JP2011219602A - Acrylic adhesive composition and adhesive film - Google Patents
Acrylic adhesive composition and adhesive film Download PDFInfo
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- JP2011219602A JP2011219602A JP2010089528A JP2010089528A JP2011219602A JP 2011219602 A JP2011219602 A JP 2011219602A JP 2010089528 A JP2010089528 A JP 2010089528A JP 2010089528 A JP2010089528 A JP 2010089528A JP 2011219602 A JP2011219602 A JP 2011219602A
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- Prior art keywords
- acrylic
- sensitive adhesive
- film
- adhesive composition
- acrylic copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 92
- 239000002313 adhesive film Substances 0.000 title abstract description 16
- 239000003522 acrylic cement Substances 0.000 title abstract description 12
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 81
- 239000000178 monomer Substances 0.000 claims abstract description 62
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 38
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 44
- 239000010410 layer Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000013522 chelant Substances 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 4
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical group C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 21
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 2
- 239000010408 film Substances 0.000 description 86
- 239000012790 adhesive layer Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 25
- -1 polyethylene terephthalate Polymers 0.000 description 22
- 239000000758 substrate Substances 0.000 description 20
- 229920000139 polyethylene terephthalate Polymers 0.000 description 16
- 239000005020 polyethylene terephthalate Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000002894 organic compounds Chemical group 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Liquid Crystal (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本発明は、フラットパネルディスプレイの表面に反射防止フィルムを貼着する際などに好適に使用される粘着フィルムと、該粘着フィルムの粘着層を形成するために好適に使用されるアクリル系粘着剤組成物に関する。 The present invention relates to an adhesive film suitably used for attaching an antireflection film to the surface of a flat panel display, and an acrylic adhesive composition suitably used for forming an adhesive layer of the adhesive film. Related to things.
近年、表示装置として、液晶ディスプレイやプラズマディスプレイパネルなどのフラットパネルディスプレイが広く普及している。これらフラットパネルディスプレイの表面には、反射防止フィルム、保護フィルムなどの光学用の表面フィルムが貼着される場合が多い。また、タッチパネルなどの表面にも、これらの表面フィルムが貼着される場合が多い。 In recent years, flat panel displays such as liquid crystal displays and plasma display panels are widely used as display devices. In many cases, an optical surface film such as an antireflection film or a protective film is attached to the surface of these flat panel displays. Moreover, these surface films are often stuck on the surface of a touch panel or the like.
このようにフラットパネルディスプレイ、タッチパネルなどの対象物（パネル基材）の表面に表面フィルムを貼着するための粘着剤には、透明性が求められるため、アクリル系の粘着剤組成物が使用されることが多い。また、その際、粘着剤組成物は、あらかじめ粘着フィルムの形態とされることが多い。
粘着フィルムとしては、粘着剤組成物からなる粘着層の両面に、表面が剥離処理された剥離フィルムを備えたノンキャリアタイプの粘着フィルム（いわゆる、両面セパレータ付フィルム。）や、粘着フィルムの片面には表面フィルムが予め貼着され、他面には剥離フィルムが設けられた表面フィルム一体型の粘着フィルムがある。剥離フィルムとしては、例えばポリエチレンテレフタレート（ＰＥＴ）などの基材フィルムの表面に、シリコーン樹脂などの剥離成分が塗布されて剥離処理されたものが使用される。
Thus, since the adhesive for sticking a surface film on the surface of objects (panel base material), such as a flat panel display and a touch panel, requires transparency, an acrylic adhesive composition is used. Often. In that case, the pressure-sensitive adhesive composition is often in the form of a pressure-sensitive adhesive film in advance.
The pressure-sensitive adhesive film is a non-carrier type pressure-sensitive adhesive film (so-called double-sided separator-attached film) provided with a release film having a surface peel-treated on both sides of a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition, or on one side of a pressure-sensitive adhesive film. There is an adhesive film integrated with a surface film in which a surface film is attached in advance and a release film is provided on the other surface. As the release film, for example, a surface of a base film such as polyethylene terephthalate (PET), which has been subjected to a release treatment by applying a release component such as a silicone resin, is used.
ところが、このような粘着フィルムの粘着層により表面フィルムをパネル基材に貼着し、これを高温高湿下においた場合には、粘着層と表面フィルムとの界面、または、粘着層とパネル基材との界面の密着性が低下することがあった。このように界面での密着性が低下すると、パネル基材のアウトガスなどによる多数の微細気泡が密着性の低下した界面で合体、成長して、目視できる程の気泡（膨れ）となり、白化が起こる場合があった。白化が起こると、パネル基材であるフラットパネルディスプレイやタッチパネルの視認性が低下してしまう。 However, when a surface film is attached to a panel substrate with an adhesive layer of such an adhesive film and placed under high temperature and high humidity, the interface between the adhesive layer and the surface film, or the adhesive layer and the panel base In some cases, the adhesion at the interface with the material deteriorated. When the adhesion at the interface is reduced in this way, a large number of fine bubbles due to the outgas of the panel base material coalesce and grow at the interface where the adhesion is reduced, resulting in bubbles (swelling) that can be visually observed, and whitening occurs. There was a case. When whitening occurs, the visibility of a flat panel display or a touch panel as a panel base material is lowered.
そこで、厳しい条件下においても、パネル基材や表面フィルムと良好に密着し、パネル基材からのアウトガスで微細気泡が生じたとしても、これらが界面で合体、成長せず、視認性が低下しない粘着層を形成できる粘着剤組成物が検討されている。
例えば特許文献１には、アルキル基の炭素数が４〜１２の（メタ）アクリル酸アルキルエステルをモノマー主成分としたアクリル系ポリマー（ａ）を含む粘着剤組成物が記載されている。そして、特許文献１の実施例には、この粘着剤組成物を用いると、７０℃のオーブン中に５時間投入した場合でも、粘着層とポリカーボネート板からなるパネル基材との界面には気泡が認められないことが示されている。
Therefore, even under harsh conditions, even if it adheres well to the panel base material and the surface film, and fine bubbles are generated due to outgas from the panel base material, these do not merge and grow at the interface, and visibility does not deteriorate An adhesive composition capable of forming an adhesive layer has been studied.
For example, Patent Document 1 describes a pressure-sensitive adhesive composition containing an acrylic polymer (a) whose main component is a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in an alkyl group. And in the Example of patent document 1, when this adhesive composition is used, even when it puts in 70 degreeC oven for 5 hours, a bubble exists in the interface of the panel base material which consists of an adhesion layer and a polycarbonate board. It is shown that it is not allowed.
しかしながら、本願発明者の検討によれば、特許文献１に記載された粘着剤組成物を用いた場合、単なる高温下では気泡の発生が認められないものの、湿度も高い高温高湿下では、気泡が発生し、視認性の低下が認められる場合があった。
また、フラットパネルディスプレイ、タッチパネルなどのパネル基材には、ポリカーボネートの他、ポリメタクリル酸メチル（ＰＭＭＡ）が用いられることもある。そのため、ポリカーボネートからなるパネル基材だけでなく、ＰＭＭＡからなるパネル基材にも密着性よく粘着し、高温高湿下でも上述したような気泡が発生しない粘着剤組成物が求められる。
However, according to the study of the inventor of the present application, when the pressure-sensitive adhesive composition described in Patent Document 1 is used, bubbles are not observed at a mere high temperature, but bubbles are not generated at a high temperature and high humidity. In some cases, a decrease in visibility was observed.
In addition to polycarbonate, polymethyl methacrylate (PMMA) may be used for panel substrates such as flat panel displays and touch panels. Therefore, a pressure-sensitive adhesive composition that adheres not only to a panel substrate made of polycarbonate but also to a panel substrate made of PMMA with good adhesion and does not generate bubbles as described above even under high temperature and high humidity is required.
本発明は上記事情に鑑みてなされたもので、透明性が優れ、高温高湿下でも優れた密着性を維持できるアクリル系粘着剤組成物と、これを用いた粘着フィルムの提供を課題とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an acrylic pressure-sensitive adhesive composition that is excellent in transparency and can maintain excellent adhesion even under high temperature and high humidity, and a pressure-sensitive adhesive film using the same. .
本願発明者が鋭意検討したところ、粘着付与剤（タッキファイヤ）として作用するアクリル共重合体（Ｂ）の構成モノマーに、メタクリル酸メチルを必須成分として採用することにより、優れた密着性が得られることに想到した。そして、このようなアクリル共重合体（Ｂ）と併用するアクリル共重合体（Ａ）の構成モノマーに、アクリル酸メチルを必須成分として採用することにより、優れた透明性も維持できることを見出した。 When the present inventor diligently studied, excellent adhesion can be obtained by employing methyl methacrylate as an essential component for the constituent monomer of the acrylic copolymer (B) that acts as a tackifier. I thought of that. And it discovered that the outstanding transparency could be maintained by employ | adopting methyl acrylate as an essential component for the constituent monomer of the acrylic copolymer (A) used together with such an acrylic copolymer (B).
本発明のアクリル系粘着剤組成物は、アクリル酸メチルと、アクリル酸メチル以外の（メタ）アクリル酸エステルと、これらと共重合可能なカルボキシル基含有モノマーおよびヒドロキシル基含有モノマーとを含むモノマー混合物（ａ）を共重合した重量平均分子量が５０万〜２００万のアクリル共重合体（Ａ）と、
メタクリル酸メチルと環状構造を有するモノマーとを含むモノマー混合物（ｂ）を共重合した重量平均分子量が１０００〜１００００であるアクリル共重合体（Ｂ）と、
架橋剤（Ｃ）とが配合され、
前記アクリル共重合体（Ａ）１００質量部に対して、前記アクリル共重合体（Ｂ）を１０〜３５質量部含むことを特徴とする。
前記アクリル酸メチルは、前記モノマー混合物（ａ）中に、３０〜６０質量％含まれることが好ましい。
前記メタクリル酸メチルは、前記モノマー混合物（ｂ）中に、５０〜９０質量％含まれることが好ましい。
前記環状構造を有するモノマーは、メタクリル酸イソボルニルであることが好ましい。
前記架橋剤（Ｃ）は、金属キレート系架橋剤と、エポキシ基を有する架橋剤とからなることが好ましい。
本発明の粘着フィルムは、前記アクリル系粘着剤組成物からなる粘着層の両面に、表面が剥離処理された剥離フィルムが設けられたことを特徴とする。
The acrylic pressure-sensitive adhesive composition of the present invention is a monomer mixture comprising methyl acrylate, a (meth) acrylic acid ester other than methyl acrylate, and a carboxyl group-containing monomer and a hydroxyl group-containing monomer copolymerizable therewith ( an acrylic copolymer (A) copolymerized with a) having a weight average molecular weight of 500,000 to 2,000,000,
An acrylic copolymer (B) having a weight average molecular weight of 1,000 to 10,000, which is obtained by copolymerizing a monomer mixture (b) containing methyl methacrylate and a monomer having a cyclic structure;
And a crosslinking agent (C),
10-35 mass parts of said acrylic copolymers (B) are included with respect to 100 mass parts of said acrylic copolymers (A).
It is preferable that 30-60 mass% of said methyl acrylate is contained in the said monomer mixture (a).
The methyl methacrylate is preferably contained in the monomer mixture (b) in an amount of 50 to 90% by mass.
The monomer having a cyclic structure is preferably isobornyl methacrylate.
The crosslinking agent (C) is preferably composed of a metal chelate-based crosslinking agent and a crosslinking agent having an epoxy group.
The pressure-sensitive adhesive film of the present invention is characterized in that a release film whose surface is peeled is provided on both sides of the pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive composition.
本発明によれば、透明性が優れ、高温高湿下でも優れた密着性を維持できるアクリル系粘着剤組成物と、これを用いた粘着フィルムを提供できる。 According to the present invention, it is possible to provide an acrylic pressure-sensitive adhesive composition that has excellent transparency and can maintain excellent adhesion even under high temperature and high humidity, and a pressure-sensitive adhesive film using the same.
以下、本発明について詳細に説明する。
［アクリル系粘着剤組成物］
本発明のアクリル系粘着剤組成物は、アクリル共重合体（Ａ）と、アクリル共重合体（Ｂ）と、架橋剤（Ｃ）とを含有する。
アクリル共重合体（Ａ）は、アクリル酸メチルと、アクリル酸メチル以外の（メタ）アクリル酸エステルと、これらと共重合可能なカルボキシル基含有モノマーおよびヒドロキシル基含有モノマーとを含むモノマー混合物（ａ）を共重合したものであって、重量平均分子量が５０万〜２００万である。
なお、（メタ）アクリル酸とは、アクリル酸、メタクリル酸を意味する。
Hereinafter, the present invention will be described in detail.
[Acrylic adhesive composition]
The acrylic pressure-sensitive adhesive composition of the present invention contains an acrylic copolymer (A), an acrylic copolymer (B), and a crosslinking agent (C).
The acrylic copolymer (A) is a monomer mixture (a) containing methyl acrylate, a (meth) acrylic acid ester other than methyl acrylate, and a carboxyl group-containing monomer and a hydroxyl group-containing monomer copolymerizable therewith. The weight average molecular weight is 500,000 to 2,000,000.
In addition, (meth) acrylic acid means acrylic acid and methacrylic acid.
アクリル酸メチルをモノマー混合物（ａ）の必須成分とすることによって、得られたアクリル共重合体（Ａ）は、後述のアクリル共重合体（Ｂ）との相溶性に優れ、優れた透明性を発揮する。
アクリル酸メチル以外の（メタ）アクリル酸エステルとしては、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸アルコキシアルキルエステルが使用できる。
（メタ）アクリル酸アルキルエステルとしては、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸エチル、（メタ）アクリル酸２−エチルヘキシルなどが挙げられる。（メタ）アクリル酸アルコキシアルキルエステルとしては、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸２−（ｎ−プロポキシ）エチル、（メタ）アクリル酸２−（ｎ−ブトキシ）エチル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸３−エトキシプロピル、アクリル酸２−（ｎ−プロポキシ）プロピル、（メタ）アクリル酸２−（ｎ−ブトキシ）プロピルなどが挙げられ、２種以上を併用してもよい。
By using methyl acrylate as an essential component of the monomer mixture (a), the obtained acrylic copolymer (A) has excellent compatibility with the acrylic copolymer (B) described later, and excellent transparency. Demonstrate.
As (meth) acrylic acid esters other than methyl acrylate, (meth) acrylic acid alkyl esters and (meth) acrylic acid alkoxyalkyl esters can be used.
Examples of the (meth) acrylic acid alkyl ester include butyl (meth) acrylate, isobutyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. (Meth) acrylic acid alkoxyalkyl esters include: (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (n-propoxy) ethyl, (meth) acrylic acid 2- (n-butoxy) ethyl, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl acrylate, 2- (n)-(meth) acrylate Butoxy) propyl and the like, and two or more may be used in combination.
アクリル酸メチルおよびアクリル酸メチル以外の（メタ）アクリル酸エステルと共重合可能なカルボキシル基含有モノマーとしては、（メタ）アクリル酸、（メタ）アクリル酸β−カルボキシエチル、（メタ）アクリル酸カルボキシペンチル、イタコン酸、クロトン酸、マレイン酸、フマル酸などが挙げられ、２種以上を併用してもよい。
アクリル酸メチルおよびアクリル酸メチル以外の（メタ）アクリル酸エステルと共重合可能なヒドロキシル基含有モノマーとしては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル、（メタ）アクリル酸８−ヒドロキシオクチル、（メタ）アクリル酸１０−ヒドロキシデシル、（メタ）アクリル酸１２−ヒドロキシラウリル、（４−ヒドロキシメチルシクロヘキシル）・メチルアクリレートなどが挙げられ、２種以上を併用してもよい。
Examples of carboxyl group-containing monomers copolymerizable with methyl acrylate and (meth) acrylic esters other than methyl acrylate include (meth) acrylic acid, β-carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. Itaconic acid, crotonic acid, maleic acid, fumaric acid and the like may be mentioned, and two or more may be used in combination.
Examples of hydroxyl group-containing monomers copolymerizable with methyl acrylate and (meth) acrylic acid esters other than methyl acrylate include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) Examples include 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) .methyl acrylate, and the like. Two or more kinds may be used in combination.
なかでも好ましいモノマー混合物（ａ）としては、十分に架橋反応が進行し、高い粘着力が得られやすいことから、アクリル酸メチル以外の（メタ）アクリル酸エステルとして（メタ）アクリル酸ｎ−ブチルを含み、カルボキシル基含有モノマーとしてアクリル酸を含み、ヒドロキシル基含有モノマーとして（メタ）アクリル酸２−ヒドロキシエチルを含む混合物が挙げられる。 Among these, as a preferable monomer mixture (a), since a crosslinking reaction sufficiently proceeds and high adhesive strength is easily obtained, n-butyl (meth) acrylate is used as a (meth) acrylate ester other than methyl acrylate. And a mixture containing acrylic acid as the carboxyl group-containing monomer and 2-hydroxyethyl (meth) acrylate as the hydroxyl group-containing monomer.
モノマー混合物（ａ）中のアクリル酸メチルの含有量は、３０〜６０質量％が好適である。３０質量％未満では、得られるアクリル共重合体（Ａ）のアクリル共重合体（Ｂ）との相溶性が低下し、アクリル系粘着剤組成物の透明性が低下する場合がある。６０質量％を超えると、得られるアクリル共重合体（Ａ）が硬くなり、アクリル系粘着剤組成物の剥離強度が低下する場合がある。
また、得られるアクリル系粘着剤組成物の粘着力などの点から、モノマー混合物（ａ）中のアクリル酸メチル以外の（メタ）アクリル酸エステルの含有量は２５〜６９質量％が好ましく、カルボキシル基含有モノマーの含有量は０．５〜１０質量％が好ましく、ヒドロキシル基含有モノマーの含有量は０．５〜５質量％が好ましい。
The content of methyl acrylate in the monomer mixture (a) is preferably 30 to 60% by mass. If it is less than 30 mass%, compatibility with the acrylic copolymer (B) of the acrylic copolymer (A) obtained may fall, and the transparency of an acrylic adhesive composition may fall. When it exceeds 60 mass%, the acrylic copolymer (A) obtained will become hard and the peeling strength of an acrylic adhesive composition may fall.
In addition, from the viewpoint of adhesive strength of the obtained acrylic pressure-sensitive adhesive composition, the content of (meth) acrylic acid ester other than methyl acrylate in the monomer mixture (a) is preferably 25 to 69% by mass, and is a carboxyl group. The content of the containing monomer is preferably 0.5 to 10% by mass, and the content of the hydroxyl group-containing monomer is preferably 0.5 to 5% by mass.
モノマー混合物（ａ）を共重合して得られるアクリル共重合体（Ａ）は、重量平均分子量が５０万〜２００万である。ここで重量平均分子量が５０万未満では、アクリル共重合体は凝集力が小さいものとなる。そのため、これを含むアクリル系粘着剤組成物から形成された粘着層は、その内部で凝集破壊しやすくなり、その結果、破壊部分において、微細気泡同士が合体して気泡が成長し、高温高湿下における透明性、視認性の低下が大きくなる。一方、２００万を超えると、アクリル共重合体の製造自体が困難となる。より好ましい重量平均分子量は、８０万〜１５０万である。 The acrylic copolymer (A) obtained by copolymerizing the monomer mixture (a) has a weight average molecular weight of 500,000 to 2,000,000. Here, when the weight average molecular weight is less than 500,000, the acrylic copolymer has a small cohesive force. For this reason, the pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition containing the same easily breaks up and breaks down in the inside thereof. Underlying transparency and visibility decrease greatly. On the other hand, when it exceeds 2 million, the production of the acrylic copolymer itself becomes difficult. A more preferable weight average molecular weight is 800,000 to 1,500,000.
また、アクリル共重合体（Ａ）のガラス転移温度は、−６０〜−１０℃が好ましく、−５０〜−１８℃がより好ましい。このような範囲未満では、凝集力が不足し、内部で凝集破壊が生じる場合があり、このような範囲を超えると、粘着力が著しく低下する場合がある。 Moreover, -60--10 degreeC is preferable and, as for the glass transition temperature of an acrylic copolymer (A), -50--18 degreeC is more preferable. If it is less than such a range, the cohesive force may be insufficient and cohesive failure may occur inside, and if it exceeds such a range, the adhesive force may be significantly reduced.
アクリル共重合体（Ａ）は、例えば過酸化ベンゾイル、アゾビスイソブチロニトリルなどの重合開始剤を用いて、溶液重合、塊状重合、乳化重合、懸濁重合などの従来公知の重合方法により製造できる。 The acrylic copolymer (A) is produced by a conventionally known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization using a polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile. it can.
アクリル共重合体（Ｂ）は、粘着付与剤（タッキファイヤ）として作用するものであって、メタクリル酸メチルと環状構造を有するモノマーとを含むモノマー混合物（ｂ）を共重合した重量平均分子量が１０００〜１００００のものである。
メタクリル酸メチルをモノマー混合物（ｂ）の必須成分とすることによって、得られたアクリル共重合体（Ｂ）が配合されたアクリル系粘着剤組成物は、ポリカーボネートからなるパネル基材やＰＥＴなどからなる表面フィルムに対してはもちろん、ＰＭＭＡからなるパネル基材に対しても、良好に密着するものとなる。
環状構造を有するモノマーとしては、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニルなどの非芳香族環（メタ）アクリル酸エステル、（メタ）アクリル酸ベンジルなどの芳香族環（メタ）アクリル酸エステルが好ましく、２種以上を併用してもよい。なかでも、非芳香族環（メタ）アクリル酸エステルが好ましく、特に（メタ）アクリル酸イソボルニルを使用することが、より高い密着性を発現する点で好ましい。
The acrylic copolymer (B) acts as a tackifier (tackifier), and has a weight average molecular weight of 1000 obtained by copolymerizing a monomer mixture (b) containing methyl methacrylate and a monomer having a cyclic structure. -10000.
By using methyl methacrylate as an essential component of the monomer mixture (b), the resulting acrylic pressure-sensitive adhesive composition containing the acrylic copolymer (B) comprises a panel substrate made of polycarbonate, PET, or the like. It adheres well not only to the surface film but also to the panel substrate made of PMMA.
Monomers having a cyclic structure include cyclohexyl (meth) acrylate, non-aromatic rings (meth) acrylate such as isobornyl (meth) acrylate, and aromatic rings (meth) acrylic acid such as benzyl (meth) acrylate. Esters are preferred, and two or more may be used in combination. Among these, non-aromatic ring (meth) acrylic acid esters are preferable, and it is particularly preferable to use isobornyl (meth) acrylate in terms of expressing higher adhesion.
また、モノマー混合物（ｂ）には、１種以上の他のモノマーが１０質量％以下の範囲で含まれてもよく、このようなモノマーとしては、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸アルコキシアルキルエステルが挙げられる。（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸アルコキシアルキルエステルとしては、先に例示したものなどを使用できる。 The monomer mixture (b) may contain one or more other monomers in the range of 10% by mass or less. Examples of such monomers include (meth) acrylic acid alkyl esters and (meth) acrylic. Examples include acid alkoxyalkyl esters. As the (meth) acrylic acid alkyl ester and the (meth) acrylic acid alkoxyalkyl ester, those exemplified above can be used.
モノマー混合物（ｂ）中のメタクリル酸メチルの含有量は、５０〜９０質量％が好適である。５０質量％未満では、ＰＭＭＡからなるパネル基材に対して、密着性が低下し、その結果、視認性が低下する場合がある。一方、９０質量％を超えると、得られるアクリル共重合体（Ｂ）のアクリル共重合体（Ａ）との相溶性が低下し、アクリル系粘着剤組成物の透明性が低下する場合がある。
また、得られるアクリル系粘着剤組成物の粘着力などの点から、モノマー混合物（ｂ）中の環状構造を有するモノマーの含有量は１０〜５０質量％が好ましい。
The content of methyl methacrylate in the monomer mixture (b) is preferably 50 to 90% by mass. If it is less than 50% by mass, the adhesion to the panel substrate made of PMMA is lowered, and as a result, the visibility may be lowered. On the other hand, when it exceeds 90 mass%, compatibility with the acrylic copolymer (A) of the acrylic copolymer (B) obtained may fall, and the transparency of an acrylic adhesive composition may fall.
In addition, the content of the monomer having a cyclic structure in the monomer mixture (b) is preferably 10 to 50% by mass from the viewpoint of the adhesive strength of the obtained acrylic pressure-sensitive adhesive composition.
モノマー混合物（ｂ）を共重合して得られるアクリル共重合体（Ｂ）は、重量平均分子量が１０００〜１００００である。ここで重量平均分子量が１０００未満では、アクリル共重合体の製造自体が困難となる。一方、１００００を超えると、アクリル共重合体（Ａ）との相溶性が低下し、アクリル系粘着剤組成物の透明性が低下する場合がある。 The acrylic copolymer (B) obtained by copolymerizing the monomer mixture (b) has a weight average molecular weight of 1000 to 10,000. Here, when the weight average molecular weight is less than 1000, it is difficult to produce the acrylic copolymer itself. On the other hand, when it exceeds 10,000, the compatibility with the acrylic copolymer (A) may decrease, and the transparency of the acrylic pressure-sensitive adhesive composition may decrease.
また、アクリル共重合体（Ｂ）のガラス転移温度は、８０℃以上が好ましく、より好ましくは１００℃以上である。このような温度未満では、凝集力が不足し、内部で凝集破壊が生じる場合がある。 Moreover, 80 degreeC or more is preferable and, as for the glass transition temperature of an acrylic copolymer (B), More preferably, it is 100 degreeC or more. Below such temperature, the cohesive force is insufficient and cohesive failure may occur inside.
アクリル共重合体（Ｂ）は、例えば過酸化ベンゾイル、アゾビスイソブチロニトリルなどの重合開始剤を用いて、溶液重合、塊状重合、乳化重合、懸濁重合などの従来公知の重合方法により製造できる。 The acrylic copolymer (B) is produced by a conventionally known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization using a polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile. it can.
アクリル共重合体（Ａ）およびアクリル共重合体（Ｂ）の質量比率は、アクリル共重合体（Ａ）１００質量部（固形分）に対して、アクリル共重合体（Ｂ）が１０〜３５質量部（固形分）である。アクリル共重合体（Ｂ）の配合量が上記範囲未満であると、配合の効果が得られにくく、アクリル系粘着剤組成物のパネル基材に対する密着性が低下し、視認性が低下する。一方、上記範囲を超えると、アクリル共重合体（Ｂ）のアクリル系共重合体（Ａ）への相溶性が低下し、アクリル系粘着剤組成物の透明性に悪影響を与える。 As for the mass ratio of an acrylic copolymer (A) and an acrylic copolymer (B), an acrylic copolymer (B) is 10-35 mass with respect to 100 mass parts (solid content) of an acrylic copolymer (A). Part (solid content). When the blending amount of the acrylic copolymer (B) is less than the above range, it is difficult to obtain the blending effect, the adhesion of the acrylic pressure-sensitive adhesive composition to the panel substrate is lowered, and the visibility is lowered. On the other hand, when the above range is exceeded, the compatibility of the acrylic copolymer (B) with the acrylic copolymer (A) is lowered, which adversely affects the transparency of the acrylic pressure-sensitive adhesive composition.
本発明のアクリル系粘着剤組成物は、架橋剤（Ｃ）を必須成分として含有し、金属キレート系架橋剤やエポキシ基を有する架橋剤が使用できるが、好ましくは、架橋剤（Ｃ）として、金属キレート系架橋剤とエポキシ基を有する架橋剤とを併用する。
金属キレート系架橋剤と、エポキシ基を有する架橋剤とを併用することによって、アクリル系粘着剤組成物のパネル基材や表面フィルムに対する密着性を十分に高めることができる。その結果、高温高湿下において、界面での気泡同士の合体を抑え、透明性、視認性の低下を抑制することができる。
The acrylic pressure-sensitive adhesive composition of the present invention contains a crosslinking agent (C) as an essential component, and a metal chelate-based crosslinking agent or a crosslinking agent having an epoxy group can be used. Preferably, as the crosslinking agent (C), A metal chelate crosslinking agent and a crosslinking agent having an epoxy group are used in combination.
By using the metal chelate-based crosslinking agent and the crosslinking agent having an epoxy group in combination, the adhesion of the acrylic pressure-sensitive adhesive composition to the panel substrate or the surface film can be sufficiently enhanced. As a result, coalescence of bubbles at the interface can be suppressed under high temperature and high humidity, and deterioration of transparency and visibility can be suppressed.
架橋剤（Ｃ）のうち、金属キレート系架橋剤は、アクリル系粘着剤組成物から形成された粘着層の表面での架橋反応をより進行させる作用を奏する。そのため、アクリル系粘着剤組成物を用いてノンキャリアタイプあるいは表面フィルム一体型の粘着フィルムの粘着層を形成した際において、粘着層と剥離フィルムの剥離面とが接しても、剥離面に塗布されている剥離成分が粘着層へ移行しにくくなる。剥離成分が粘着層に移行すると、粘着層の粘着力は低下してしまい、表面フィルムやパネル基材との密着性が不十分となる。そのため、このような移行を防止することが密着性を十分に高めるために重要である。
一方、エポキシ基を有する架橋剤は、粘着層の内部など粘着層の全体の架橋反応を進行させ、粘着層全体としての粘着力を高めるように作用する。
特に、表面フィルムがＰＥＴ製である場合、表面フィルムとアクリル系粘着剤組成物からなる粘着層との密着性は不十分となることがあるが、このように金属キレート系架橋剤とエポキシ基を有する架橋剤とを併用することにより、表面フィルムがＰＥＴ製である場合でも、十分な密着性を確保することができる。
Among the cross-linking agents (C), the metal chelate-based cross-linking agent has an effect of further promoting a cross-linking reaction on the surface of the pressure-sensitive adhesive layer formed from the acrylic pressure-sensitive adhesive composition. Therefore, when the pressure-sensitive adhesive layer of the non-carrier type or surface film integrated type pressure-sensitive adhesive film is formed using the acrylic pressure-sensitive adhesive composition, even if the pressure-sensitive adhesive layer and the release surface of the release film are in contact with each other, it is applied to the release surface. It becomes difficult for the peeling component which moves to transfer to the adhesion layer. When the peeling component moves to the pressure-sensitive adhesive layer, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is reduced, and the adhesion to the surface film or the panel substrate becomes insufficient. Therefore, it is important to prevent such transition to sufficiently increase the adhesion.
On the other hand, the crosslinking agent having an epoxy group acts to advance the entire crosslinking reaction of the adhesive layer such as the inside of the adhesive layer and to increase the adhesive force of the entire adhesive layer.
In particular, when the surface film is made of PET, the adhesion between the surface film and the pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive composition may be insufficient. Even when the surface film is made of PET, sufficient adhesion can be secured by using the crosslinking agent in combination.
金属キレート系架橋剤としては、多価金属が有機化合物と共有結合または配位結合しているものが挙げられる。多価金属原子としては、Ａｌ、Ｚｒ、Ｃｏ、Ｃｕ、Ｆｅ、Ｎｉ、Ｖ、Ｚｎ、Ｉｎ、Ｃａ、Ｍｇ、Ｍｎ、Ｙ、Ｃｅ、Ｓｒ、Ｂａ、Ｍｏ、Ｌａ、Ｓｎ、Ｔｉなどが挙げられる。これらのなかでも、Ａｌ、Ｚｒ、Ｔｉが好ましい。特にＡｌが着色が無く、透明性が良い点で好ましい。
また、共有結合または配位結合する有機化合物中の原子としては酸素原子などが挙げられ、有機化合物としては、アルキルエステル、アルコール化合物、カルボン酸化合物、エーテル化合物、ケトン化合物などが挙げられる。
具体的には、特に安定で取り扱いが容易なアルミニウムトリスアセチルアセトネートなどが好適に使用される。また、金属キレート系架橋剤としては、２種以上の化合物を併用してもよい。
Examples of the metal chelate-based crosslinking agent include those in which a polyvalent metal is covalently or coordinately bonded to an organic compound. Examples of the polyvalent metal atom include Al, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. . Among these, Al, Zr, and Ti are preferable. In particular, Al is preferred because it is not colored and has good transparency.
In addition, examples of the atom in the organic compound that is covalently or coordinately bonded include an oxygen atom, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.
Specifically, aluminum trisacetylacetonate that is particularly stable and easy to handle is preferably used. Moreover, as a metal chelate type crosslinking agent, you may use 2 or more types of compounds together.
エポキシ基を含有する架橋剤としては、アクリル共重合体（Ａ）を十分に架橋できることから、１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサンが好適に使用される。その他には、例えば、Ｎ，Ｎ，Ｎ，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、ビスフェノールＡ−エピクロルヒドリン型のエポキシ樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリジジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミンなども使用でき、２種以上を併用してもよい。 As the crosslinking agent containing an epoxy group, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane is preferably used because the acrylic copolymer (A) can be sufficiently crosslinked. In addition, for example, N, N, N, N′-tetraglycidyl-m-xylenediamine, bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin Triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diglycidyl amine and the like may be used, and two or more kinds may be used in combination.
架橋剤（Ｃ）の配合量は、アクリル共重合体（Ａ）１００質量部（固形分）に対して、金属キレート系架橋剤は０．０５〜１．６質量部、エポキシ基を含有する架橋剤は０．０５〜０．４質量部である。より好ましくは、金属キレート系架橋剤は０．０５〜０．８質量部、エポキシ基を含有する架橋剤は０．０５〜０．２質量部である。 The compounding amount of the crosslinking agent (C) is 0.05 to 1.6 parts by mass of a metal chelate crosslinking agent and an epoxy group-containing crosslinking agent with respect to 100 parts by mass (solid content) of the acrylic copolymer (A). An agent is 0.05-0.4 mass part. More preferably, the metal chelate-based crosslinking agent is 0.05 to 0.8 parts by mass, and the epoxy group-containing crosslinking agent is 0.05 to 0.2 parts by mass.
金属キレート系架橋剤の配合量が上記範囲未満であると、剥離フィルムからの剥離成分の粘着層への移行を防止できない可能性がある。また、エポキシ基を有する架橋剤の配合量が上記範囲未満であると、粘着層全体としての粘着力が不十分となる可能性がある。これらの場合には、粘着層と表面フィルムやパネル基材との界面における気泡同士の合体、成長を抑制するほどには、これらを密着できない可能性が生じる。一方、金属キレート系架橋剤の配合量が上記範囲を超えると、粘着層表面の架橋反応が進行しすぎ、また、エポキシ基を含有する架橋剤の配合量が上記範囲を超えると、粘着層全体としての架橋反応が進行しすぎ、その結果、いずれの場合でも、粘着層は剥離性が低下し、糊残りがしやすいものとなる。 When the compounding amount of the metal chelate-based crosslinking agent is less than the above range, there is a possibility that migration of the release component from the release film to the adhesive layer cannot be prevented. Moreover, when the compounding quantity of the crosslinking agent which has an epoxy group is less than the said range, the adhesive force as the whole adhesion layer may become inadequate. In these cases, there is a possibility that the bubbles cannot be brought into close contact to the extent that the coalescence and growth of bubbles at the interface between the pressure-sensitive adhesive layer and the surface film or panel substrate are suppressed. On the other hand, when the compounding amount of the metal chelate-based crosslinking agent exceeds the above range, the crosslinking reaction on the surface of the adhesive layer proceeds excessively, and when the compounding amount of the crosslinking agent containing an epoxy group exceeds the above range, the entire adhesive layer As a result, the cross-linking reaction of the adhesive layer proceeds excessively, and as a result, in any case, the peelability of the pressure-sensitive adhesive layer is reduced, and the adhesive remains easily.
本発明のアクリル系粘着剤組成物は、上記アクリル共重合体（Ａ）および（Ｂ）と、架橋剤（Ｃ）と、さらに必要に応じて、紫外線吸収剤、酸化防止剤、防腐剤、防黴剤、可塑剤、消泡剤、濡れ性調製剤等など添加剤を混合することにより製造できる。また、アクリル系粘着剤組成物は、通常、アクリル共重合体（Ａ）および（Ｂ）の製造工程に由来した溶媒を含有するが、さらに適当な溶媒が加えられ、粘着層を形成するのに適した粘度となるように希釈されたものであってもよい。 The acrylic pressure-sensitive adhesive composition of the present invention comprises the acrylic copolymers (A) and (B), the crosslinking agent (C), and, if necessary, an ultraviolet absorber, an antioxidant, a preservative, It can be produced by mixing additives such as glazes, plasticizers, antifoaming agents, wettability adjusting agents and the like. In addition, the acrylic pressure-sensitive adhesive composition usually contains a solvent derived from the production process of the acrylic copolymers (A) and (B), but an appropriate solvent is further added to form an adhesive layer. It may be diluted to a suitable viscosity.
［粘着フィルム］
本発明のアクリル系粘着剤組成物は、各種用途に使用でき、特に、粘着フィルムの粘着層に好適に使用される。粘着フィルムとしては、粘着剤組成物からなる粘着層の両面に、表面が剥離処理された剥離フィルムを備えたノンキャリアタイプの粘着フィルムや、粘着フィルムの片面には表面フィルムが予め貼着され、他面には剥離フィルムが設けられた表面フィルム一体型の粘着フィルムがある。本発明のアクリル系粘着剤組成物は、いずれの粘着フィルムにも使用できるが、ノンキャリアタイプの粘着フィルムは、表面フィルムをあらかじめ具備したものではないため、需要に応じて、貼着させる表面フィルムの種類をその都度選択できる。よって、在庫管理などの点で非常にメリットがある。
[Adhesive film]
The acrylic pressure-sensitive adhesive composition of the present invention can be used for various applications, and is particularly preferably used for the pressure-sensitive adhesive layer of pressure-sensitive adhesive films. As an adhesive film, on both sides of an adhesive layer made of an adhesive composition, a non-carrier type adhesive film provided with a release film whose surface has been subjected to a release treatment, a surface film is attached in advance to one side of the adhesive film, On the other side, there is an adhesive film integrated with a surface film provided with a release film. The acrylic pressure-sensitive adhesive composition of the present invention can be used for any pressure-sensitive adhesive film, but the non-carrier-type pressure-sensitive adhesive film is not provided with a surface film in advance. You can select the type each time. Therefore, there is a great merit in terms of inventory management.
ノンキャリアタイプの粘着フィルムを製造する場合には、まず、表面が剥離処理された剥離フィルムを用意し、この表面に、アクリル系粘着剤組成物を塗布する。その後、塗布されたアクリル系粘着剤組成物を８０〜１３０℃で加熱して、溶媒を除去、乾燥するとともに、架橋反応を進行させ、粘着層を形成する。ここで粘着層１１の厚みには特に制限はないが、２５〜１５０μｍの範囲が好ましい。
ついで、形成された粘着層の上に、表面が剥離処理された別の剥離フィルムを配置し、貼り合わせることにより、ノンキャリアタイプの粘着フィルムを製造することができる。この際、剥離フィルムの剥離処理された表面が粘着層に接するように配置する。
In the case of producing a non-carrier type pressure-sensitive adhesive film, first, a release film whose surface is peeled is prepared, and an acrylic pressure-sensitive adhesive composition is applied to the surface. Thereafter, the applied acrylic pressure-sensitive adhesive composition is heated at 80 to 130 ° C. to remove and dry the solvent, and the crosslinking reaction is advanced to form an adhesive layer. Although there is no restriction | limiting in particular in the thickness of the adhesion layer 11, The range of 25-150 micrometers is preferable here.
Next, a non-carrier type pressure-sensitive adhesive film can be produced by disposing and bonding another release film having a surface peel-treated on the formed pressure-sensitive adhesive layer. Under the present circumstances, it arrange | positions so that the surface by which the peeling process of the peeling film contacted the adhesion layer.
ここで剥離フィルムとしては、ポリエチレンやポリプロピレンなどのポリオレフィン類、剥離処理したＰＥＴなどが使用される。特にＰＥＴからなる基材フィルムの表面に、シリコーン樹脂などを含む剥離成分が塗布されたものが好適に使用される。剥離フィルムの厚みは、通常２０〜１２５μｍ程度である。 Here, as the release film, polyolefins such as polyethylene and polypropylene, PET subjected to release treatment, and the like are used. In particular, the surface of a base film made of PET is preferably used in which a release component containing a silicone resin or the like is applied. The thickness of the release film is usually about 20 to 125 μm.
こうして製造されたノンキャリアタイプの粘着フィルムを用いて、反射防止フィルム、保護フィルムなどの表面フィルムをフラットパネルディスプレイ、タッチパネルなどのパネル基材の表面に貼着する場合には、粘着層の片面側の剥離フィルムを剥がし、露出した粘着層上に、まず、表面フィルムを貼着する。その後、もう一方の剥離フィルムを剥がし、露出した粘着層上に、パネル基材の表面を密着させればよい。 When sticking a surface film such as an antireflection film or a protective film to the surface of a panel substrate such as a flat panel display or a touch panel using the non-carrier type adhesive film thus manufactured, one side of the adhesive layer First, a surface film is stuck on the exposed adhesive layer. Thereafter, the other release film is peeled off, and the surface of the panel substrate may be adhered to the exposed adhesive layer.
このように本発明のアクリル系粘着剤組成物からなる粘着層により、表面フィルムが貼着されたパネル基材では、粘着層とパネル基材との界面、粘着層と表面フィルムとの界面のいずれにおいても、密着性が非常に優れる。そのため、このパネル基材を高温高湿下におき、パネル基材からアウトガスが発生するなどし、これらの界面に多数の微細な気泡が形成された場合でも、多数の微細な気泡同士の合体が起こりにくい。そのため、透明性、視認性の低下を抑制することができる。 Thus, in the panel base material with which the surface film was stuck by the adhesion layer which consists of an acrylic adhesive composition of this invention, any of the interface of an adhesion layer and a panel substrate, and the interface of an adhesion layer and a surface film Also, the adhesion is very excellent. Therefore, even if this panel substrate is placed under high temperature and high humidity, outgas is generated from the panel substrate, and many fine bubbles are formed at these interfaces, many fine bubbles are coalesced. Hard to happen. Therefore, it is possible to suppress a decrease in transparency and visibility.
なお、本発明のアクリル系粘着剤組成物は、反射防止フィルム、保護フィルムといった表面フィルムの貼着に適しているが、例えば、偏光子フィルム、位相差フィルム、光学補償フィルム、輝度向上フィルム、導光板、プリズムシート、電磁波シールドフィルム、近赤外線吸収フィルムなどの光学用フィルムなどを貼着する際に使用されてもよく、制限はない。また、これらの材質としてもＰＥＴが使用される場合が多いが、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン−酢酸ビニル共重合体フィルムなどでもよく、制限はない。
パネル基材としては、透明性などの点から、ポリカーボネートや（メタ）アクリル樹脂であるＰＭＭＡが使用される場合が多いが、例えば、トリアセチルセルロールなどのセルロース樹脂、ポリエステル樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリオレフィン樹脂、環状ポリオレフィン樹脂（ノルボルネン系樹脂）、ポリアリレート樹脂、ポリスチレン樹脂、ポリビニルアルコール樹脂などでもよく、制限はない。
また、粘着の対象物は、表面フィルムおよびパネル基材に限定されない。
The acrylic pressure-sensitive adhesive composition of the present invention is suitable for attaching a surface film such as an antireflection film or a protective film. For example, a polarizer film, a retardation film, an optical compensation film, a brightness enhancement film, a conductive film, etc. It may be used when an optical film such as an optical plate, a prism sheet, an electromagnetic wave shielding film, or a near-infrared absorbing film is attached, and is not limited. Also, PET is often used as these materials. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polybutylene. A terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film or the like may be used without any limitation.
As the panel base material, polycarbonate or (meth) acrylic resin PMMA is often used from the viewpoint of transparency, for example, cellulose resin such as triacetyl cellulose, polyester resin, polyethersulfone resin, etc. Polysulfone resin, polyamide resin, polyimide resin, polyolefin resin, cyclic polyolefin resin (norbornene resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin and the like may be used without any limitation.
Moreover, the adhesion target is not limited to the surface film and the panel substrate.
以下、本発明について、具体例を挙げて説明する。
［アクリル共重合体（Ａ）］
表１に示す各モノマー混合物（ａ）を以下のように共重合して、アクリル共重合体（Ａ１）〜（Ａ６）を製造した。
Hereinafter, the present invention will be described with specific examples.
[Acrylic copolymer (A)]
Each monomer mixture (a) shown in Table 1 was copolymerized as follows to produce acrylic copolymers (A1) to (A6).
（１）アクリル共重合体（Ａ１）の製造
アクリル酸メチル（ＭＡ）４０質量部、アクリル酸ブチル（ＢＡ）５８質量部、アクリル酸（ＡＡ）１質量部、２−ヒドロキシルエチルアクリレート（２ＨＥＡ：アクリル酸２−ヒドロキシエチル）１質量部、酢酸エチル１００質量部、過酸化ベンゾイル０．１質量部を反応容器に入れた。ついで、この反応容器内の空気を窒素ガスで置換し、窒素雰囲気中、攪拌下で、反応容器内の反応溶液を７５℃まで昇温し、１２時間反応させた。
反応後、反応容器内の液を酢酸エチルで希釈し、固形分２５質量％に調整し、ガラス転移温度−３１℃、重量平均分子量９５万のアクリル共重合体（Ａ１）の溶液を得た。
なお、重量平均分子量は、ゲルパーミエーションクロマトグラフ法で測定を行い、ポリスチレン換算での数値とした。
(1) Production of acrylic copolymer (A1) 40 parts by mass of methyl acrylate (MA), 58 parts by mass of butyl acrylate (BA), 1 part by mass of acrylic acid (AA), 2-hydroxylethyl acrylate (2HEA: acrylic 1 part by mass of acid 2-hydroxyethyl), 100 parts by mass of ethyl acetate, and 0.1 part by mass of benzoyl peroxide were placed in a reaction vessel. Next, the air in the reaction vessel was replaced with nitrogen gas, and the reaction solution in the reaction vessel was heated to 75 ° C. and stirred for 12 hours in a nitrogen atmosphere under stirring.
After the reaction, the liquid in the reaction vessel was diluted with ethyl acetate and adjusted to a solid content of 25% by mass to obtain a solution of an acrylic copolymer (A1) having a glass transition temperature of −31 ° C. and a weight average molecular weight of 950,000.
The weight average molecular weight was measured by a gel permeation chromatograph method and was a numerical value in terms of polystyrene.
（２）アクリル共重合体（Ａ２）〜（Ａ６）の製造
モノマー混合物（ａ）の組成を表１に示すように変えた以外は、アクリル共重合体（Ａ１）と同様の方法により、表１に示す重量平均分子量およびガラス転移温度のアクリル共重合体（Ａ２）〜（Ａ５）の溶液を得た。
なお、アクリル共重合体（Ａ６）については、以下のように製造した。
まず、アクリル酸メチル（ＭＡ）４０質量部、アクリル酸ブチル（ＢＡ）５８質量部、アクリル酸（ＡＡ）１質量部、２−ヒドロキシルエチルアクリレート（２ＨＥＡ：アクリル酸２−ヒドロキシエチル）１質量部、酢酸エチル１００質量部、アゾビスイソブチロニトリル０．１質量部を反応容器に入れた。ついで、この反応容器内の空気を窒素ガスで置換し、窒素雰囲気中、攪拌下で、反応容器内の反応溶液を８０℃まで昇温し、１２時間反応させた。
反応後、反応容器内の液を酢酸エチルで希釈し、固形分２５質量％に調整し、ガラス転移温度−３１℃、重量平均分子量３０万のアクリル共重合体（Ａ６）の溶液を得た。
(2) Production of acrylic copolymers (A2) to (A6) Table 1 was prepared in the same manner as acrylic copolymer (A1) except that the composition of monomer mixture (a) was changed as shown in Table 1. A solution of acrylic copolymers (A2) to (A5) having the weight average molecular weight and glass transition temperature shown in FIG.
In addition, about the acrylic copolymer (A6), it manufactured as follows.
First, methyl acrylate (MA) 40 parts by mass, butyl acrylate (BA) 58 parts by mass, acrylic acid (AA) 1 part by mass, 2-hydroxylethyl acrylate (2HEA: 2-hydroxyethyl acrylate) 1 part by mass, 100 parts by mass of ethyl acetate and 0.1 parts by mass of azobisisobutyronitrile were put in a reaction vessel. Next, the air in the reaction vessel was replaced with nitrogen gas, and the reaction solution in the reaction vessel was heated to 80 ° C. and stirred for 12 hours in a nitrogen atmosphere with stirring.
After the reaction, the liquid in the reaction vessel was diluted with ethyl acetate and adjusted to a solid content of 25% by mass to obtain a solution of an acrylic copolymer (A6) having a glass transition temperature of −31 ° C. and a weight average molecular weight of 300,000.
［アクリル共重合体（Ｂ）］
表２に示す各モノマー混合物（ｂ）を以下のように共重合して、アクリル共重合体（Ｂ１）〜（Ｂ８）を製造した。
[Acrylic copolymer (B)]
Each monomer mixture (b) shown in Table 2 was copolymerized as follows to produce acrylic copolymers (B1) to (B8).
（１）アクリル共重合体（Ｂ１）の製造
メタクリル酸メチル（ＭＭＡ）７５質量部、メタクリル酸イソボルニル（ＩＢＸＭＡ）２５質量部、トルエン１００質量部、アゾビスイソブチロニトリル１０質量部を反応容器に入れた。ついで、この反応容器内の空気を窒素ガスで置換し、窒素雰囲気中、攪拌下で、反応容器内の反応溶液を１００℃まで昇温し、５時間反応させた。
反応後、反応容器内の液をトルエンで希釈し、固形分３０質量％に調整し、ガラス転移温度１１６℃、重量平均分子量５５００のアクリル共重合体（Ｂ１）の溶液を得た。
なお、重量平均分子量は、ゲルパーミエーションクロマトグラフ法で測定を行い、ポリスチレン換算での数値とした。
(1) Production of acrylic copolymer (B1) 75 parts by mass of methyl methacrylate (MMA), 25 parts by mass of isobornyl methacrylate (IBXMA), 100 parts by mass of toluene, and 10 parts by mass of azobisisobutyronitrile are used in a reaction vessel. I put it in. Next, the air in the reaction vessel was replaced with nitrogen gas, and the reaction solution in the reaction vessel was heated to 100 ° C. and allowed to react for 5 hours under stirring in a nitrogen atmosphere.
After the reaction, the liquid in the reaction vessel was diluted with toluene and adjusted to a solid content of 30% by mass to obtain a solution of an acrylic copolymer (B1) having a glass transition temperature of 116 ° C. and a weight average molecular weight of 5500.
The weight average molecular weight was measured by a gel permeation chromatograph method and was a numerical value in terms of polystyrene.
（２）アクリル共重合体（Ｂ２）〜（Ｂ８）の製造
モノマー混合物（ｂ）の組成を表２に示すように変えた以外は、アクリル共重合体（Ｂ１）と同様の方法により、表２に示す重量平均分子量およびガラス転移温度のアクリル共重合体（Ｂ２）〜（Ｂ７）の溶液を得た。
なお、表２中のｉ−ＢＭＡはメタクリル酸イソブチル、ＣＨＭＡはメタクリル酸シクロヘキシルを意味する。
また、アクリル共重合体（Ｂ８）については、モノマー混合物（ｂ）の組成を表２に示すように変えるとともに、アゾビスイソブチロニトリルの量を１質量部とした以外は、アクリル共重合体（Ｂ１）と同様の方法によりその溶液を得た。
(2) Production of acrylic copolymers (B2) to (B8) Table 2 was prepared in the same manner as for acrylic copolymer (B1) except that the composition of monomer mixture (b) was changed as shown in Table 2. A solution of acrylic copolymers (B2) to (B7) having the weight average molecular weight and glass transition temperature shown in FIG.
In Table 2, i-BMA means isobutyl methacrylate and CHMA means cyclohexyl methacrylate.
For the acrylic copolymer (B8), the acrylic copolymer was changed except that the composition of the monomer mixture (b) was changed as shown in Table 2 and the amount of azobisisobutyronitrile was 1 part by mass. The solution was obtained by the same method as (B1).
［実施例１］
表３に示す配合により、アクリル系粘着剤組成物を製造した。表中の数値は、固形分の質量部である。
なお、架橋剤（Ｃ）には、金属キレート系架橋剤として、川研ファインケミカル社製のアルミニウムトリスアセチルアセトネート（表中、アルミキレートＡ（Ｗ）と表記。）を使用し、エポキシ基を有する架橋剤として、三菱瓦斯化学社製の１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサン（表中、ＴＥＴＲＡＤ−Ｃと表記。）を使用した。
ついで、シリコーン樹脂を含む剥離成分により剥離処理された軽剥離タイプの剥離ＰＥＴフィルム（厚さ３８μｍ）の剥離面に、製造されたアクリル系粘着剤組成物を乾燥後の厚み（形成された粘着層としての厚み）が５０μｍとなるように塗布し、１００℃で溶媒を除去して乾燥するとともに架橋反応させ、粘着層を形成した。
ついで、この粘着層上に、シリコーン樹脂を含む剥離成分により剥離処理された重剥離タイプの剥離ＰＥＴフィルム（厚み３８μｍ）を剥離面側が粘着層に接するように貼り合わせ、２３℃、５０％ＲＨで７日間放置し、粘着層の両面に、表面（剥離面）が剥離処理された剥離フィルムが設けられたノンキャリアタイプの粘着フィルムを得た。なお、軽剥離、重剥離とは、剥離しやすさの程度であり、軽剥離は、重剥離よりも剥離しやすいことを意味する。
[Example 1]
An acrylic pressure-sensitive adhesive composition was produced according to the formulation shown in Table 3. The numerical value in a table | surface is a mass part of solid content.
In addition, as a metal chelate type cross-linking agent, the cross-linking agent (C) uses an aluminum trisacetylacetonate (indicated in the table as aluminum chelate A (W)) manufactured by Kawaken Fine Chemical Co., and has an epoxy group. As the cross-linking agent, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane (indicated in the table as TETRAD-C) manufactured by Mitsubishi Gas Chemical Co., Ltd. was used.
Next, the thickness (formed pressure-sensitive adhesive layer formed) after drying the manufactured acrylic pressure-sensitive adhesive composition on the release surface of a light-release type release PET film (thickness 38 μm) that was release-treated with a release component containing a silicone resin The thickness of the adhesive layer was 50 μm, and the solvent was removed at 100 ° C., followed by drying and a crosslinking reaction to form an adhesive layer.
Next, a heavy release type release PET film (thickness: 38 μm) which has been subjected to release treatment with a release component containing a silicone resin is bonded onto the adhesive layer so that the release surface side is in contact with the adhesive layer, and at 23 ° C. and 50% RH. The film was left for 7 days to obtain a non-carrier type pressure-sensitive adhesive film in which a release film whose surface (peeled surface) was peeled was provided on both sides of the pressure-sensitive adhesive layer. In addition, light peeling and heavy peeling are the grades of ease of peeling, and light peeling means that it is easy to peel rather than heavy peeling.
得られた粘着フィルムについて、以下の評価を行った。結果を表３に示す。
（１）粘着層の透明性
粘着フィルムを５０ｍｍ×５０ｍｍに裁断した後、軽剥離タイプの剥離ＰＥＴフィルムを剥がし、光学用のＰＥＴ製表面フィルムを貼着した。その後、これを２３℃、５０％ＲＨで２４時間放置した。その後、重剥離ＰＥＴを剥がし、厚さ２ｍｍのガラス板に貼り合わせて２４時間静置し、透明性評価用の積層体を得た。
次に、光学用のＰＥＴ製表面フィルム、ガラス板および透明性評価用の積層体について、ヘイズメーター（村上色彩研究所製、ＨＭ−６５Ｗ）でヘイズ値（曇り度）を測定し、下記の式で粘着層のヘイズ値を算出した。
粘着層のヘイズ値＝（透明性評価用の積層体のヘイズ値）−（光学用のＰＥＴ製表面フィルムのヘイズ値＋ガラス板のヘイズ値）
得られた粘着層のヘイズ値を以下の３段階で評価した。
○：ヘイズ値 ０．１〜０．５
△：ヘイズ値 ０．６〜０．９
×：ヘイズ値 １以上
The following evaluation was performed about the obtained adhesive film. The results are shown in Table 3.
(1) Transparency of adhesive layer After the adhesive film was cut into 50 mm x 50 mm, the light release type release PET film was peeled off, and an optical PET surface film was attached. Thereafter, this was left at 23 ° C. and 50% RH for 24 hours. Thereafter, the heavy peeled PET was peeled off, bonded to a glass plate having a thickness of 2 mm, and allowed to stand for 24 hours to obtain a laminate for evaluating transparency.
Next, the haze value (cloudiness) is measured with a haze meter (manufactured by Murakami Color Research Laboratory, HM-65W) for a PET surface film for optics, a glass plate, and a laminate for transparency evaluation. Thus, the haze value of the adhesive layer was calculated.
Haze value of adhesive layer = (Haze value of laminate for transparency evaluation) − (Haze value of optical PET surface film + Haze value of glass plate)
The haze value of the obtained adhesive layer was evaluated in the following three stages.
○: Haze value 0.1-0.5
Δ: Haze value 0.6 to 0.9
X: Haze value 1 or more
（２）耐気泡性
上記（１）の透明性の評価において、「○」の結果が得られたものについて、次のように耐気泡性を評価した。結果を表３に示す。
粘着フィルムを５０ｍｍ×５０ｍｍに裁断した後、軽剥離タイプの剥離ＰＥＴを剥がし、光学用のＰＥＴ製表面フィルムを貼着した。その後、これを２３℃、５０％ＲＨで２４時間放置した。その後、重剥離タイプの剥離ＰＥＴを剥がし、厚さ１ｍｍのポリカーボネート基材または厚さ１ｍｍのＰＭＭＡ基材（アクリル基材）に貼り合わせて、２４時間静置した。
このようにして、粘着層を介して基材表面に光学用のＰＥＴ製表面フィルムが貼着された積層体を得た。
この積層体を８０℃、９５％ＲＨで４８時間放置した後、２３℃、５０％ＲＨで２４時間放置して、積層体の表面における気泡生成の様子をルーペで観察した。
耐気泡性について、以下の４段階で評価した。
○：直径０．５ｍｍ以上の気泡が観察されない。
△：直径０．５ｍｍ以上の気泡が部分的に観察される。
×：直径０．５ｍｍ以上の気泡が表面のほぼ全面に観察される。
(2) Bubble resistance In the evaluation of the transparency in (1) above, the bubble resistance of the ones with the result of “◯” was evaluated as follows. The results are shown in Table 3.
After the adhesive film was cut into 50 mm × 50 mm, the light release type peeled PET was peeled off, and an optical PET surface film was attached. Thereafter, this was left at 23 ° C. and 50% RH for 24 hours. Thereafter, the heavy release type peeled PET was peeled off and bonded to a 1 mm thick polycarbonate substrate or a 1 mm thick PMMA substrate (acrylic substrate) and allowed to stand for 24 hours.
Thus, the laminated body by which the surface film made from optical PET was stuck on the base-material surface through the adhesion layer was obtained.
This laminate was allowed to stand at 80 ° C. and 95% RH for 48 hours, and then allowed to stand at 23 ° C. and 50% RH for 24 hours, and the state of bubble formation on the surface of the laminate was observed with a loupe.
The bubble resistance was evaluated in the following four stages.
○: Bubbles having a diameter of 0.5 mm or more are not observed.
Δ: Bubbles having a diameter of 0.5 mm or more are partially observed.
X: Bubbles having a diameter of 0.5 mm or more are observed on almost the entire surface.
［実施例２〜１０、比較例１〜８］
表３および４に示す配合により、アクリル系粘着剤組成物を製造した。
そして、実施例１と同様にして粘着フィルムおよび積層体を製造し、同様に評価した。
結果を表３および４に示す。
[Examples 2 to 10, Comparative Examples 1 to 8]
An acrylic pressure-sensitive adhesive composition was produced according to the formulation shown in Tables 3 and 4.
And the adhesive film and the laminated body were manufactured like Example 1, and evaluated similarly.
The results are shown in Tables 3 and 4.
表の結果からわかるように、各実施例の粘着層は、透明性が優れ、高温高湿下でも優れた密着性を維持し、耐気泡性が優れていた。なお、実施例６では、アクリル共重合体（Ａ４）を構成するモノマー混合物（ａ）中のアクリル酸メチル量が好ましい範囲をやや外れているため、粘着層の透明性がやや低下した。また、実施例９では、アクリル共重合体（Ｂ４）を構成するモノマー混合物（ｂ）中のメタクリル酸メチル量、環状構造を有するモノマー量が好ましい範囲をやや外れているため、アクリル基材に対する耐気泡性がやや低下した。また、実施例１０では、アクリル共重合体（Ｂ５）を構成するモノマー混合物（ｂ）中に含まれる環状構造を有するモノマーが、メタクリル酸イソボルニルでなくメタクリル酸シクロヘキシルであるため、アクリル基材に対する耐気泡性がやや低下した。
一方、比較例１では、アクリル共重合体（Ａ５）を構成するモノマー混合物（ａ）が、アクリル酸メチルを含まないため、アクリル共重合体（Ａ５）とアクリル共重合体（Ｂ１）との相溶性が悪く、透明性が悪かった。
比較例２では、アクリル共重合体（Ｂ６）を構成するモノマー混合物（ｂ）中に、メタクリル酸メチルが含まれないため、アクリル基材に対する耐気泡性が悪かった。
比較例３では、アクリル共重合体（Ｂ７）を構成するモノマー混合物（ｂ）中に環状構造を有するモノマーが含まれず、メタクリル酸メチル量が多いため、透明性が悪かった。
比較例４では、アクリル共重合体（Ａ６）の重量平均分子量が小さいため、粘着層は内部で凝集破壊しやすく、耐気泡性が悪かった。
比較例５では、アクリル共重合体（Ｂ８）の重量平均分子量が大きいため、アクリル共重合体（Ａ１）との相溶性が悪く、透明性が悪かった。
比較例６では、アクリル共重合体（Ｂ１）が少ないため、耐気泡性が悪かった。
比較例７では、アクリル共重合体（Ｂ１）が多いため、アクリル共重合体（Ａ１）とアクリル共重合体（Ｂ１）との相溶性が悪く、透明性が悪かった。
As can be seen from the results in the table, the adhesive layer of each example was excellent in transparency, maintained excellent adhesion even under high temperature and high humidity, and excellent in bubble resistance. In Example 6, since the amount of methyl acrylate in the monomer mixture (a) constituting the acrylic copolymer (A4) was slightly out of the preferred range, the transparency of the adhesive layer was slightly lowered. In Example 9, since the amount of methyl methacrylate and the amount of monomer having a cyclic structure in the monomer mixture (b) constituting the acrylic copolymer (B4) are slightly outside the preferred ranges, The air bubbles were slightly reduced. In Example 10, since the monomer having a cyclic structure contained in the monomer mixture (b) constituting the acrylic copolymer (B5) is cyclohexyl methacrylate instead of isobornyl methacrylate, The air bubbles were slightly reduced.
On the other hand, in Comparative Example 1, since the monomer mixture (a) constituting the acrylic copolymer (A5) does not contain methyl acrylate, the phase of the acrylic copolymer (A5) and the acrylic copolymer (B1) The solubility was poor and the transparency was poor.
In Comparative Example 2, since the monomer mixture (b) constituting the acrylic copolymer (B6) did not contain methyl methacrylate, the bubble resistance against the acrylic base material was poor.
In Comparative Example 3, the monomer mixture (b) constituting the acrylic copolymer (B7) did not contain a monomer having a cyclic structure, and the amount of methyl methacrylate was large, so that the transparency was poor.
In Comparative Example 4, since the weight average molecular weight of the acrylic copolymer (A6) was small, the pressure-sensitive adhesive layer was easy to cohesively break inside, and the bubble resistance was poor.
In Comparative Example 5, since the acrylic copolymer (B8) had a large weight average molecular weight, the compatibility with the acrylic copolymer (A1) was poor and the transparency was poor.
In Comparative Example 6, since the acrylic copolymer (B1) was small, the bubble resistance was poor.
In Comparative Example 7, since there were many acrylic copolymers (B1), the compatibility between the acrylic copolymer (A1) and the acrylic copolymer (B1) was poor, and the transparency was poor.
Claims (6)
メタクリル酸メチルと環状構造を有するモノマーとを含むモノマー混合物（ｂ）を共重合した重量平均分子量が１０００〜１００００であるアクリル共重合体（Ｂ）と、
架橋剤（Ｃ）とが配合され、
前記アクリル共重合体（Ａ）１００質量部に対して、前記アクリル共重合体（Ｂ）を１０〜３５質量部含むことを特徴とするアクリル系粘着剤組成物。 The weight average molecular weight obtained by copolymerizing a monomer mixture (a) containing methyl acrylate, a (meth) acrylic acid ester other than methyl acrylate, and a carboxyl group-containing monomer and a hydroxyl group-containing monomer copolymerizable therewith is 50. 10,000 to 2,000,000 acrylic copolymer (A),
An acrylic copolymer (B) having a weight average molecular weight of 1,000 to 10,000, which is obtained by copolymerizing a monomer mixture (b) containing methyl methacrylate and a monomer having a cyclic structure;
And a crosslinking agent (C),
An acrylic pressure-sensitive adhesive composition comprising 10 to 35 parts by mass of the acrylic copolymer (B) with respect to 100 parts by mass of the acrylic copolymer (A).
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| JP2014196376A (en) * | 2013-03-29 | 2014-10-16 | 東洋インキＳｃホールディングス株式会社 | Adhesive mass and adhesive sheet using the same |
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