CN108884368A - Adhesion agent composition and adhesive sheet - Google Patents
Adhesion agent composition and adhesive sheet Download PDFInfo
- Publication number
- CN108884368A CN108884368A CN201780017767.7A CN201780017767A CN108884368A CN 108884368 A CN108884368 A CN 108884368A CN 201780017767 A CN201780017767 A CN 201780017767A CN 108884368 A CN108884368 A CN 108884368A
- Authority
- CN
- China
- Prior art keywords
- methyl
- adhesive sheet
- monomer
- active energy
- energy beam
- 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.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 181
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 181
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 153
- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 239000000178 monomer Substances 0.000 claims abstract description 141
- 229920000642 polymer Polymers 0.000 claims abstract description 83
- 239000011159 matrix material Substances 0.000 claims abstract description 76
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- -1 pentyl ester Chemical class 0.000 claims description 79
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 72
- 150000002148 esters Chemical class 0.000 claims description 34
- 229920002223 polystyrene Polymers 0.000 claims description 33
- 239000004793 Polystyrene Substances 0.000 claims description 31
- 238000003860 storage Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 5
- HJYKVGWOAOLIKY-UHFFFAOYSA-N methyl 2-methylidenenonanoate Chemical compound CCCCCCCC(=C)C(=O)OC HJYKVGWOAOLIKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- MKKWZRQENPYYAM-UHFFFAOYSA-N C(C(=C)C)(=O)O.CCCCCCCCCCC Chemical compound C(C(=C)C)(=O)O.CCCCCCCCCCC MKKWZRQENPYYAM-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 79
- 239000010408 film Substances 0.000 description 73
- 239000002904 solvent Substances 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 239000004973 liquid crystal related substance Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000001678 irradiating effect Effects 0.000 description 10
- 238000010030 laminating Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000007639 printing Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 150000003440 styrenes Chemical class 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 230000003252 repetitive effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229940117958 vinyl acetate Drugs 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003044 adaptive effect Effects 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 3
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910020388 SiO1/2 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
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- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229960005222 phenazone Drugs 0.000 description 2
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- VOXYRZQCFVVAOZ-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CC(O)COC(C)COC(C)CO VOXYRZQCFVVAOZ-UHFFFAOYSA-N 0.000 description 1
- BBDGCEOSTKYTOQ-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethanol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.OCCOCCOCCOCCO BBDGCEOSTKYTOQ-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- ZTHJQCDAHYOPIK-UHFFFAOYSA-N 3-methylbut-2-en-2-ylbenzene Chemical compound CC(C)=C(C)C1=CC=CC=C1 ZTHJQCDAHYOPIK-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
-
- 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
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J7/29—Laminated material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Project of the present invention is to provide a kind of adhesive sheet, is the adhesive sheet formed by double curing type adhesion agent compositions, and relative dielectric constant is substantially low and excellent in te pins of durability.The present invention contains about following adhesion agent composition and the adhesive sheet formed by the adhesion agent composition, adhesion agent composition：Matrix polymer (A), monomer (B), crosslinking agent (C) and polymerization initiator (D), the matrix polymer (A) contain unit (a1) and the unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group as derived from non-crosslinked property (methyl) acrylate with the branched alkyl groups below of carbon number 5 or more and 9；The monomer (B) at least contains a polymerism unsaturated group；The crosslinking agent (C) is reacted using heat with matrix polymer (A) generation；The polymerization initiator (D) makes the polymerization reaction of monomer (B) start to carry out using the irradiation of active energy beam.
Description
Technical field
The present invention is about adhesion agent composition and adhesive sheet.
Background technique
In recent years, the inputs such as display devices or Trackpad such as liquid crystal display (LCD) dress is widely used in various fields
The trend set.In the manufacture of the display devices such as this or input unit, the purposes for being just bonded optical component uses transparent adhesion
Piece also uses transparent adhesive sheet with being bonded for input unit with regard to display device.
When forming adhesive sheet used in such purposes, using the active energy ray curable containing matrix polymer
Adhesion agent composition or thermohardening type adhesion agent composition.To ask transparency etc. excellent, used for example as matrix polymer：
(methyl) alkyl acrylate, amine Ethyl formate (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) propylene
The acrylic acid series matrix polymers containing acrylic monomer units such as acid esters, polyethers (methyl) acrylate.
Furthermore form the polymerization of the matrix polymer of adhesive sheet, it is known to such as following several polymerizations.Specifically
Have：(1) polymerization implemented using heat；(2) polymerization implemented using active-energy；(3) it is applied using hot (or active energy beam)
After row polymerization, active-energy (or heat) is recycled to implement two sections of polymerizations of polymerization；(4) after implementing polymerization using active-energy, then
The method of two sections of polymerizations of polymerization is implemented using active-energy.
In recent years, the application method of the adhesive sheet as used in such use has use to utilize heat (or active energy by (3)
Measure ray) implement polymerization after, recycle active-energy (or heat) to implement two sections of polymerizations of polymerization, and implement the feelings of cured method
Condition.Because such adhesive sheet is by having the adhesion agent composition of both Thermocurable and active energy ray-curable (hereinafter referred to as
" double curing type adhesion agent compositions ") it is formed, thus there is Thermocurable and active energy ray-curable.So with quilt
Before viscous object fitting, and such as can tentatively adhere by heat cure is only implemented, be then allowed to solid by using active energy beam again
Change and adherend can be adhered to securely.That is, such adhesive sheet is to take into account initial stage adhesion strength and retentivity.
As double curing type adhesion agent compositions used in adhesive sheet, motion, which has to blend in matrix polymer, to be assigned
The crosslinking agent of Thermocurable ingredient, the monomer and Photoepolymerizationinitiater initiater for assigning active energy ray-curable ingredient.Sticker group
It closes and contains active energy ray-curable ingredient in object, constitute the irradiation for utilizing active energy beam, adhesive sheet can be made more to solidify.
Such as Patent Documents 1 to 3 disclose：Double curing type stickers containing acrylic acid series sticker and Photoepolymerizationinitiater initiater
Composition and adhesive sheet is formed by by the adhesion agent composition.Patent document 1 is by making (methyl) acrylic ester copolymer
While object is grafted (methyl) acryloyl group, also it is crosslinked metal ion, can obtain lamination and can borrow at room temperature
The adhesive sheet of ultraviolet curing.In addition, adhesion agent composition disclosed Patent Document 2, contains：200,000 or more weight average molecular weight
And 900,000 or less and containing both (methyl) acrylate copolymers of quantitative (methyl) acrylic acid and active energy ray-curable at
Point.In addition, adhesion agent composition disclosed Patent Document 3, contains：Non-crosslinked property acrylic ester unit has bridging property official
The matrix polymer containing acrylic monomer units, crosslinking agent and the active energy ray-curable ingredient of energy base.Patent document 3
The composition monomer of matrix polymer uses butyl acrylate and acrylic acid -4- hydroxy butyl ester etc..
[citation]
[patent document]
No. 5415658 bulletins of [patent document 1] Japanese Patent No.
[patent document 2] Japanese patent application discloses 2014-196451 bulletin
No. 5610085 bulletins of [patent document 3] Japanese Patent No..
Summary of the invention
Problems to be solved by the invention
It is formed by adhesive sheet by that such as above-mentioned double curing type adhesion agent composition by using, can be obtained preliminary
The bumps of adherend, the adhesive sheet that can be adhered to securely on adherend after active energy beam irradiates are tracked when adhesion.So
And, it is known that be formed by adhesive sheet by double curing type adhesion agent compositions, opposite before and after active energy beam irradiation is situated between
Electric constant is higher, and especially the relative dielectric constant after active energy beam irradiates is not substantially low.
Such as in projection direct capacitance Trackpad, the direct capacitance if finger is by near surface between multiple electrodes can same time-varying
Change, position detection can be carried out in high precision by the ratio of the measurement magnitude of current.But if by which enlargement, location identification
Become to be not easy, the malfunction of Trackpad is caused to increase.To have consideration lower using relative dielectric constant in response to such problem
Adhesive sheet, but the relative dielectric constant of double curing type adhesive sheets is not substantially low, can not be used in double curing type adhesive sheets and take
It is loaded in the display device of the Trackpad through enlargement.
That is, known adhesive sheet fails to take into account concave-convex traceability and low relative dielectric constant, seeks to develop and have
There are double curing type adhesive sheet characteristics, and the adhesive sheet that relative dielectric constant is substantially low.
Furthermore, it is known that be formed by adhesive sheet by double curing type adhesion agent compositions, have the situation of durability deficiency,
The research of people etc. is learnt according to the present invention, has the case where bubble is generated between adhesive sheet and adherend according to usage mode.
Then, present inventor etc. are to solve the problems, such as such known technology, and it is an object of the present invention to provide a kind of glued by double curing types
Agent composition formed adhesive sheet, be the substantially low adhesive sheet of relative dielectric constant, and the purpose is studied.This
Outside, the adhesive sheet for being designed to provide one kind and not having bubble generation etc. and excellent in te pins of durability of present inventor etc., and with regard to the mesh
Carry out study.
Means for solving the problems
The inventors of the present invention are deeply studied intensively in order to solve the above problem, as a result, it has been found that by double curing type adhesion agent compositions
Middle addition has the matrix polymer of set composition, can obtain the substantially low adhesive sheet of relative dielectric constant.In addition, of the invention
The discovery such as person is when using such adhesive sheet, even if not having bubble generation still after implementing solidification using active energy beam,
Excellent durability can be played, completes the present invention then.
Specifically, the present invention has following composition.
[1] a kind of adhesion agent composition, contains：Matrix polymer (A), monomer (B), crosslinking agent (C) and polymerization initiator
(D)；Above-mentioned matrix polymer (A) is contained by non-crosslinked property (methyl) propylene with the branched alkyl groups below of carbon number 5 or more and 9
Unit derived from acid esters (a1) and the unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group；
Above-mentioned monomer (B) at least contains a polymerism unsaturated group；Above-mentioned crosslinking agent (C) is produced using heat with matrix polymer (A)
Raw reaction；Above-mentioned polymerization initiator (D) makes the polymerization reaction of monomer (B) start to carry out using the irradiation of active energy beam.
[2] adhesion agent composition as documented by [1], wherein the molal volume of monomer (B) is 180ml/mol or more, single
The density of body (B) is 1.0g/cm3Below.
[3] adhesion agent composition as documented by [1] or [2], wherein monomer (B) has the alkyl of 5 or more carbon number.
[4] adhesion agent composition as documented by any one of [1]~[3], wherein monomer (B) is from (methyl) propylene
Sour pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) n-octyl, (methyl) acrylic acid are different pungent
Ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) Isodecyl
Ester, (methyl) acrylic acid n-undecane base ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) propylene
Selected in the group that the different stearyl ester of acid, (methyl) isobornyl acrylate and (methyl) acrylic acid-2-ethyl caproite are constituted to
It is a kind few.
[5] adhesion agent composition as documented by any one of [1]~[4], wherein above-mentioned matrix polymer (A) more into
One step contains polystyrene condensate.
[6] a kind of adhesive sheet, has adhering agent layer, the adhering agent layer contain matrix polymer (A), monomer (B) and
Polymerization initiator (D)；Above-mentioned matrix polymer (A) is contained：By with the non-crosslinked of the branched alkyl groups below of carbon number 5 or more and 9
Unit (a1) derived from property (methyl) acrylate and derived by (methyl) acrylic monomers with bridging property functional group
Unit (a2)；Above-mentioned monomer (B) at least contains a polymerism unsaturated group；The polymerization initiator (D) utilizes active-energy
The irradiation of ray and make the polymerization reaction of monomer (B) start to carry out.
[7] adhesive sheet as documented by [6], wherein will be normal to the opposite dielectric before adhesive sheet irradiation active energy beam
Number is set as P, and when will irradiate the relative dielectric constant after active energy beam to adhesive sheet and being set as Q, P-Q value is 0.3 or more.
[8] adhesive sheet as documented by [6] or [7], wherein using the irradiation of active energy beam, in 23 DEG C, frequency
Storage modulus under 1Hz is up to 1.0 × 106Pa or more.
[9] adhesive sheet as documented by any one of [6]~[8], wherein before active energy beam being irradiated to adhesive sheet
Storage modulus be set as S, and when will irradiate the storage modulus after active energy beam to adhesive sheet and being set as T, 0 DEG C to 45 DEG C of T/
S value is 5 or more.
[10] adhesive sheet as documented by any one of [6]~[9], wherein active energy beam will be irradiated to adhesive sheet
Preceding storage modulus is set as S, and when will irradiate the storage modulus after active energy beam to adhesive sheet and being set as T, 3 DEG C to 35 DEG C
T/S value is 10 or more.
[11] adhesive sheet as documented by any one of [6]~[10], wherein above-mentioned adhesive sheet is double-faced pressure-sensitive adhesive sheet.
[12] a kind of manufacturing method of laminate comprising：Make the viscous of adhesive sheet documented by any one of [6]~[11]
Oxidant layer the step of contacting to adherend surface, irradiating active energy beam in this case and adhering agent layer is fully cured.
[13] a kind of application method of adhesive sheet makes the sticker of adhesive sheet documented by any one of [6]~[11]
The step of layer is contacted to adherend surface, irradiates active energy beam in this case and adhering agent layer is fully cured.
Invention effect
It can get according to the present invention and be formed by adhesive sheet by double curing type adhesion agent compositions, and relative dielectric constant fills
Divide low adhesive sheet.In addition, can get the adhesive sheet for not having bubble generation etc. and excellent in te pins of durability according to the present invention.
Adhesive sheet of the invention is except concave-convex traceability is excellent, can be adhered to and be glued securely after active energy beam irradiates
Except object, even because relative dielectric constant is low, durability is also excellent, thus it is preferable to use aobvious equipped with Trackpad in constituting
The bonding of the optical component of showing device.
Detailed description of the invention
Fig. 1 is the cross-sectional view for showing composition an example of adhesive sheet of attached stripping film of the invention.
Fig. 2 is the cross-sectional view for showing composition an example of laminate of the present invention.
Specific embodiment
Hereinafter, the present invention is described in detail for needle.The explanation of documented constitutive requirements below, sometimes according to generation
Embodiment, the concrete example of table and carry out, but the present invention is not limited merely to such embodiment.
(adhesion agent composition)
The present invention is about containing：The adhesion of matrix polymer (A), monomer (B), crosslinking agent (C) and polymerization initiator (D)
Agent composition.Matrix polymer (A) contains：By the non-crosslinked property (methyl) third with the branched alkyl groups below of carbon number 5 or more and 9
Unit derived from olefin(e) acid ester (a1) and the unit as derived from (methyl) acrylic monomers with bridging property functional group
(a2).Monomer (B) at least contains a polymerism unsaturated group.Crosslinking agent (C) carries out anti-using heat and with matrix polymer (A)
The crosslinking agent answered.Polymerization initiator (D) makes the polymerization reaction of monomer (B) start progress using the irradiation of active energy beam
Polymerization initiator.
In the present invention, because matrix polymer (A) contains：By the non-friendship with the branched alkyl groups below of carbon number 5 or more and 9
Unit (a1) and by (methyl) acrylic monomers institute with bridging property functional group derived from connection property (methyl) acrylate
Derivative unit (a2), thus the adhesion agent composition by containing matrix polymer (A), it is substantially low can to form relative dielectric constant
Adhering agent layer.Even if the relative dielectric constant of adhering agent layer is still substantially low after active energy ray-curable, have such
It is preferable to use in the bonding for the optical component for constituting the display device equipped with Trackpad for the adhesive sheet of adhering agent layer.
Because contained by matrix polymer (A) by the non-crosslinked property with the branched alkyl groups below of carbon number 5 or more and 9
Unit (a1) derived from (methyl) acrylate, the alkyl with 5 or more carbon number, and such alkyl is the structure for belonging to branch
It makes, thus molal volume is big, density is small.So the molal volume of matrix polymer (A) can be increased, reduce density.In addition, borrowing
By making unit (a1) that there is the alkyl below of carbon number 9, judges cubical contraction when can inhibit to form polymer, make matrix polymerisations
The molal volume of object (A) maintains the larger value.The result of the grade can form the adhering agent layer of lower relative dielectric constant.
(matrix polymer (A))
Matrix polymer (A) contains：By the non-crosslinked property (methyl) third with the branched alkyl groups below of carbon number 5 or more and 9
Unit derived from olefin(e) acid ester (a1) and the unit as derived from (methyl) acrylic monomers with bridging property functional group
(a2).Matrix polymer (A) preferably has the transparency for the degree for not causing inspecting property of display device to reduce.In addition, this explanation
In book, " unit ", which refers to, constitutes polymeric repetitive unit (monomeric unit).
<The unit (a1) as derived from non-crosslinked property (methyl) acrylate>
The unit (a1) as derived from non-crosslinked property (methyl) acrylate, is by with 5 or more and 9 below points of carbon number
Repetitive unit derived from (methyl) alkyl acrylate of branch alkyl.Such (methyl) alkyl acrylate can be enumerated：(first
Base) isoamyl acrylate, (methyl) Isohexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid different heptan
Ester, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid etc..This etc. can be used alone a kind, can also be used in combination of two or more.
Wherein, it is preferable to use (methyl) acrylic acid-2-ethyl caproites for non-crosslinked property (methyl) acrylic ester unit (a1).
The branched alkyl groups carbon number that the unit (a1) as derived from non-crosslinked property (methyl) acrylate has, as long as 5 or more
And 9 or less, preferably 7 or more and 9 or less.It within the above range, can be formed by by the carbon number setting of branched alkyl groups
The substantially low adhering agent layer of relative dielectric constant.In addition, set within the above range by by the carbon number of branched alkyl groups, it can be easily
Ground controls the degree of polymerization of matrix polymer (A), can obtain the adhesion agent composition of excellent in workability.
The amount of the unit (a1) as derived from non-crosslinked property (methyl) acrylate in matrix polymer (A), relatively
It is preferably 40 mass % or more, more preferably 50 mass % or more, particularly preferably 60 matter in matrix polymer (A) gross mass
Measure % or more.In addition, the amount of unit (a1) is preferably 90 mass % or less, more preferably 85 mass % or less.By general
The amount setting of unit (a1) within the above range, can sufficiently reduce the relative dielectric constant of adhering agent layer, more can be improved
The durability of adhering agent layer.
<The unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group>
The unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group can be enumerated：Hydroxyl monomer
Unit, amino-contained monomeric unit, containing glycidyl (Glycidyl) monomeric unit, carboxyl group-containing monomer unit etc..The equal monomers list
Member can be a kind, also can be two or more.
Hydroxyl monomeric unit is the repetitive unit as derived from hydroxyl monomer.Hydroxyl monomer can be enumerated：(methyl)
(methyl) acrylic acid hydroxyl alkane such as acrylic acid -2- hydroxyl ethyl ester, (methyl) acrylic acid -4- hydroxy butyl ester, (methyl) 2-hydroxypropyl acrylate
Base ester；(methyl) acrylic acid list (binaryglycol ester) etc. (methyl) acrylic acid [(mono-, di- or poly-) stretches alkyl diol ester], (methyl)
Acrylic acid list caprolactone etc. (methyl) acryliclactones.
Amino-contained monomeric unit can be enumerated：(methyl) acrylamide, allylamine etc. are repeated as derived from amino-contained monomer
Unit.
Monomeric unit containing glycidyl can be enumerated：(methyl) Glycidyl Acrylate etc. is derived by monomer containing glycidyl
Repetitive unit.
Carboxyl group-containing monomer unit can be enumerated：Acrylic acid, methacrylic acid.
The unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group in matrix polymer (A)
Amount, relative to matrix polymer (A) gross mass, preferably 0.01 mass % or more, more preferably 0.5 mass % or more.
In addition, the amount of unit (a2) is preferably 40 mass % or less, more preferably 35 mass % or less.If unit (a2's) contains
Amount reaches the lower limit value of above range or more, just sufficiently has for that can maintain bridging property required for semi-cured state, if above-mentioned
The upper limit value of range is hereinafter, necessary adhesion physical property can be maintained, and can form the substantially low adhering agent layer of relative dielectric constant.
<Other monomers unit>
Matrix polymer (A) optionally also can be containing except the unit (a1) as derived from non-crosslinked property (methyl) acrylate
With the other monomers unit other than (methyl) acrylic monomer units (a2) with bridging property functional group.Other monomers can be lifted
(methyl) acrylic ester unit of 4 or less carbon number or 10 or more carbon number out.It can specifically enumerate：(methyl) methyl acrylate, (first
Base) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl)
Lauryl acrylate, (methyl) stearyl acrylate etc..In addition, other (methyl) acrylic ester units also can be containing with carbon
(methyl) acrylic ester unit of the straight chained alkyl below of number 5 or more and 9.It can specifically enumerate：(methyl) acrylic acid n-pentyl ester,
(methyl) the just own ester of acrylic acid, the positive heptyl ester of (methyl) acrylic acid, (methyl) n-octyl, the positive nonyl ester of (methyl) acrylic acid
Deng.In addition, other (methyl) acrylic ester units can be enumerated：(methyl) cyclohexyl acrylate, (methyl) benzyl acrylate etc.
(methyl) acrylic ester unit with cyclic group；And (methyl) acrylonitrile, vinylacetate, styrene, vinyl chloride, ethylene
Base Pyrrolizidine ketone, vinylpyridine etc..The other monomers unit amount of matrix polymer (A) be preferably 20 mass % or less,
More preferably 15 mass % or less.
<Polystyrene condensate>
Matrix polymer (A) used in the present invention preferably further contains polystyrene condensate.Matrix polymer
(A) it can individually contain a kind of polystyrene condensate, can also divide equally containing two or more in the polymeric composition of polystyrene or again
The difference persons such as son amount.
Polystyrene condensate is in hydrophobicity.So by making matrix polymer (A) to contain polystyrene condensate,
Polystyrene condensate meeting locality concentrates near the interface of adhering agent layer under hygrothermal environment, and moisture can be inhibited to flow into adhesion
Oxidant layer.As a result, the humidity resistance of adhering agent layer can be improved in judgement.
The polymeric styrenic monomers of polystyrene, which can be constituted, to be enumerated：Styrene, ring-alkylated styrenes (methylbenzene second
Alkene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl, triethylbenzene ethylene, propylstyrene,
Butylstyrene, hexyl styrene, octyl styrene), halogenated styrenes (chloro styrene, brominated styrene) etc. there is benzene second
The monomer of alkene skeleton.Wherein, styrenic monomers just from do not have can with the aitiogenic functional group of crosslinking agent and can take easily
The viewpoint obtained is, it is preferable to use styrene.
Polystyrene condensate can be the condensate of one kind or two or more styrenic monomers, also can be styrenic monomers
With the copolymer of other monomers.As the copolymers of styrenic monomers and other monomers, there is no particular limitation, can enumerate benzene
The copolymer of vinyl monomer and n-butyl acrylate, methyl methacrylate, butadiene, acrylonitrile etc..
Polystyrene condensate can be hydride (below also known as " hydrogenated styrene system condensate ").When polystyrene polymerize
Body is the polymeric situation of hydrogenated styrene system, the polymeric hydrogenation ratio (unit of hydrogenated styrene system：%) have no special limit
It is fixed, such as 10% or more and 99% or less can be set as.
The polymeric hydrogenation ratio of hydrogenated styrene system be using1H-NMR, from 0.5ppm or more and 3.0ppm main chain below
Polystyrene condensate and the aryl being hydrogenated peak integrated value and 6.5ppm or more and 7.2ppm or less be not hydrogenated
Aryl peak integrated value ratio in seek.
The polymeric weight average molecular weight of polystyrene is preferably 1000 or less, more preferably 700 or less.In addition, styrene
It is that polymeric weight average molecular weight is preferably 400 or more.It is above-mentioned by the polymeric weight average molecular weight of polystyrene to be set in
In range, the intermiscibility between above-mentioned (methyl) acrylic polymeric body that can make becomes more preferably, can form humidity resistance more
Excellent adhering agent layer.In addition, setting by by the polymeric weight average molecular weight of polystyrene within the above range, even if wet
It is still not likely to produce bubble under thermal environment, the superior adhering agent layer of durability can be formed.
The polymeric weight average molecular weight of polystyrene be using gel infiltration chromatograph (GPC), according to following (1)~
(3) value measured.
(1) the polymeric solution coating of polystyrene is dried 2 minutes according to 100 DEG C on peeling paper, obtains film-form
Polystyrene condensate.
(2) by above-mentioned (1) film-form polystyrene condensate obtained, according to the mode for becoming 0.2 mass % of solid
It is dissolved in tetrahydrofuran.
(3) gel infiltration chromatograph (GPC) is used, under the following conditions, is measured according to standard polystyren scaled value
The polymeric weight average molecular weight of polystyrene.
GPC：HLC-8220GPC (Tosoh (stock) system)
Tubing string：It uses 4 TSK-GEL GMHXL (Tosoh (stock) system)
Mobile phase solvent：Tetrahydrofuran
Flow velocity：0.6mL/ points
Tubing string Warm degree：40℃
The polymeric amount of polystyrene, relative to the gross mass of matrix polymer (A), preferably 0.01 mass % with
Upper, more preferably 0.1 mass % or more.In addition, the polymeric amount of polystyrene be preferably 20 mass % or less, more preferably
It is 15 mass % or less, is particularly preferably 10 mass % or less.Above-mentioned model is set in by by the polymeric amount of polystyrene
In enclosing, the relative dielectric constant of adhering agent layer can be more effectively reduced, the adhering agent layer of excellent in te pins of durability can be formed.
Commercially available object can be used in polystyrene condensate.Example as commercially available object can be enumerated：EASTMAN CHEMICAL company
Piccolastic A5 (trade name, styrene list polymers, weight average molecular weight of system：500), Regalrez 1018 (trade name,
The hydride of styrene list polymers, weight average molecular weight：500), (trade name, styrene list polymers, weight are equal by Piccolastic A75
Molecular weight：1200)；The YS resin SX100 of YASUHARA CHEMICAL (stock) system (styrene list polymers, divide equally again by trade name
Son amount：2500) etc..
When using manufacture polystyrene condensate is polymerize, there is no particular limitation for manufacturing method, can suitably select
Select commonly used polymerization.Polymerization can be enumerated：Solution polymerization process, emulsion polymerization method, suspension polymerization etc..This etc.
Among, polymerization is just from the viewpoint that can be more simply manufactured, preferably solution polymerization process.
<The physical property of matrix polymer (A)>
The weight average molecular weight of matrix polymer (A) is preferably 100,000 or more and 2,000,000 or less, more preferably 300,000 or more and
1500000 or less.Within the above range, the semi-cured state of adhesive sheet can be maintained, and can be really by by weight average molecular weight setting
Protect adequately concave-convex traceability.In addition, before the weight average molecular weight of matrix polymer (A) is crosslinked using crosslinking agent (C)
Value.Weight average molecular weight is measured using gel infiltration chromatograph (GPC), the value acquired according to polystyrene benchmark.Matrix is poly-
Closing object (A) can be used commercially available object, also can be used and close winner using known method.
The determination condition of gel infiltration chromatograph (GPC) is as follows：
Solvent：Tetrahydrofuran
Tubing string：Shodex KF801, KF803L, KF800L, KF800D (Showa electrician (stock) system, used by 4 connections)
Tubing string temperature：40℃
Sample concentration：0.5 mass %
Detector：RI-2031plus (JASCO system)
Pump：RI-2080plus (JASCO system)
Flow (flow velocity)：0.8ml/min
Injection rate：10μl
Calibration curve：Using by standard polystyren Shodex standard polystyrene (Showa electrician (stock) system) Mw
Calibration curve made by=1320~2,500,000 10 samples.
The glass transition temperature (Tg) of matrix polymer (A) is preferably -55 DEG C or more and -15 DEG C or less, more preferably -40
DEG C or more and -18 DEG C or less, be particularly preferably -35 DEG C or more and -18 DEG C or less.It is shifted by by the glass of matrix polymer (A)
Temperature (Tg) is set within the above range, cohesiveness when more can improve to form adhering agent layer.Whereby, it can get durability
Excellent and excellent adhesion strength adhering agent layer.
<The amount of matrix polymer (A)>
The amount of matrix polymer (A), relative to the gross mass of adhesion agent composition, preferably 75 mass % or more,
It more preferably 80 mass % or more, is particularly preferably 85 mass % or more.In addition, the amount of matrix polymer (A) is preferably 98
It quality % or less, more preferably 95 mass % or less, is particularly preferably 90 mass % or less.
(monomer (B))
Monomer (B) is the monomer at least containing a polymerism unsaturated group.Monomer (B) also can be containing at least with one
The mono-functional monomers (b1) of polymerism unsaturated group and multiple functional radical monomer with 2 or more polymerism unsaturated groups
(b2) one at least in.Polymerism unsaturated group can enumerate the base of the double bond containing ethylene, can be such as：(methyl) acryloyl
Base, vinyl etc..Monomer (B) can also contain any one of mono-functional monomers (b1) or multiple functional radical monomer (b2), also may be used
Contain for mono-functional monomers (b1) and multiple functional radical monomer (b2) both sides.
Adhesion agent composition of the invention can make to adhere by monomer (B) is contained according to the 1st stage (semi-solid preparation step)
When agent composition heat cured, the adhesive sheet of thermosetting compound can be made in semi-cured state, and active energy ray-curable.This
Outside, when solidifying adhesion agent composition using active energy beam irradiation in the 1st stage, the adhesive sheet of photocured product is solid in half
Change state, and there is Thermocurable.In addition, the present invention implements once again after the 1st stage execution heat cure and in semi-cured state
The heat cure in the 2nd stage can make to be fully cured.
Monomer (B) also can be used the vapour pressure at 25 DEG C in 300Pa or less person.Whereby, coating adaptive can be promoted, when to viscous
Agent composition implement coating and when heat cure, the less heavy wall end that generates can be formed in the case where selectively evaporating solvent
The few adhering agent layer of coating defects such as generation or blast hole.
25 DEG C of vapour pressures of monomer (B) can in 200Pa or less, also can be in 100Pa or less.The lower limit of vapour pressure, just from viscous
The coating adaptive viewpoint of agent composition, there is no particular limitation.The vapour pressure of monomer (B) can be according to 2258 " crude oil of JIS K
And fuel oil-steam pressure test method-Lei Shi method " etc. be measured, in addition, using such as website http：//
Www.chemspider.com/ or ACD/PhysChem Suite software can acquire predicted value.
Furthermore the fusing point of monomer (B) can be at 25 DEG C or less.The transparency (the mist degree for being formed by adhesive sheet can be promoted whereby
Deng) etc..In addition, the fusing point of monomer (B) can 20 DEG C or less, also can be at 15 DEG C or less.The lower limit of fusing point is not particularly limited.It is single
The fusing point of body (B) is according to JIS K 0064：1992 " fusing points and fusion range measuring method of chemicals " etc. can measure.
As the concrete example of mono-functional monomers workable for the present invention (b1), can enumerate：(methyl) amyl acrylate,
(methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (first
Base) the positive nonyl ester of acrylic acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (first
Base) acrylic acid n-undecane base ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) acrylic acid is different hard
Rouge ester, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite etc..As fusing point in 25 DEG C of single officials below
Energy base monomer (b1) can be enumerated：(methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl)
N-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl)
The positive last of the ten Heavenly stems ester of acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid n-undecane base ester, (methyl) lauryl acrylate,
(methyl) isostearyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite.
Multiple functional radical monomer (b2) can be enumerated：Two (methyl) acrylic acid glycol esters, two (methyl) acrylic acid triethylene glycols
Ester, two (methyl) acrylic acid -1,3-BDO ester, two (methyl) acrylic acid -1,4-butanediol ester, two (methyl) acrylic acid -1,
9- nonanediol ester, diacrylate -1,6- hexylene glycol ester, two (methyl) acrylic acid polybutadiene alcohol esters, two (methyl) acrylic acid new penta
Diol ester, two (methyl) acrylic acid tetraethylene glycol esters, two (methyl) acrylic acid tripropylene glycol esters, two (methyl) acrylic acid poly- the third two
Alcohol ester, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylate, pentaerythritols, four (methyl) acrylic acid Ji Wusi
(methyl) esters of acrylic acid of the polyalcohols such as alcohol ester；Vinyl methacrylate etc..
In addition, monomer (B), which can also not have, to be presented instead with functional group contained by (methyl) acrylic monomer units (a2)
The functional group of answering property.Such as monomer (B) can have functional group's (such as hydroxyl) identical as (methyl) acrylic monomer units (a2),
Or can also not have functional group.
The molal volume of monomer (B) is preferably 90ml/mol or more, more preferably 180ml/mol or more, is particularly preferably
It 190ml/mol or more, is most preferably 200ml/mol or more.In addition, the molal volume of monomer (B) be preferably 500ml/mol with
Under.In addition, the density of monomer (B) is preferably 1.0g/cm3Below, it is more preferably 0.9g/cm3Below.In the present invention, by using
Molal volume is larger and the lesser monomer of density (B), can obtain the lower adhering agent layer of relative dielectric constant, in order to can more have
Improve the durability of adhering agent layer in effect ground.In addition, molal volume is larger and the lesser monomer of density (B) by using, when will have
It, can when the adhesive sheet of standby adhering agent layer is used in the fittings of input units such as display devices, the Trackpads such as liquid crystal display (LCD)
Inhibit from liquid crystal display panel side.
The alkyl that monomer (B) is preferably 5 or more with carbon number, the alkyl for being more preferably 10 or more with carbon number.In addition, single
The branched alkyl groups that body (B) is more preferably 5 or more with carbon number, the branched alkyl groups for being particularly preferably 10 or more with carbon number.By list
Body (B) contains the alkyl with set construction, can obtain the lower adhering agent layer of relative dielectric constant, can more effectively improve
The durability of adhering agent layer.In addition, being used in the displays such as liquid crystal display (LCD) dress if will be provided with the adhesive sheet of adhering agent layer
Set, the fitting of input units such as Trackpad when, can inhibit from liquid crystal display panel side.
Monomer (B) polymerization is usually set to become higher molecular weight body, the more short then monomer of chain length atomicity is easier to each other
Bond, can generate superior solidification.But the present invention can promote monomer (B) by using such as above-mentioned monomer (B)
With being entangled with for matrix polymer (A).Whereby, judge that adhesion agent composition is easy solidify, can play excellent retentivity.
Monomer (B) with carbon number for 5 or more alkyl can be enumerated：(methyl) amyl acrylate, (methyl) acrylic acid oneself
Ester, (methyl) heptylacrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid,
The different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid n-undecane
Base ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) isostearyl acrylate, (methyl) acrylic acid
Isobornyl thiocyanoacetate and (methyl) acrylic acid-2-ethyl caproite etc..Monomer (B) preferably selects from above-mentioned group at least one kind of.
Furthermore monomer (B) can also have multiring structure.Whereby, superior retentivity can be played after being fully cured.Tool
The monomer for having multiring structure can be multicyclic aliphatic monomer, also can be Ppolynuclear aromatic monomer.Multiring structure can enumerate bicyclic structure
It makes and is constructed with tricyclic.The substituent groups such as alkyl can be also bonded on the grade multiring structures.The concrete example of multiring structure can illustrate such as：
Norbornene ring, adamantane ring etc..
<The amount of monomer (B)>
The amount of monomer (B) in adhesion agent composition cooperates composition, molecular weight or the crosslinking of matrix polymer (A)
Density etc. is suitably selected, and is not particularly limited, relative to 100 mass parts of matrix polymer (A), preferably 5 mass parts with
Above, 10 mass parts or more are more preferably, are particularly preferably 15 mass parts or more.In addition, the amount of monomer (B) is preferably 150 matter
Below amount part, more preferably 120 be below the mass, particularly preferably 90 below the mass.
Furthermore the amount of monomer (B), relative to the gross mass of adhesion agent composition, preferably 1 mass % or more, more
It preferably 2 mass % or more, is particularly preferably 5 mass % or more.In addition, the amount of monomer (B) be preferably 60 mass % or less,
It more preferably 50 mass % or less, is particularly preferably 35 mass % or less.
If monomer (B) is the case where mono-functional monomers (b1) contains with multiple functional radical monomer (b2) both sides, cooperation is poly-
The appropriate selection of row again such as composition, molecular weight or the crosslink density of object (A) is closed, there is no particular limitation, relative to matrix polymer
(A) 100 mass parts, mono-functional monomers (b1) can preferably be set as 4 mass parts or more and 120 below the mass, more preferably 8 matter
Amount part more than and 100 be below the mass, particularly preferably 12 mass parts or more and 80 below the mass.Multiple functional radical monomer (b2) is excellent
Choosing can be set as 1 mass parts or more and 30 below the mass, more than more preferably 2 mass parts and 20 below the mass, be particularly preferably 3
More than mass parts and 10 below the mass.In addition, mono-functional monomers (b1) and multiple functional radical monomer (b2's) contains mass ratio
It can be set as 2: 1, preferably 3：It 1, is particularly preferably 5: 1.
(crosslinking agent (C))
Crosslinking agent (C) will be with matrix polymer (A) aitiogenic crosslinking agent using heat.As crosslinking agent (C), from example
Such as：Isocyanate compound, epoxide, oxazoline compound, aziridine cpd, metal chelate compound, butylation
Known in melamine compound etc. in crosslinking agent, considered and matrix polymer (A) possessed by it is anti-between bridging property functional group
Answering property and suitably select.Such as when bridging property functional group contains hydroxyl the case where, for the reactive view from hydroxyl, it can make
Use isocyanate compound.Just from the unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group can be made
, it is preferable to use isocyanate compound, epoxide for the viewpoint being crosslinked easily.
Isocyanate compound can be enumerated：Toluene-2,4-diisocyanate stretches xylylene diisocyanate (xylene
Diisocyanate, XDI), hexamethylene diisocyanate, isophorone diisocyanate etc..
Epoxide can be enumerated：Ethylene glycol Diglycidyl, polyethylene glycol Diglycidyl, propylene glycol diepoxy third
Ether, polypropylene glycol Diglycidyl, glycerol Diglycidyl, neopentyl glycol Diglycidyl, 1,6- hexylene glycol Diglycidyl,
Bis- (N, the N- 2-glycidyl aminomethyl) hexamethylenes of four glycidyl dimethylphenylene diamines, 1,3-, trimethylolpropane polycyclic oxygen
Propyl ether, the poly- glycidyl ethers of two glycerol, the poly- glycidyl ethers of polyglycereol, the poly- glycidyl ethers of D-sorbite etc..
Crosslinking agent (C) can be used alone a kind, can also be used in combination of two or more.Crosslinking agent (C's) in adhesion agent composition contains
The amount of having cooperates the appropriate selection of row again such as desired bonding physical property, is not particularly limited, relative to 100 matter of matrix polymer (A)
Measure part, can preferably be set as 0.01 mass parts or more and 5 below the mass, more than more preferably 0.03 mass parts and 3 mass parts
Below.
Furthermore the amount of crosslinking agent (C) is preferably set to 0.01 mass % relative to the gross mass of adhesion agent composition
Above and 5.0 mass % or less, more preferably 0.02 mass % or more and 2.0 mass % or less.
(polymerization initiator (D))
Polymerization initiator (D) makes the polymerization reaction of monomer (B) start to carry out using the irradiation of active energy beam.Polymerization
Initiator (D) is as long as just can start the polymerization reaction of progress monomer (B) using the irradiation of active energy beam, using light
Object known in polymerization initiator etc..
Herein, so-called " active energy beam ", which refers to, has quanta of energy person in electromagnetic wave or charge-particle beam, can be such as：
Ultraviolet light, electron beam, luminous ray, X-ray, ion beam etc..Wherein, for the viewpoint from versatility, preferably ultraviolet light
Or electron beam, more preferably ultraviolet light.
Polymerization initiator (D) can be enumerated：Acetophenone series initiators, benzoin ether series initiators, diphenylketone series initiators,
Hydroxyalkyl phenones series initiators, thioxanthones series initiators, amine system initiator etc..
Acetophenone series initiators can specifically be enumerated：Diethoxy acetophenone, benzyl dimethyl ketal etc..
Benzoin ether series initiators can specifically be enumerated：Benzoin, benzoin methylether etc..
Diphenylketone series initiators can specifically be enumerated：Diphenylketone, o-benzoyl yl benzoic acid methyl esters etc..
Hydroxyalkyl phenones series initiators can specifically be enumerated：1- hydroxyl-cyclohexyl-phenyl -one etc..
Thioxanthones series initiators can specifically be enumerated：2-isopropylthioxanthone, 2,4- dimethyl thioxanthone etc..
Amine system initiator can specifically be enumerated：Triethanolamine, 4- mesitylenic acid ethyl ester etc..
Polymerization initiator (D) can be used alone a kind, can also be used in combination of two or more.Polymerization initiator in adhesion agent composition
(D) the active energy beam exposure etc. when amount cooperates the amount of monomer (B), is allowed in semi-solid preparation or is fully cured
The appropriate selection of row again, is not particularly limited, relative to the gross mass of monomer (B), preferably 0.05 mass % or more and 10 matter
Measure % or less, more preferably 0.1 mass % or more and 5.0 mass % or less.
Furthermore the amount of polymerization initiator (D), relative to 100 mass parts of matrix polymer (A), preferably 0.1 mass
Part or more and 10 below the mass, more than more preferably 1 mass parts and 5 below the mass.
(solvent (E))
Adhesion agent composition of the invention also can further contain solvent (E).Solvent (E) is to promote sticker group
It closes the coating adaptive of object and uses.
Such solvent (E) can enumerate：Hexane, heptane, octane, toluene, dimethylbenzene, ethylbenzene, hexamethylene, hexahydrotoluene etc.
Hydro carbons；The halogenated hydrocarbons such as methylene chloride, trichloroethanes, trichloro ethylene, tetrachloro-ethylene, dichloropropane；It is methanol, ethyl alcohol, propyl alcohol, different
The alcohols such as propyl alcohol, butanol, isobutanol, diacetone alcohol；The ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran；Acetone, first
The ketones such as ethyl ketone, methylisobutylketone, isophorone, cyclohexanone；Methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate,
The esters such as amyl acetate, ethyl butyrate；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol list
The polyalcohols such as methyl ether, dihydroxypropane single-ether, propylene glycol monomethyl ether acetate and its derivative.
Solvent (E) can be enumerated without polymerism unsaturated group and 25 DEG C of vapour pressures solvent high compared with monomer (B).Monomer
(B) bigger with the vapour pressure deficit of solvent (E), then coating defects are fewer, more easy to manufacture, thus the vapour pressure of solvent (E) is preferred
It is set as 2000Pa or more, more preferably 5000Pa or more.Though the upper limit is not particularly limited, so it is practical on be in 50000Pa or less.It is molten
Using JIS-K 2258-2, " Crude Oil & Petroleum Products-vapour pressure asks Fa-the 2 to the vapour pressure of agent (E)：3 plavinis " etc.
It can measure, in addition, utilizing such as website http：//www.chemspider.com or ACD/PhysChem Suite software
It can predict.
Without polymerism unsaturated group and 25 DEG C of vapour pressures solvent high compared with monomer (B) can be enumerated：Hexane, heptane, ring
Hexane, benzene, toluene, ethyl alcohol, isopropanol, diisopropyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, methylisobutylketone, ethyl acetate etc..
Above-mentioned solvent can be according to the type appropriate selection of row again of monomer (B).
Furthermore 25 DEG C of surface tension of solvent (E) can be set as 20mN/m or more and less than 40mN/m, can also be set as 22mN/m
Above and less than 36N/m.If surface tension is above-mentioned lower limit value or more, can inhibit to become orange peel (orange peel) shape, if
Less than above-mentioned upper limit value is then less prone to the coating defects such as the generation of heavy wall end (frame).
The solubility parameter difference of solvent (E) and monomer (B) may be provided in 2 [(cal/cm3)1/2] within, can also be set in 1.5
[(cal/cm3)1/2] within.Whereby, it is not easy to cause and causes orange peel (orange peel) because promoting the evaporation of solvent (E) extremely
The coating defects of generation.Solubility parameter is the pointer as dissolution, has following formula connotation.
δ=(Δ E/V) 1/2
Herein, δ is solubility parameter, and Δ E is molar energy of vaporization (cal/mol), and V is molal volume (ml/mol).Dissolution
Property parameter δ value to each other can excellent dissolution close to person.The rule of thumb of excellent dissolution is consistent to each other with fellow.Dissolubility ginseng
Number can be sought using various methods, and this specification utilizes Fedors method, and chemically composition calculates.
Solvent (E) can be used alone a kind, can also be used in combination of two or more.In adhesion agent composition, the amount of solvent (E) is simultaneously
Be not particularly limited, relative to 100 mass parts of matrix polymer (A) preferably may be set to 25 mass parts or more and 500 mass parts with
Under, more preferably more than 30 mass parts and 400 below the mass.
Furthermore the amount of solvent (E) preferably may be set to 10 mass % or more relative to adhesion agent composition gross mass
And 90 below mass %, more preferably 20 mass % or more and 80 mass % or less.
(plasticizer)
Adhesion agent composition of the invention can also contain plasticizer.In the case where containing plasticizer, plasticizer contains
Amount relative to 100 mass parts of matrix polymer (A), be preferably set to 50 below the mass, more preferably 30 below the mass, it is special
Preferably 10 below the mass.
Plasticizer can be used without function mafic acrylic polymer.So-called " no function mafic acrylic polymer " refers to only
By do not have it is acrylate-based other than functional group the condensate that is constituted of acrylic monomer units or by not having acrylic acid
The acrylic monomer units of functional group other than ester group polymerize with what the non-acrylic monomer units for not having functional group were constituted
Body.
Acrylic monomer units without the functional group other than acrylate-based can be enumerated and non-crosslinked property (methyl) third
Olefin(e) acid ester units (a1) are same person.
Non- acrylic monomer units without functional group can be enumerated：Vinylacetate, vinyl propionate, butyric acid ethylene
Ester, vinyl caproate, sad vinyl acetate, caprate, vinyl laurate, tetradeconic acid vinyl acetate, vinyl palmitate,
The generating vinyl carboxylates esters or styrene etc. such as stearic acid vinyl ester, cyclohexane carboxylic vinyl acetate, vinyl benzoate.
(any ingredient)
Adhesion agent composition can also contain other compositions other than the above in the range of will not undermine effect of the present invention.
Other compositions optionally can from the known ingredient of the additive as sticker, such as：Antioxidant, preventing metal corrosion agent,
The middle selection of the light stabilizers such as tackifiers, silane coupling agent, ultraviolet absorbing agent, the amine compound that is obstructed etc..
Antioxidant can be enumerated：Phenolic antioxidant, amine antioxidant, lactone system antioxidant, phosphorous antioxidant,
Sulfur antioxidant etc..The grade antioxidants can be used alone a kind, can also be used in combination of two or more.
Preventing metal corrosion agent can enumerate enumerate BTA system resin.
Tackifiers can be enumerated：Rosin system resin, terpenic series resin, terpenes phenol resin, coumarone-indenes system resin, benzene second
Alkene system resin, diformazan benzene series resin, phenol resin, Petropols etc..
Silane coupling agent can enumerate mercaptoalkoxysilane compound (such as sulfydryl substituted alkoxy oligomer etc.) etc..
Ultraviolet absorbing agent can be enumerated：Benzotriazole based compound, diphenylketone based compound etc..But when being fully cured
When active energy ray use ultraviolet light when, it is necessary to added in the range of will not inhibit polymerization reaction.
(adhesive sheet)
For the present invention about a kind of adhesive sheet, which, which contains, utilizes heating or active-energy for above-mentioned adhesion agent composition
Semi-solid preparation that ray makes and the adhering agent layer formed.Adhesive sheet of the invention has adhering agent layer, which contains：Base
Matter polymer (A), monomer (B) and polymerization initiator (D)；The matrix polymer (A) contains：By with carbon number 5 or more and 9 or less
Branched alkyl groups non-crosslinked property (methyl) acrylate derived from unit (a1) and by with bridging property functional group's
Unit (a2) derived from (methyl) acrylic monomers.The monomer (B) at least contains a polymerism unsaturated group.The polymerization is drawn
Send out agent (D) makes the polymerization reaction of monomer (B) start to carry out using the irradiation of active energy beam.
Adhesive sheet of the invention has adhering agent layer.Adhesive sheet can be the single layer adhesive sheet being only made of adhering agent layer.This
Outside, adhesive sheet of the invention can be single side adhesive sheet, also can be double-faced pressure-sensitive adhesive sheet.
Single side adhesive sheet can enumerate on supporter lamination the multilayer tablet of adhering agent layer.In addition, in supporter and adhesion
Also settable other layer between oxidant layer.
Double-faced pressure-sensitive adhesive sheet can be enumerated：The single layer adhesive sheet that is made of adhering agent layer, by adhering agent layer through the more of multiple laminations
Layer adhesive sheet, between adhering agent layer and adhering agent layer lamination the multilayer adhesive sheet of other adhering agent layers, adhering agent layer with
Between adhering agent layer lamination the multilayer adhesive sheet of supporter.When double-faced pressure-sensitive adhesive sheet has the case where supporter, supporter is preferred
Use transparent supporting body.Such double-faced pressure-sensitive adhesive sheet is because the transparency of whole adhesive sheet is also excellent, thus is applicable to optics structure
The bonding of part to each other.
Among above-mentioned, adhesive sheet of the invention is preferably carrier-free formula, and the single layer being preferably made of adhering agent layer glues
Piece or the multilayer adhesive sheet by the multiple laminations of adhering agent layer, the single-layer double-side adhesive sheet being more preferably made of adhering agent layer.
When adhesive sheet of the invention has supporter, can be enumerated as supporter：Polystyrene, Styrene And Chloroalkyl Acrylates
The plastic cement such as copolymer, acrylic resin, polyethylene terephthalate, polycarbonate, polyether-ether-ketone, Triafol T are thin
Film；The optical thin film etc. of anti-reflective film, electromagnetic shielded film etc..
The surface of adhering agent layer of the invention preferably utilizes stripping film to cover.That is, the present invention also can be for stripping film
Adhesive sheet.
It is the cross-sectional view with composition an example of the adhesive sheet of stripping film shown in Fig. 1.Adhesive sheet 11 shown in Fig. 1 has removing
Piece (12a, 12b).In addition, the adhesive sheet 11 of Fig. 1 is the single layer adhesive sheet of carrier-free formula, and belong to double-faced pressure-sensitive adhesive sheet.
Stripping film can be enumerated：Have stripping film substrate and set removing on the single side of the stripping film substrate
The fissility laminated chip of oxidant layer；Or the polyolefin films such as polyethylene film, polypropylene film of low polar substrates.
Stationery, macromolecule membrane can be used with substrate in the stripping film of fissility laminated chip.Constitute the remover of peeling agent layer
For example general poly- silicon oxygen series stripping agent of add-on type or condensed type, the compound containing chain alkyl can be used.In particular, it is preferable to use
The higher additive poly silicon oxygen series stripping agent of reactivity.
Poly- silicon oxygen series stripping agent can specifically be enumerated：The BY24- of TorayDow Coming Silicones corporation
4527, SD-7220 etc.；KS-3600, KS-774, X62-2600 etc. of SHIN-ETSU HANTOTAI's chemical industry (stock) system.In addition, can also contain
There is SiO in poly- silicon oxygen series stripping agent2Unit and (CH3)3SiO1/2Unit or CH2=CH (CH3)SiO1/2Unit it is siliconated
Close the polysilicone of object.The concrete example of polysilicone can illustrate such as：TorayDow Coming Silicones corporation
SHIN-ETSU HANTOTAIs' chemical industry (stock) system such as BY24-843, SD-7292, SHR-1404 KS-3800, X92-183 etc..
For stripping film 12 can be removed easily, stripping film 12a is preferably set as different from the fissility of stripping film 12b.That is,
It, can be easily by the higher stripping in advance of stripping film 12 of fissility if the fissility of one of them is different from the fissility of another one
From.This situation, if cooperation applying method or coating squence, then adjust the stripping of the stripping film 12 of stripping film 12a and stripping film 12b
From property.
The thickness of adhering agent layer can cooperate purposes, and row is suitably set again, and there is no particular limitation, it is usually preferred to be at 10 μm
Above and in 500 μm or less of range, more preferably 20 μm or more and 450 μm or less, be further preferred that 30 μm or more and 450
μm or less, be even more preferably 40 μm or more and 400 μm or less, be most preferably 40 μm or more and 350 μm or less, be particularly preferably
40 μm or more and 300 μm or less.It is set within the above range by by the thickness of adhering agent layer, can substantially ensure concave-convex tracking
Property, durability more can be improved.In addition, setting within the above range by by the thickness of adhering agent layer, double-faced pressure-sensitive adhesive sheet can be made
Manufacture is relatively easy to.
In the present invention, P will be set as to the relative dielectric constant before adhesive sheet irradiation active energy beam, adhesive sheet will be shone
When relative dielectric constant after penetrating active energy beam is set as Q, the value of P-Q is preferably 0.3 or more.That is, the present invention lives through irradiation
Property energy-ray after, relative dielectric constant is reduced to more than both quantitative.According to this, the present invention has through irradiating active energy beam
Afterwards, the lower feature of relative dielectric constant.
Above-mentioned relative dielectric constant is the relative dielectric constant under specific frequency, special specifically within the scope of 1KHz to 1MHz
Determine the relative dielectric constant under frequency.Such as the relative dielectric constant under 100KHz or 1MHz frequency, it is according to JIS C 2138
The method of defined is calculated.Relative dielectric constant P before irradiating active energy beam to adhesive sheet, is 100KHz frequency
Under relative dielectric constant when, to adhesive sheet irradiate active energy beam after relative dielectric constant Q be also under 100KHz frequency
Relative dielectric constant.
Furthermore adhesive sheet of the invention is irradiated by active energy beam, and the storage modulus at 23 DEG C, frequency 1Hz is excellent
Choosing is 1.0 × 106Pa or more.The present invention also has the biggish spy of adhesive sheet storage modulus after active energy beam irradiates
Sign.It is fixed within the above range by the adhesive sheet energy storage mould amount Let after irradiating active energy beam, it can more improve durable
Property, it can inhibit to float peeling generation situation by adherend.In addition, being stored up by by the adhesive sheet after active energy beam irradiates
The setting of energy modulus within the above range, also can inhibit and generate bubble between adherend and adhesive sheet.
In the present invention, S will be set as to the storage modulus before adhesive sheet irradiation active energy beam, and will irradiate to adhesive sheet
When storage modulus after active energy beam is set as T, from 0 DEG C to 45 DEG C at T/S value be preferably 5 or more.In addition, from 3 DEG C to
T/S value at 35 DEG C is preferably 10 or more.That is, also there is the present invention storage modulus after irradiating active energy beam can become larger
Feature.Whereby, the durability of the adhesive sheet after active energy beam irradiates can more efficiently be improved.In addition, by work
The irradiation of property energy-ray, can make the bonding force between adhesive sheet and adherend stronger.
The storage modulus of above-mentioned adhesive sheet is the dynamic viscoelastic device (trade name using UBM limited liability company：
Rheogel-E4000 the value) measured.Determination condition is set to 2 DEG C frequency 1Hz, heating rate/min, according to 1 DEG C of stepping temperature
The measured value at 0 DEG C, 23 DEG C, 30 DEG C, 45 DEG C is measured within the scope of -50 DEG C to 150 DEG C.
The adhesion strength of adhesive sheet of the invention is preferably 30N/25mm or more, more preferably 40N/25mm or more.On in addition,
Stating adhesion strength is the adhesion strength irradiated after active energy beam to adhesive sheet.
In the present invention, that is, be convenient for 0 degree of water contact angle or more and less than 90 degree of adherend, adhesion strength still reach 40N/25mm with
On.In addition, i.e. convenient for 90 degree of water contact angle or more and 100 degree of adherends below, adhesion strength still reach 30N/25mm or more.
The surface treated polarizer of protective film, surface treated PMMA (polymethyl methacrylate) resin plate or warp
PC (polycarbonate) resin plate of surface treatment, using being that the hard coat film mainly formed is surface-treated with acrylic resin,
Most water contact angles is 90 degree or more.On the other hand, the adhesion strength relative to this general known adhesive sheet is mostly less than
30N/25mm.Though in addition, the water contact angle of ito film be 90 degree or more, the adhesion strength relative to this general known adhesive sheet
Then less than 20N/25mm, the improvement of adhesion strength become project mostly.
The adhesion strength of adhesive sheet of the invention, such as above-mentioned, i.e., the quilt for being not easy to soak for being 90 degree or more convenient for water contact angle
Viscous object, can still show the adhesion strength up to 30N/25mm or more, have the good feature of adhesion between adherend.
In addition, the adhesion strength of the relatively above-mentioned adherend of adhesive sheet is to imitate JIS Z0237 measurement to apply each adherend
180 ° of values stretched when peeling off adhesion strength.
Haze value of the adhesive sheet of the present invention in the environment of 23 DEG C, relative humidity 50% is preferably 2% or less, is more preferably
It 0% or more and 1.5% or less, is particularly preferably 0% or more and 1% or less.If haze value is within the above range, adhesive sheet can be met
It is used in the transparency required when optical component.In addition, if haze value is 2% hereinafter, being just suitable for optical applications.
Furthermore adhesive sheet of the invention saves 500 hours in the environment of 85 DEG C, relative humidity 85%, in 23 DEG C, it is opposite
Haze value after just taking out under 50% environment of humidity is preferably less than 5%.More preferably less than 2%.Just from resistance to humidification gonorrhoea
Viewpoint for, preferably within the above range in the haze value that postpones of hot and humid environment decentralization.
The full light transmittance of adhesive sheet of the invention in the environment of 23 DEG C, relative humidity 50% is (according to JIS K
7361-1：The value of 1997 measurements) it is preferably up to 80% or more, more preferably 90% or more.If full light transmittance is in above range
Interior, then the transparency is high, is suitable for optical applications.
Adhesive sheet of the invention saves 500 hours under 85 DEG C of dry environments, takes under 23 DEG C, 50% environment of relative humidity
B after 24 hours out*Value, preferably less than 1, more preferably less than 0.5.If b*Value reaches above range, if can meet adhesive sheet use
Required transparency when optical component.So-called " under dry environment " is influenced by the ambient atmos humidity supplied, phase
To humidity under 3% humidity environment below.
The temperature dependency of the aftermentioned relative dielectric constant of adhesive sheet of the present invention is preferably below 20%, more preferably
It 10% or less, is particularly preferably 5% or less.If relative dielectric constant temperature dependency be 20% hereinafter, if Trackpad be not easy
Malfunction is generated, and the body temperature of use environment or manipulation Trackpad is not easy to influence its temperature change, is not likely to produce mistake
Movement.Herein, when calculating the temperature dependency of relative dielectric constant, adhesive sheet is respectively at -30 DEG C, 0 DEG C, 23 DEG C, 45 DEG C
It is respectively placed under dry environment 30 minutes, then measures the relative dielectric constant under frequency 100KHz.It is normal from the opposite dielectric measured
In number, minimum value is selected to calculate again from following formula with maximum value.
Temperature dependency (%)=(maximum value-minimum value)/minimum value × 100
(manufacturing method of adhesive sheet)
Adhesive sheet of the invention is allowed to half admittedly by heating or irradiation active energy ray is implemented to adhesion agent composition
Change, at least part of monomer (B) is contained with unreacted state, and selected in crosslinking agent (C) and polymerization initiator (D)
At least one in, contained at least partially with unreacted state.That is, the manufacturing method of adhesive sheet of the invention includes：It is right
The step of adhesion agent composition heating or irradiation active energy ray.Wherein, the manufacturing method of adhesive sheet of the invention preferably includes
There is the step of heating adhesion agent composition.
Adhesive sheet of the invention can be also made of adhering agent layer and other layers, but be preferably only made of adhering agent layer.
Other layers, which can be enumerated, is formed by adhering agent layer, supporter, stripping film etc. by adhesion agent composition other than the above.Supporter can
It enumerates：Polystyrene, Styrene-acrylic copolymer, acrylic resin, polyethylene terephthalate, polycarbonate, polyethers
The plastic films such as ether ketone, Triafol T；Optical thin films such as anti-reflective film, electromagnetic shielded film etc..
The manufacturing step of adhesive sheet of the invention includes：Adhesion agent composition is coated on stripping film and forms film
Step；And to the film using heating and become semi-solid preparation object the step of or by the film irradiate active energy ray and
The step of as semi-solid preparation object.
Add hereinafter, being directed to the step of coating adhesion agent composition on stripping film forms film and being utilized to the film
Heat and become semi-solid preparation object the step of be illustrated for representative.
By heating progress matrix polymer (A) of film and reacting for crosslinking agent (C), (adhesion of semi-solid preparation object is just formed
Piece).That is, when heating, because monomer (B) polymerization reaction caused by not will do it in film because of polymerization initiator (D), or
Even if having progress but only carrying out slightly, thus sticker combination can be remained in semi-solid preparation object (adhesive sheet) obtained
Monomer contained in object (B) and polymerization initiator (D).So the active energy ray-curable of adhesive sheet of the present invention.To make
Adhesion agent composition is in semi-cured state, also can be after removing coating after solvent, and execution stands adhesive sheet at a certain temperature
Maturation processing during certain.Maturation processing can be enumerated to be stood 7 days and implements at 23 DEG C.
Known apparatus for coating can be used to implement for the coating for forming the adhesion agent composition of adhesive sheet.Apparatus for coating can be enumerated：
Knife type coater, Kohler coater, roll coater, bar coater, gravure coater, micro- gravure coater, stick leaf coating machine (rod
Blade coater), lip type coating machine, die coater, leaching curtain coater etc..
Furthermore heating device known in heating furnace, infrared lamp etc. can be used to implement for the heating of film.
(application method of adhesive sheet)
The application method of adhesive sheet of the present invention is that the adhering agent layer of adhesive sheet is made to be contacted with adherend surface, in this state
Lower irradiation active energy beam and adhering agent layer is fully cured.
Because the adhering agent layer of adhesive sheet is in semi-cured state, even if thus adherend before irradiating active energy beam
With segment difference section, the still traceable bumps of adhering agent layer.It is bonded adhesive sheet according to this, after tracking is concave-convex, recycles active-energy
Adhering agent layer is fully cured in ray, and improves the cohesiveness of adhering agent layer, promotes the adherence to adherend.
Active energy ray can be enumerated：Ultraviolet light, electron beam, luminous ray, X-ray, ion line etc. can cooperate in adhesive sheet
The appropriate selection of row again of contained polymerization initiator (D).Wherein, just from the viewpoint of versatility, preferably ultraviolet light or electron beam, more
Preferably ultraviolet light.
The light source of ultraviolet light is using for example：High-pressure mercury-vapor lamp, Cooper-Hewitt lamp, extra-high-pressure mercury vapour lamp, metal halid lamp, carbon
Arc, xenon arc, electrodeless uv lamp etc..
Electron beam can be used from for example：Ke Kelaofu-Wo Er gulps down (Cockroft-Walton) type, all De Graff types
(Van-de-Graaff type), resonance variable-pressure, insulating core transformer typ, linear type, that rice (Dynamitron) type, height
The electron beam that the various electron-beam accelerators such as frequency type release.
(laminate)
The present invention is about the laminate for being above equipped with adherend on one side at least in above-mentioned adhesive sheet.Adherend is preferably structure
At the optical component of the image display with liquid crystal module, and preferably being equipped with composition has liquid crystal to laminate of the invention
The optical component of the image display of mould group.Laminate of the invention is glued via being contacted with the adhering agent layer of adhesive sheet
Object surface, the step of irradiating active energy beam in this case, adhering agent layer is fully cured and obtain
Fig. 2 is the composition an example for indicating to fit in adhesive sheet 21 of the present invention the laminate 20 of adherend 22 and adherend 24
Cross-sectional view.As shown in Fig. 2, adherend 22 and 24 can also have segment difference section (27a, 27b, 27c, 27d).In Fig. 2, adherend 22
With segment difference section (27a, 27b), adherend 24 has segment difference section (27c, 27d).In addition, segment difference section (27a, 27b, 27c, 27d)
Thickness be usually 5 μm or more and 60 μm or less.According to this, adhesive sheet 21 of the invention can also fit in the structure with segment difference section
Part, the traceable bumps generated by segment difference section.
Adherend is preferably optical component.Optical component can be enumerated in the optical goods such as Trackpad, image display
Each member of formation.The member of formation of Trackpad can be enumerated：The ito thin film of ito film is equipped on transparent resin film, in glass plate
Surface is equipped with the ito glass of ito film, the transparent conducting film of applying conductive polymer, hard on transparent resin film
Coated film, anti-finger printing film etc..The member of formation of image display can be enumerated：Antireflection used in liquid crystal display device
Film, alignment film, light polarizing film, phase-contrast film, luminance promote film etc..
Material used in the grade components can be enumerated：Glass, polycarbonate, polyethylene terephthalate, poly- methyl-prop
E pioic acid methyl ester, polyethylene naphthalate, cyclic olefin polymer, Triafol T, polyimides, acylated cellulose etc..
When adhesive sheet of the present invention is double-faced pressure-sensitive adhesive sheet the case where, it can be used in the fitting of 2 adherends.This situation,
Adhesive sheet of the invention can be used in for example：Between the fitting to each other of ito thin film inside Trackpad, ito thin film and ito glass
Fitting, ito thin film and being bonded between liquid crystal display panel of Trackpad, coverslip and being bonded between ito thin film, coverslip and decoration
Fitting etc. between film.
(manufacturing method of laminate)
The present invention also relates to the manufacturing method of laminate.The manufacturing method of laminate of the invention includes：Make above-mentioned half
The adhesive sheet of solid state is contacted with adherend surface, and irradiation active energy beam keeps adhering agent layer completely solid in this case
The step of change.
Active energy beam can enumerate above-mentioned energy-ray, preferably ultraviolet light or electron beam, more preferably ultraviolet light.
Ultraviolet irradiation output, integral luminous flux are preferably 100mJ/cm2Above and 10000mJ/cm2Below, more preferably
It is 500mJ/cm2Above and 5000mJ/cm2Below.
In the manufacturing method of laminate, because the adhering agent layer of adhesive sheet is in semi-solid preparation before irradiating active energy beam
State, even if thus adherend have segment difference section, the still traceable bumps of adhering agent layer.It is being bonded adhesive sheet according to this and is tracking recessed
After convex, adhering agent layer is fully cured by using active energy beam, cohesiveness, the promotion pair of adhering agent layer can be improved
The adherence of adherend.
[embodiment]
By the following examples with comparative example, more specific description is carried out for feature of the invention.Shown in following embodiment
Material, usage amount, ratio, process content, processing sequence etc. can suitably change under the premise of not escaping present subject matter.So
The scope of the invention should not be construed as circumscribed due to concrete example as shown below.
(embodiment 1)
[production of adhesive sheet]
Matrix polymer (A) uses α.Matrix polymer α is made in ethyl acetate using polymerisation in solution.By methyl
Acrylic acid-2-ethyl caproite (2-EHMA), acrylic acid-2-ethyl caproite (2-EHA) and acrylic acid -2- hydroxyl ethyl ester (2-HEA),
It is deployed according to mass ratio as 100: 28: 14 mode, then makes the 2 of radical polymerization initiator, 2 '-azos bis- (2,4- bis-
Methyl valeronitrile) it is dissolved in solution.Solution is heated to 60 DEG C and is allowed to carry out random copolymerization, obtains matrix polymer α.Base
23 DEG C of solution viscosities of 45% solution of matter polymer α are 5500mPas.
Relative to 100 mass parts of matrix polymer α, addition：As the isostearyl acrylate of monomer (B), (Osaka is organic
Chemical industry (stock) system) 15 mass parts, the xylene diisocyanate based compound (Mitsui Chemicals (stock) as crosslinking agent (C)
System, D-110N) 0.15 mass parts and polymerization initiator (D) 1- hydroxyl-cyclohexyl-phenyl -one (BASF Japan (stock) system,
IRGACURE184) 1.0 mass parts, and the mode according to solid concentration as 40 mass % adds the acetic acid second as solvent (E)
Ester, and obtain adhesion agent composition.
Above-mentioned adhesion agent composition is coated on the 1st stripping film, and (Supreme Being people's DuPont Film (stock) is made, through release processed poly-
Ethylene terephthalate film) on.Coating is implemented using YOSHIMITSU Jing Ji limited liability company system, doctor YD type
Coating is heated 3 minutes using air drier according to 100 DEG C.Then, the processing of execution maturation in 7 days is stood at 23 DEG C, forms thickness
200 μm of semi-cured state adhesive sheet (double-faced pressure-sensitive adhesive sheet).
Fissility is bonded on the single side of the adhesive sheet compared with the 1st stripping film height and through release processed 2nd stripping film (Supreme Being
People's DuPont Film (stock) system), obtain the adhesive sheet with stripping film.
[production of laminate (1)]
On the surface of glass plate (long 90mm × wide 50mm × thickness 0.5mm), by ultraviolet curable ink according to coating
Thickness implements picture frame shape (long 90mm × wide 50mm, width 5mm) screen painting as 5 μm of mode.Then, irradiate ultraviolet light and
Solidify printed above-mentioned ultraviolet curable ink.It repeats this step to amount to 8 times, obtains the printing with 40 μm of segment differences
Segment difference glass.
Adhesive sheet obtained is cut into growth 90mm × wide 50mm shape, the 1st stripping film is torn, uses laminating machine
(YOUBON limited liability company system, IKO-650EMT), according to the entire mode of printing of the picture frame shape of covering printing segment difference glass
It is bonded adhering agent layer.Then, the 2nd stripping film is torn, in the sticker level exposed, is bonded glass using above-mentioned laminating machine
Plate (long 90mm × wide 50mm × thickness 0.5mm), after implementing thermal compressor processing (40 DEG C, 0.5MPa, 30min), utilization is ultraviolet
Line illuminator (EYE GRAPHICS system, ECS-301G1) irradiation integral luminous flux 1500mJ/cm2, just obtain laminate (1).
[laminate (2)]
Adhesive sheet obtained is cut into growth 90mm × wide 50mm shape, the 1st stripping film is torn, uses laminating machine
(YOUBON limited liability company system, IKO-650EMT), it is used when according to covering laminate (1) production that there are 40 μm of segment differences
The entire mode of printing for printing the picture frame shape of segment difference glass, is bonded.
Adherend is in advance to cut polarizer (Polatechno (stock) system, SKN-18243T) to be and glass plate (length
90mm × wide 50mm × thickness 0.5mm) the identical size of single side, and 30 μm of centre of dispersion partial size of the glass in above-mentioned polarisation plate face
Prepared by glass pearl about 0.05mg.
It will tear, fitted in using laminating machine above-mentioned in the 2nd stripping film of integrated laminate with printing segment difference glass
The polarisation plate face of adherend.Then, after implementing thermal compressor processing (40 DEG C, 0.5MPa, 30min), ultraviolet radiation device is utilized
(EYE GRAPHICS system, ECS-301G1) irradiation integral luminous flux 1500mJ/cm2, obtain laminate.In addition, ultraviolet light be from
Printing segment difference glass side is irradiated.
(embodiment 2)
In addition to using lauryl acrylate (Sartomer Japan (stock) system, SR335) as monomer (B), remaining is
Adhesion agent composition, adhesive sheet and laminate are obtained similarly to Example 1.
(embodiment 3)
Except as monomer (B) using isobornyl acrylate (common prosperity society chemistry (stock) system, Light Acrylate IB-
XA except), remaining obtains adhesion agent composition, adhesive sheet and laminate similarly to Example 1.
(embodiment 4)
Except as monomer (B) using in addition to hexyl methacrylate (Tokyo chemical conversion industry (stock) system), remaining with implementation
Example 1 similarly obtains adhesion agent composition, adhesive sheet and laminate.
(embodiment 5)
In addition to using ethyl acrylate (Tokyo chemical conversion industry (stock) system) as monomer (B), remaining is same with embodiment 1
Obtain to sample adhesion agent composition, adhesive sheet and laminate.
(embodiment 6)
In addition to using butyl acrylate (Tokyo chemical conversion industry (stock) system) as monomer (B), remaining is same with embodiment 1
Obtain to sample adhesion agent composition, adhesive sheet and laminate.
(embodiment 7)
In addition to using matrix polymer γ as matrix polymer (A), remaining is adhered similarly to Example 1
Agent composition, adhesive sheet and laminate.Matrix polymer γ is made in ethyl acetate using polymerisation in solution.By methyl-prop
Olefin(e) acid -2- ethylhexyl (2-EHMA), acrylic acid-2-ethyl caproite (2-EHA) and 2-hydroxyethyl methacry-late (2-
HEMA), become 100 according to weight ratio：28：14 mode is deployed, by the 2 of radical polymerization initiator, 2 '-azos bis- (2,4- bis-
Methyl valeronitrile) it is dissolved in solution.Solution is heated to 60 DEG C to be allowed to carry out random copolymerization, obtains matrix polymer γ.Base
45% solution of Quality polymer γ is 5500mPas in 23 DEG C of solution viscosity.
(comparative example 1)
Except the unused isostearyl acrylate as monomer (B) and as 1- hydroxyl-cyclohexyl-of polymerization initiator (D)
Except phenyl ketone, remaining obtains adhesion agent composition, adhesive sheet and laminate similarly to Example 1.
(comparative example 2)
In addition to using matrix polymer B as matrix polymer (A), remaining is adhered similarly to Example 1
Agent composition, adhesive sheet and laminate.Matrix polymer B is made in ethyl acetate using polymerisation in solution.By acrylic acid
N-butyl (BA), acrylic acid (AAC) and acrylic acid -2- hydroxyl ethyl ester (2-HEA) become 100 according to mass ratio：12.5：12.5 side
Formula allotment, then the azobis isobutyronitrile of radical polymerization initiator is dissolved in solution.By solution be heated to 60 DEG C be allowed into
Row random copolymerization obtains matrix polymer β.The 35 Quality amount % solution of Ji Quality polymer β are in 23 DEG C of Rong Ye Nian Du Department
5500mPa·s。
(evaluation)
(evaluation 1：Relative dielectric constant)
Relative dielectric constant system before active energy beam irradiation implements according to following sequence.Adhering agent layer (is passed through from viscous
On piece tear the 1st stripping film and the 2nd stripping film person) be folded between 2 copper foils, implement thermal compressor processing (40 DEG C, 0.5MPa,
30min).Then, it using dielectric constant measurement system (Dongyang science and technology (stock) system, 1260 types), is surveyed according to JIS C 2138
It is fixed.Frequency, determination of the environment are measured according to following conditions.
Frequency：100KHz,1MHz
Determination of the environment：23 DEG C, relative humidity 55%
Relative dielectric constant system after active energy beam irradiation implements according to following sequence.Tear the 1st stripping of adhesive sheet
It from piece, is fitted on 1 copper foil using laminating machine, implements thermal compressor processing (40 DEG C, 0.5MPa, 30min).Then, purple is utilized
Outside line illuminator is according to integral luminous flux 1500mJ/cm2Irradiation, tears the 2nd stripping film, the sticker that will be exposed using laminating machine
Layer fits on 1 copper foil, implements thermal compressor processing (40 DEG C, 0.5MPa, 30min).Then it is measured in the same manner as said sequence
Relative dielectric constant.
(evaluation 2：The measurement of direct capacitance change rate)
<The assembling of direct capacitance Trackpad>
The 1st stripping film for tearing commercially available adhesive sheet OC8173D (LG system, relative dielectric constant 5.7), using laminating machine,
It has been formed with the first transparent membrane (200 μm of transparent membrane thickness, relative dielectric constant 3.1, the reception of transparent conductive electrode pattern
Side ITO electrode) on, fit in the one side to form transparent conductive electrode pattern.Then, the 2nd stripping film is torn, is pasted using laminating machine
Closing lid slide (thickness 1.0mm, relative dielectric constant 7.4).It is set to laminate (3).
Secondly, tearing the 1st stripping film of Examples and Comparative Examples adhesive sheet obtained, using laminating machine, formed
Have on the second transparent membrane (transmission side ITO electrode) of transparent conductive electrode pattern, fits in and formed transparent conductive electrode figure
The one side of case.Then, the 2nd stripping film is torn, using laminating machine, fits in the not formed receiving side ITO electrode of above-mentioned laminate (3)
Transparent conductive electrode pattern one side, obtain laminate (4).First transparent membrane and the second transparent membrane and projection electrostatic
Capacitance type similarly arranges quadrangle transparent conductive electrode pattern respectively, and the first transparent membrane detects X and arranges (row), the second thin transparent
Film detects Y row (file).The area size of used each material is all set to 194mm × 345mm.
<The measurement of direct capacitance change rate>
It is the receiving side ITO electricity before measuring finger touching Trackpad as the direct capacitance change rate of touch control sensor sensitivity index
Direct capacitance C between pole and transmission side ITO electrodeITOAnd refer to quiet between receiving side ITO electrode after touch and transmission side ITO electrode
Capacitor CfingerThe ratio between Δ C (%)=Cfinger/CITO×100.Direct capacitance is surveyed using Agilent corporation LCR meter (4284A)
It is fixed.
(evaluation 3：The location identification of sensor)
Make the Stylus contact of commercially available stylus in the coverslip side surface of laminate (4), by sequentially measurement XY sensor
Between capacitor change, and detect and touch the location coordinate in portion.Location identification is according to benchmark evaluation below.
◎：Touch location with detection coordinate between at a distance from less than 5mm.
○：Touch location with detection coordinate between at a distance from be 5mm or more and less than 10mm.
△：Touch location with detection coordinate between at a distance from be 10mm or more and less than 20mm.
×：Touch location with detection coordinate between at a distance from reach 20mm or more.
(evaluation 4：Storage modulus)
Storage modulus before active energy beam irradiation is to go out 5mm from the laminate punching of adhering agent layer obtained
(vertical 5mm × horizontal 5mm), is fitted in fixed shear fixture, utilizes UBM limited liability company dynamic viscoplasticity device (quotient
The name of an article：Rheogel-E4000 measurement) is implemented.Determination condition is set as 2 DEG C frequency 1Hz, heating rate/min, according to stepping temperature 1
DEG C -50 DEG C to 150 DEG C within the scope of, be measured at 0 DEG C, 23 DEG C, 30 DEG C, 45 DEG C.
Storage modulus system after active energy beam irradiates removes the laminate to adhering agent layer obtained, and utilization is ultraviolet
Line illuminator is according to integral luminous flux 1500mJ/cm2Except irradiation, remaining is implemented in the same manner as said sequence obtained by measurement.
(evaluation 5：Segment difference traceability)
Utilize microscope (multiplying power：25 times) observation laminate (1) and laminate (2) printing segment difference section, according to following base
The segment difference traceability of quasi- evaluation adhesive sheet.
○：Segment difference is buried completely.
△：There is air residual in a portion of segment difference part.
×：Segment difference part entirety has air residual.
(evaluation 6：Appearance durability)
<Float peeling>
Laminate (1) is implemented 240 hours in the environment of 85 DEG C, relative humidity 85% and is handled, and microscope (multiplying power is utilized：
25 times) observe whether sample entirety has generation bubble or peeling, according to following benchmark evaluation.
○：It absolutely not generates bubble, peel off.
△：Occur several bubbles.
×：Generate a lot of bubbles.
<Burying property of foreign matter>
Laminate (2) is implemented 24 hours in the environment of 85 DEG C, relative humidity 85% and is handled, and microscope (multiplying power is utilized：25
Times) the bead distribution part of observation after processing, according to the burying property of foreign matter of following benchmark evaluation adhesive sheet.
○：There is no generate new bubble from bead periphery.
×：Have from bead periphery and generates new bubble.
(evaluation 7：Adhesion strength (adhesion strength after active energy beam irradiation))
For adhesive sheet, adhesion strength is peeled off according to 180 ° of stretchings that JIS Z 0237 measures each adherend.Test film according to
Following sequentially built.The 1st stripping film for tearing adhesive sheet fits in 50 μm of thickness of optics PET film, tears the 2nd stripping film,
Each adherend is crimped on according to 2kg.Then, integral luminous flux 1500mJ/cm is irradiated using ultraviolet radiation device2, through in 23 DEG C, phase
It is measured to being implemented after standing 24 hours in the environment of humidity 50%.
Each adherend uses following 5 kinds：
Soda-lime glass：Commercially available soda-lime glass.Water contact angle=54 °
The face TAC of polarizer：Polatechno (stock) system, SKN-18243T, water contact angle=22 °
The face HC of polarizer：Polatechno (stock) system, SKN-18243T-HC, water contact angle=49 °
The face HC of MR200：Mitsubishi Rayon (stock) system, water contact angle=89 °
Ito surface：Tail vat (stock) system, KB300, water contact angle=96 °
(evaluation 8：The temperature dependency of relative dielectric constant)
Using the relative dielectric constant sample for evaluation used in evaluation 1 after active energy beam irradiates, phase is evaluated
To the temperature dependency of dielectric constant.Specifically by the relative dielectric constant sample for evaluation after active energy beam irradiates,
It is respectively placed 30 minutes under -30 DEG C, 0 DEG C, 23 DEG C, 45 DEG C of dry environments respectively, measures the opposite dielectric at frequency 100KHz
Constant.From the relative dielectric constant measured, minimum value and maximum value are selected, and calculate temperature dependency according to following formula
(%).
Temperature dependency (%)=(maximum value-minimum value)/minimum value × 100
It is learnt by table 1 and 2, the relative dielectric constant of embodiment adhesive sheet obtained is low, through irradiating activity to adhesive sheet
Relative dielectric constant after energy-ray more reduces.In addition, being shone by embodiment adhesive sheet obtained through active energy beam
Storage modulus after penetrating is larger, excellent in te pins of durability.Learn that the adhesive sheet after irradiating active energy beam is floating there is no generating
It rises and peels off, particularly effectively bubble is inhibited to generate.
Furthermore in the liquid crystal display panel using embodiment adhesive sheet obtained, because especially lowering relative dielectric constant,
Thus inhibit to generate the noise from liquid crystal display panel side.
【Symbol description】
The adhesive sheet of 1 attached stripping film
11 adhesive sheets (adhering agent layer)
12a, 12b stripping film
20 laminates
21 adhesive sheets (adhering agent layer)
22 adherends
24 adherends
The segment difference section 27a, 27b, 27c, 27d.
Claims (13)
1. a kind of adhesion agent composition, which is characterized in that contain：
Matrix polymer (A) contains by non-crosslinked property (methyl) propylene with the branched alkyl groups below of carbon number 5 or more and 9
Unit derived from acid esters (a1) and the unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group；
Monomer (B) contains at least one polymerism unsaturated group；
Crosslinking agent (C) is reacted using heat with the matrix polymer (A) generation；And
Polymerization initiator (D) starts the polymerization reaction of the monomer (B) using the irradiation of active energy beam.
2. adhesion agent composition according to claim 1, wherein the molal volume of the monomer (B) be 180ml/mol with
On, the density of the monomer (B) is 1.0g/cm3Below.
3. adhesion agent composition according to claim 1 or 2, wherein the monomer (B) has the alkyl of 5 or more carbon number.
4. adhesion agent composition according to any one of claim 1 to 3, wherein the monomer (B) is from (methyl) third
Olefin(e) acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) n-octyl, (methyl) acrylic acid are different
Monooctyl ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) acrylic acid are different
Last of the ten Heavenly stems ester, (methyl) acrylic acid n-undecane base ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate, (methyl) third
It is selected in the group that the different stearyl ester of olefin(e) acid, (methyl) isobornyl acrylate and (methyl) acrylic acid-2-ethyl caproite are constituted
It is at least one kind of.
5. adhesion agent composition according to any one of claim 1 to 4, wherein the matrix polymer (A) is more into one
Step contains polystyrene condensate.
6. a kind of adhesive sheet, which is characterized in that have adhering agent layer,
The adhering agent layer contains：
Matrix polymer (A), contains：By non-crosslinked property (methyl) propylene with the branched alkyl groups below of carbon number 5 or more and 9
Unit derived from acid esters (a1) and the unit (a2) as derived from (methyl) acrylic monomers with bridging property functional group；
Monomer (B) contains at least one polymerism unsaturated group；And
Polymerization initiator (D) starts the polymerization reaction of the monomer (B) using the irradiation of active energy beam.
7. adhesive sheet according to claim 6, wherein will be to opposite Jie before adhesive sheet irradiation active energy beam
Electric constant is set as P, and when will irradiate the relative dielectric constant after active energy beam to the adhesive sheet and being set as Q, P-Q value is
0.3 or more.
8. adhesive sheet according to claim 6 or 7, wherein using the irradiation of active energy beam, in 23 DEG C, frequency 1Hz
Under storage modulus up to 1.0 × 106Pa or more.
9. the adhesive sheet according to any one of claim 6 to 8, wherein active-energy will be irradiated to the adhesive sheet and penetrated
Storage modulus before line is set as S, and when will irradiate the storage modulus after active energy beam to the adhesive sheet and being set as T, 0 DEG C extremely
45 DEG C of T/S value is 5 or more.
10. adhesive sheet according to any one of claims 6 to 9, wherein active-energy will be irradiated to the adhesive sheet and penetrated
Storage modulus before line is set as S, and when will irradiate the storage modulus after active energy beam to the adhesive sheet and being set as T, 3 DEG C extremely
35 DEG C of T/S value is 10 or more.
11. the adhesive sheet according to any one of claim 6 to 10, wherein the adhesive sheet is double-faced pressure-sensitive adhesive sheet.
12. a kind of manufacturing method of laminate, which is characterized in that including：Make the adhesive sheet of any one of claim 6 to 11
Adhering agent layer is contacted to adherend surface, irradiates active energy beam in this case and the adhering agent layer is fully cured
Step.
13. a kind of application method of adhesive sheet, which is characterized in that make the adhesion of the adhesive sheet of any one of claim 6 to 11
Oxidant layer is contacted to adherend surface, irradiates active energy beam in this case and the adhering agent layer is fully cured.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016053587 | 2016-03-17 | ||
| JP2016-053587 | 2016-03-17 | ||
| PCT/JP2017/010684 WO2017159788A1 (en) | 2016-03-17 | 2017-03-16 | Adhesive composition and adhesive sheet |
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| CN108884368A true CN108884368A (en) | 2018-11-23 |
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| JP (2) | JP7070398B2 (en) |
| KR (1) | KR102179018B1 (en) |
| CN (1) | CN108884368A (en) |
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| JP6504987B2 (en) * | 2015-09-30 | 2019-04-24 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JPWO2019004107A1 (en) * | 2017-06-30 | 2020-07-16 | 王子ホールディングス株式会社 | Adhesive composition, adhesive sheet and laminate |
| JP6922650B2 (en) * | 2017-10-26 | 2021-08-18 | 王子ホールディングス株式会社 | Adhesive composition, adhesive sheet and laminate |
| JP7013793B2 (en) * | 2017-10-26 | 2022-02-01 | 王子ホールディングス株式会社 | Adhesive composition, adhesive sheet and laminate |
| JP6693490B2 (en) * | 2017-11-15 | 2020-05-13 | 王子ホールディングス株式会社 | Adhesive sheet, laminated body manufacturing method and laminated body |
| JP6693491B2 (en) * | 2017-11-15 | 2020-05-13 | 王子ホールディングス株式会社 | Adhesive sheet, laminated body manufacturing method and laminated body |
| JP2020111628A (en) * | 2019-01-08 | 2020-07-27 | 王子ホールディングス株式会社 | Adhesive sheet, adhesive sheet with release sheet, laminate, and method of manufacturing laminate |
| KR102221720B1 (en) * | 2019-05-07 | 2021-03-02 | 크루셜텍(주) | Fingerprint sensor module including multi color layer and method for manufacturing the same |
| TWI837359B (en) * | 2019-05-08 | 2024-04-01 | 日商王子控股股份有限公司 | Manufacturing method of adhesive sheet and laminated body, and laminated body |
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Also Published As
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|---|---|
| TW201805312A (en) | 2018-02-16 |
| KR20180117705A (en) | 2018-10-29 |
| KR102179018B1 (en) | 2020-11-16 |
| JP7070398B2 (en) | 2022-05-18 |
| TWI795355B (en) | 2023-03-11 |
| JPWO2017159788A1 (en) | 2019-01-24 |
| JP2022100406A (en) | 2022-07-05 |
| WO2017159788A1 (en) | 2017-09-21 |
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