (peel strength).
〔ベンディング(反り)〕
実施例・比較例で得られた粘着剤層付き偏光板(PETフィルム/粘着剤層/偏光板からなる積層体)を35mm×400mm(延伸軸方向)の大きさに裁断して試験片を作成した。試験片からPETフィルムを剥離し、ラミネーターロールを用いて、粘着剤層/偏光板からなる積層体を厚さ0.7mm、40mm×410mmのガラス板の片面に、粘着剤層とガラス板とが接するように貼着した。得られた積層体を、23℃/50%RH環境下に24時間放置した後、60℃のオーブン中に72時間保持した。片方の末端を床面に対して垂直な壁面に固定し、逆側末端の浮き上がり量を定規で測定した。オーブンから取り出し直後、および24時間後に測定を実施した。 [Bending (warping)]
The adhesive layer-attached polarizing plate (PET film / adhesive layer / laminated plate laminate) obtained in Examples and Comparative Examples is cut into a size of 35 mm × 400 mm (stretching axis direction) to prepare a test piece did. The PET film is peeled off from the test piece, and using a laminator roll, the pressure-sensitive adhesive layer and the glass plate are laminated on one side of a glass plate with a thickness of 0.7 mm and 40 mm × 410 mm using a pressure-sensitive adhesive layer / polarizing plate. I stuck to touch. The resulting laminate was left in a 23 ° C./50% RH environment for 24 hours, and then held in an oven at 60 ° C. for 72 hours. One end was fixed to a wall perpendicular to the floor surface, and the amount of floating of the opposite end was measured with a ruler. The measurements were carried out immediately after removal from the oven and after 24 hours.
〔耐久性試験〕
実施例・比較例で得られた粘着剤層付き偏光板(PETフィルム/粘着剤層/偏光板からなる積層体)を150mm×250mmの大きさに裁断して試験片を作成した。試験片からPETフィルムを剥離し、ラミネーターロールを用いて、粘着剤層/偏光板からなる積層体を厚さ2mmのガラス板の片面に、粘着剤層とガラス板とが接するように貼着した。得られた積層体を、50℃/5気圧に調整されたオートクレーブ中に20分間保持して、試験板を作成した。同様の試験板を2枚作成した。前記試験板を、温度80℃の条件下(耐熱性)または温度60℃/湿度90%RHの条件下(耐湿熱性)で500時間放置し、以下の基準で発泡および断裂の発生を観察して評価した。発泡は凝集力不足の場合に発生し、断裂は応力緩和不足の場合に発生する。 [Durability test]
A polarizing plate with a pressure-sensitive adhesive layer (a laminate comprising a PET film / pressure-sensitive adhesive layer / a polarizing plate) obtained in Examples and Comparative Examples was cut into a size of 150 mm × 250 mm to prepare a test piece. The PET film was peeled off from the test piece, and the laminate consisting of the pressure-sensitive adhesive layer / polarizing plate was attached using a laminator roll so that the pressure-sensitive adhesive layer and the glass plate were in contact with one side of a 2 mm-thick glass plate. . The obtained laminate was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes to prepare a test plate. Two similar test plates were made. The test plate is left for 500 hours under conditions of temperature 80 ° C. (heat resistance) or conditions of temperature 60 ° C./humidity 90% RH (moisture and humidity resistance), and observation of foaming and breakage is observed based on the following criteria: evaluated. Foaming occurs when the cohesion is insufficient and tearing occurs when the stress relaxation is insufficient.
(発泡)
・AA:発泡が全く見られない。
・BB:発泡の面積が全体の1%未満である。
・CC:発泡の面積が全体の1%以上5%未満である。
・DD:発泡の面積が全体の5%以上である。(Foaming)
AA: no foaming was observed at all.
BB: The area of foaming is less than 1% of the whole.
CC: The area of the foam is 1% or more and less than 5% of the whole.
DD: The area of the foam is 5% or more of the whole.
(断裂)
・AA:断裂が全く見られない。
・BB:断裂の面積が全体の1%未満である。
・CC:断裂の面積が全体の1%以上5%未満である。
・DD:断裂の面積が全体の5%以上である。(Rupture)
AA: no tears are seen at all.
BB: The area of fracture is less than 1% of the total.
CC: The area of fracture is 1% or more and less than 5% of the whole.
DD: The area of fracture is 5% or more of the whole.
比較例1および2では、分岐度が0.59の(メタ)アクリル系共重合体を用いている。このため、ゲル分率が高い系(比較例1)では、24時間後のベンディング評価が悪く(5.0mm以上)、また耐久性評価において発泡は認められなかったものの、断裂が多く発生した。また、ゲル分率が低い系(比較例2)では、発泡が多く発生した。 In Comparative Examples 1 and 2, a (meth) acrylic copolymer having a branching degree of 0.59 is used. For this reason, in the system (comparative example 1) with a high gel fraction, although bending evaluation after 24 hours is bad (5.0 mm or more) and although foaming was not recognized in durability evaluation, many tears generate | occur | produced. In addition, in the system with a low gel fraction (Comparative Example 2), a large amount of foaming occurred.
比較例1での共重合体は直鎖型ポリマーであるため、凝集力発現は、架橋剤と共重合体中の官能基との結合のみに依存する。そのため、ゲル分率を高く設定することが、凝集力維持のために必要となる。しかし、ゲル分率が高いと、比較例1の系では応力緩和特性が低くなるため、ベンディングおよび耐久性(耐断裂)の悪化が見られている。 Since the copolymer in Comparative Example 1 is a linear polymer, the cohesive force development depends only on the bond between the crosslinking agent and the functional group in the copolymer. Therefore, it is necessary to set the gel fraction high for maintaining the cohesion. However, when the gel fraction is high, in the system of Comparative Example 1, the stress relaxation property is lowered, so that deterioration in bending and durability (resistance to fracture) is observed.
一方実施例では、分岐度が0.55以下の(メタ)アクリル系共重合体を用い、かつ架橋剤としてイソシアネート化合物および金属キレート化合物を併用しているため、24時間後のベンディング評価が高く(3.0mm以下)、また耐久性評価において発泡および断裂の発生は許容できる範囲にあった。 On the other hand, in the example, since a (meth) acrylic copolymer having a branching degree of 0.55 or less is used and an isocyanate compound and a metal chelate compound are used in combination as a crosslinking agent, bending evaluation after 24 hours is high ( In the evaluation of durability, the occurrence of foaming and tearing was within an acceptable range.
ポリマーに分岐鎖を多く発生させたことにより、架橋剤と共重合体中の官能基との結合に加えて、分岐部分で絡み合いが生じるため、低ゲル分率においても凝集力が発現する。そのため、高温では、絡み合いが緩むため、ベンディングが良好であり、更に耐久性向上の傾向が見られる。 By generating a large number of branched chains in the polymer, in addition to the bond between the crosslinker and the functional group in the copolymer, entanglement occurs in the branched portion, so cohesive force is developed even at a low gel fraction. Therefore, at high temperatures, entanglement is relaxed, so bending is good, and a tendency to improve the durability can be seen.
Claims (9)
(B1)イソシアネート化合物と、
(B2)金属キレート化合物と
を含有し、
前記イソシアネート化合物(B1)と前記金属キレート化合物(B2)との合計含有量が、前記(メタ)アクリル系共重合体(A)100質量部に対して、0.01〜2.5質量部である
ことを特徴とする偏光板用粘着剤組成物。 (A) obtained by copolymerizing a monomer component containing a (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms of an alkyl group and a carboxyl group-containing monomer, and gel permeation chromatography method / multi-angle laser light scattering a detector (GPC-MALS) der degree of branching less than 0.55 as measured by is, acid value Ru 0.1~7.8mgKOH / g der (meth) acrylic copolymer,
(B1) an isocyanate compound,
(B2) containing a metal chelate compound ,
The total content of the isocyanate compound (B1) and the metal chelate compound (B2) is 0.01 to 2.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer (A) A pressure-sensitive adhesive composition for a polarizing plate, characterized by:
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JP2014055116 | 2014-03-18 | ||
JP2014055116 | 2014-03-18 | ||
PCT/JP2015/054775 WO2015141380A1 (en) | 2014-03-18 | 2015-02-20 | Adhesive composition for polarizing plate, adhesive sheet and polarizing plate with adhesive layer |
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JP (1) | JP6530376B2 (en) |
KR (1) | KR20160134679A (en) |
CN (1) | CN106103623A (en) |
WO (1) | WO2015141380A1 (en) |
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JP6880647B2 (en) * | 2016-10-20 | 2021-06-02 | 東洋インキScホールディングス株式会社 | Acrylic resin composition, acrylic film, decorative film and decorative molded body |
JP6363156B2 (en) * | 2016-12-07 | 2018-07-25 | リンテック株式会社 | Battery adhesive sheet and lithium ion battery |
WO2019021843A1 (en) * | 2017-07-25 | 2019-01-31 | 大塚化学株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive film |
JP6879414B1 (en) | 2020-06-30 | 2021-06-02 | 東洋インキScホールディングス株式会社 | Adhesives and adhesive sheets |
KR20230075396A (en) * | 2020-09-25 | 2023-05-31 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Release polarizing plate with adhesive layer |
KR102612236B1 (en) * | 2020-12-11 | 2023-12-08 | 삼성에스디아이 주식회사 | Adhesive composition for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same |
CN115287022B (en) * | 2022-08-24 | 2023-12-15 | 苏州赛伍应用技术股份有限公司 | Environment-friendly high-solid low-adhesive and preparation method and application thereof |
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JPH0782542A (en) * | 1993-09-09 | 1995-03-28 | Sekisui Chem Co Ltd | Pressure-sensitive adhesive for polarizing plate or phase plate |
JPH1046124A (en) * | 1996-08-01 | 1998-02-17 | Nippon Synthetic Chem Ind Co Ltd:The | Self-adhesive composition |
JPH1054906A (en) * | 1996-08-09 | 1998-02-24 | Sekisui Chem Co Ltd | Phase difference plate and elliptic polarizing plate |
JP2003049143A (en) * | 2001-05-31 | 2003-02-21 | Soken Chem & Eng Co Ltd | Adhesive for optical film and optical film using the adhesive |
JP2003114331A (en) * | 2001-08-03 | 2003-04-18 | Oji Paper Co Ltd | Transparent self-adhesive film for protecting polarizing plate |
JP4381686B2 (en) * | 2003-01-22 | 2009-12-09 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition for polarizing film |
JP2006077139A (en) * | 2004-09-10 | 2006-03-23 | Toyo Ink Mfg Co Ltd | Removable pressure sensitive adhesive and removable pressure sensitive adhesive sheet |
JP4883749B2 (en) | 2005-02-08 | 2012-02-22 | 日東電工株式会社 | Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer and production method thereof, optical member with pressure-sensitive adhesive, and image display device |
CN101248152B (en) * | 2005-09-02 | 2011-06-22 | 东洋油墨制造株式会社 | Pressure sensitive adhesive and its preparation, and pressure sensitive adhesion piece |
JP2009132752A (en) | 2007-11-28 | 2009-06-18 | Cheil Industries Inc | Adhesive composition and optical member |
JP5588755B2 (en) * | 2010-06-18 | 2014-09-10 | 株式会社寺岡製作所 | Adhesive for optical members |
JP5554735B2 (en) * | 2010-08-24 | 2014-07-23 | 綜研化学株式会社 | Adhesive for polarizing plate and polarizing plate with adhesive using the same |
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- 2015-02-20 JP JP2016508612A patent/JP6530376B2/en active Active
- 2015-02-20 CN CN201580013854.6A patent/CN106103623A/en active Pending
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WO2015141380A1 (en) | 2015-09-24 |
CN106103623A (en) | 2016-11-09 |
KR20160134679A (en) | 2016-11-23 |
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