JP5961427B2 - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- JP5961427B2 JP5961427B2 JP2012081251A JP2012081251A JP5961427B2 JP 5961427 B2 JP5961427 B2 JP 5961427B2 JP 2012081251 A JP2012081251 A JP 2012081251A JP 2012081251 A JP2012081251 A JP 2012081251A JP 5961427 B2 JP5961427 B2 JP 5961427B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- mass
- sensitive adhesive
- adhesive composition
- oxazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 133
- 239000000853 adhesive Substances 0.000 title claims description 65
- 230000001070 adhesive effect Effects 0.000 title claims description 65
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 143
- 239000000178 monomer Substances 0.000 claims description 73
- 229920006243 acrylic copolymer Polymers 0.000 claims description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 46
- -1 oxazine compound Chemical class 0.000 claims description 41
- 239000003431 cross linking reagent Substances 0.000 claims description 32
- CQTRKDFIQFOAQV-UHFFFAOYSA-N 1',3',3'-trimethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound C1=CC=CC2=C(N=CC3(C(C)(C)C4=CC=CC=C4N3C)O3)C3=CC=C21 CQTRKDFIQFOAQV-UHFFFAOYSA-N 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 239000012790 adhesive layer Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000004893 oxazines Chemical class 0.000 claims description 3
- HSGIKWSAFYCPDL-UHFFFAOYSA-N 1',3',3',5',6'-pentamethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound C1=CC=CC2=C(N=CC3(C(C)(C)C4=CC(C)=C(C)C=C4N3C)O3)C3=CC=C21 HSGIKWSAFYCPDL-UHFFFAOYSA-N 0.000 claims description 2
- YAWJWXXKKHOMQT-UHFFFAOYSA-N 1',3',3'-trimethyl-6-piperidin-1-ylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound CN1C2=CC=CC=C2C(C)(C)C1(C=NC1=C2C=CC=CC2=2)OC1=CC=2N1CCCCC1 YAWJWXXKKHOMQT-UHFFFAOYSA-N 0.000 claims description 2
- YVYVCXOQZYPIOP-UHFFFAOYSA-N 1'-benzyl-3',3'-dimethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound O1C2=CC=C3C=CC=CC3=C2N=CC11C(C)(C)C2=CC=CC=C2N1CC1=CC=CC=C1 YVYVCXOQZYPIOP-UHFFFAOYSA-N 0.000 claims description 2
- LWQUIEPGNGERFR-UHFFFAOYSA-N 3'-ethyl-1',3',5',6'-tetramethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound C1=CC=CC2=C(N=CC3(N(C)C4=CC(C)=C(C)C=C4C3(C)CC)O3)C3=CC=C21 LWQUIEPGNGERFR-UHFFFAOYSA-N 0.000 claims description 2
- VODQUQTUKIYWSU-UHFFFAOYSA-N 5'-chloro-1',3',3'-trimethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound C1=CC=CC2=C(N=CC3(C(C)(C)C4=CC(Cl)=CC=C4N3C)O3)C3=CC=C21 VODQUQTUKIYWSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 claims description 2
- PVTXJGJDOHYFOX-UHFFFAOYSA-N 2h-1,4-benzoxazine Chemical compound C1=CC=C2N=CCOC2=C1 PVTXJGJDOHYFOX-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 description 52
- 239000000463 material Substances 0.000 description 47
- 239000011347 resin Substances 0.000 description 44
- 229920005989 resin Polymers 0.000 description 44
- 239000000047 product Substances 0.000 description 42
- 239000000975 dye Substances 0.000 description 40
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 33
- 238000011156 evaluation Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000126 substance Substances 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 239000010410 layer Substances 0.000 description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 13
- 239000000123 paper Substances 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 11
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000004611 light stabiliser Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 238000004040 coloring Methods 0.000 description 7
- 238000002845 discoloration Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 238000003851 corona treatment Methods 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 238000004381 surface treatment Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- FWWWRCRHNMOYQY-UHFFFAOYSA-N 1,5-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C=C1N=C=O FWWWRCRHNMOYQY-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- HXQKJEIGFRLGIH-UHFFFAOYSA-N 1-ethenyl-2h-pyrazine Chemical compound C=CN1CC=NC=C1 HXQKJEIGFRLGIH-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- DCRYNQTXGUTACA-UHFFFAOYSA-N 1-ethenylpiperazine Chemical compound C=CN1CCNCC1 DCRYNQTXGUTACA-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- BFYSJBXFEVRVII-UHFFFAOYSA-N 1-prop-1-enylpyrrolidin-2-one Chemical compound CC=CN1CCCC1=O BFYSJBXFEVRVII-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical class C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
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- 239000003429 antifungal agent Substances 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002651 laminated plastic film Substances 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- MXXWOMGUGJBKIW-YPCIICBESA-N piperine Chemical compound C=1C=C2OCOC2=CC=1/C=C/C=C/C(=O)N1CCCCC1 MXXWOMGUGJBKIW-YPCIICBESA-N 0.000 description 1
- 229940075559 piperine Drugs 0.000 description 1
- WVWHRXVVAYXKDE-UHFFFAOYSA-N piperine Natural products O=C(C=CC=Cc1ccc2OCOc2c1)C3CCCCN3 WVWHRXVVAYXKDE-UHFFFAOYSA-N 0.000 description 1
- 235000019100 piperine Nutrition 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、可逆的に色調が変化する光透過性のある粘着剤組成物、及びこの粘着剤組成物からなる粘着剤層を有する粘着シートに関する。 The present invention relates to a light-transmitting pressure-sensitive adhesive composition whose color tone reversibly changes and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of this pressure-sensitive adhesive composition.
従来から、窓ガラスや壁面、間仕切り用のガラスや透明樹脂板、ブラックライトが照射される空間内で使用されるイルミネーション用のガラスや透明樹脂板、自動車、バス、電車等の車輌、サングラス、眼鏡等のレンズ等において、光の透過性を調節する目的で使用される着色シートが提案されている。
しかしながら、このような着色シートは、特に、自動車、バス、電車等の車輌のウィンドーに貼って使用すると、屋内、雨天又は曇天、夜間又はトンネルの中では、光の透過性が低いために十分な視野が確保できず、安全性の面において問題があった。
Conventionally, window glass and wall surfaces, partition glass and transparent resin plates, illumination glass and transparent resin plates used in spaces illuminated by black light, vehicles such as cars, buses, trains, sunglasses, glasses Colored sheets used for the purpose of adjusting the light transmittance of lenses such as these have been proposed.
However, such a colored sheet is sufficient when used on a window of a vehicle such as an automobile, a bus, or a train, because it has low light permeability indoors, in rainy or cloudy weather, at night, or in a tunnel. There was a problem in terms of safety because the field of view could not be secured.
近年、このような問題を解決するため、フォトクロミック性染料を使用した着色シートが提案されている（特許文献１〜５参照）。フォトクロミック性染料は、光照射により可逆的に色調が変化する。つまり、フォトクロミック性染料は、日光やブラックライト等による紫外線を受光することで着色する一方、紫外線が照射されない環境下では無色に戻るという特性を有している。
特許文献１〜５に開示された着色シートは、このような特性を有するフォトクロミック性染料を着色シートに使用しているため、紫外線が照射されている環境下でのみ遮光性を示し、それ以外の環境下では透明性を示すことが可能とされている。
In recent years, in order to solve such a problem, a colored sheet using a photochromic dye has been proposed (see Patent Documents 1 to 5). The photochromic dye reversibly changes its color tone upon light irradiation. That is, the photochromic dye has a characteristic that it is colored by receiving ultraviolet rays from sunlight, black light, or the like, but returns to colorless in an environment where the ultraviolet rays are not irradiated.
Since the colored sheet disclosed in Patent Documents 1 to 5 uses a photochromic dye having such characteristics for the colored sheet, the colored sheet exhibits a light shielding property only under an environment irradiated with ultraviolet rays. It is possible to show transparency in the environment.
しかしながら、特許文献１〜５に開示された着色シートは、有色から無色への色調変化の速度が遅い点が問題となる。つまり、これらの着色シートを自動車、バス、電車等の車輌のウィンドーに貼付して使用した場合、日中の屋外走行では紫外線の量が十分であるため、ある程度の遮光効果が得られるものの、トンネル内等の紫外線が遮断される環境下へ入った直後は、無色に戻る速度が遅いため、ウィンドーの視野が確保されず、交通事故等の原因を誘発する可能性がある。 However, the colored sheets disclosed in Patent Documents 1 to 5 have a problem in that the speed of change in color tone from colored to colorless is slow. In other words, when these colored sheets are attached to the window of a vehicle such as an automobile, bus or train, the amount of ultraviolet rays is sufficient when running outdoors during the day. Immediately after entering an environment where the inside ultraviolet rays are blocked, the speed of returning to colorless is slow, so the visual field of the window is not secured, and there is a possibility of causing a traffic accident or the like.
また、これらの着色シートは、長時間使用した場合に、含有する染料のフォトクロミック性能（発色性）の低下や、本来無色であるべき紫外線非照射の環境下でも変色するといった性能低下が長時間使用した場合において起こる問題も有する。
特に、特許文献５に開示されているような、一般的なアクリル系共重合体を含む粘着剤組成物を用いた着色シートは、長時間使用された後では、紫外線非照射の環境下でも変色した状態が恒常化してしまうという、耐候性の問題を有する。
In addition, when these colored sheets are used for a long time, the deterioration of the photochromic performance (color developability) of the contained dye and the performance deterioration such as discoloration in the environment of non-ultraviolet irradiation that should be essentially colorless are used for a long time. It also has problems that occur in the case of
In particular, a colored sheet using a pressure-sensitive adhesive composition containing a general acrylic copolymer as disclosed in Patent Document 5 is discolored even in a non-ultraviolet irradiation environment after being used for a long time. There is a problem of weather resistance that the state becomes constant.
本発明は、上記課題を解決するためになされたものであり、例えば屋外で長時間使用された後でも、フォトクロミック性能の低下を抑制しつつ、紫外線非照射の環境下での変色が恒常化することを防ぎ得る、優れた耐候性を有し、また、有色から無色への色調変化の速度が速い粘着剤組成物及び粘着シートを提供することを目的とする。 The present invention has been made to solve the above-mentioned problems. For example, even after being used outdoors for a long time, discoloration in a non-ultraviolet irradiation environment is made constant while suppressing a decrease in photochromic performance. An object of the present invention is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having excellent weather resistance that can prevent this, and a rapid color change from colored to colorless.
本発明者らは、特定の構成単位を有するアクリル系共重合体に対して、架橋剤、及びオキサジン系化合物からなるフォトクロミック性染料を所定の割合で含有した粘着剤組成物が上記課題を解決しうることを見出した。
すなわち、本発明は、下記［１］〜［４］を提供するものである。
［１］アルキル（メタ）アクリレート（ａ１）’由来の構成単位（ａ１）及び官能基含有モノマー（ａ２）’由来の構成単位（ａ２）を有し、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位の含有量がそれぞれ３．０質量％以下であるアクリル系共重合体（Ａ）、架橋剤（Ｂ）、及びオキサジン系化合物からなるフォトクロミック性染料（Ｃ）を含有する粘着剤組成物であって、フォトクロミック性染料（Ｃ）の配合量が、アクリル系共重合体（Ａ）１００質量部に対して、０．４０〜８．００質量部である、粘着剤組成物。
［２］官能基含有モノマー（ａ２）’由来の構成単位（ａ２）の含有量が、アクリル系共重合体（Ａ）の全構成単位に対して、０．０１〜３５質量％である、上記［１］に記載の粘着剤組成物。
［３］官能基含有モノマー（ａ２）’がヒドロキシ基含有モノマーである、上記［１］又は［２］に記載の粘着剤組成物。
［４］上記［１］〜［３］のいずれかに記載の粘着剤組成物からなる粘着剤層を有する、粘着シート。
The present inventors have solved the above-mentioned problems with a pressure-sensitive adhesive composition containing a crosslinking agent and a photochromic dye comprising an oxazine compound in a predetermined ratio with respect to an acrylic copolymer having a specific structural unit. I found out.
That is, the present invention provides the following [1] to [4].
[1] It has a structural unit (a1) derived from alkyl (meth) acrylate (a1) ′ and a structural unit (a2) derived from functional group-containing monomer (a2) ′, and contains a carboxyl group-containing monomer and a primary amino group A pressure-sensitive adhesive containing a photochromic dye (C) composed of an acrylic copolymer (A), a crosslinking agent (B), and an oxazine compound each having a monomer-derived constitutional unit content of 3.0% by mass or less. It is a composition, Comprising: The adhesive composition whose compounding quantity of a photochromic dye (C) is 0.40-8.00 mass parts with respect to 100 mass parts of acrylic copolymers (A).
[2] The content of the structural unit (a2) derived from the functional group-containing monomer (a2) ′ is 0.01 to 35% by mass with respect to all the structural units of the acrylic copolymer (A). The pressure-sensitive adhesive composition according to [1].
[3] The pressure-sensitive adhesive composition according to the above [1] or [2], wherein the functional group-containing monomer (a2) ′ is a hydroxy group-containing monomer.
[4] A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to any one of [1] to [3].
本発明の粘着剤組成物及び粘着シートは、長時間使用された後でも、フォトクロミック性能の低下を抑制しつつ、紫外線非照射の環境下での変色が恒常化することを防ぎ得る、優れた耐候性を有し、また、有色から無色への色調変化の速度が速い。 The pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention have excellent weather resistance, which can prevent the discoloration in an environment not irradiated with ultraviolet rays from becoming permanent, while suppressing deterioration of photochromic performance even after being used for a long time. In addition, the speed of color change from colored to colorless is high.
［粘着剤組成物］
本発明の粘着剤組成物は、アルキル（メタ）アクリレート（ａ１）’由来の構成単位（ａ１）及び官能基含有モノマー（ａ２）’由来の構成単位（ａ２）を有し、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位の含有量がそれぞれ３．０質量％以下であるアクリル系共重合体（Ａ）、架橋剤（Ｂ）、及びオキサジン系化合物からなるフォトクロミック性染料（Ｃ）を含有する粘着剤組成物であって、フォトクロミック性染料（Ｃ）の配合量が、アクリル系共重合体（Ａ）１００質量部に対して、０．４０〜８．００質量部である。
本発明者らは、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位の含有量がそれぞれ３．０質量％以下であるアクリル系共重合体（Ａ）を、特定量のオキサジン系化合物からなるフォトクロミック性染料（Ｃ）と共に含有する粘着剤組成物が、アクリル系共重合体（Ａ）が有する優れた粘着力を発現させつつ、上述の耐候性の低下を抑え得ることを見出し、本発明を完成させている。
[Adhesive composition]
The pressure-sensitive adhesive composition of the present invention has a structural unit (a1) derived from an alkyl (meth) acrylate (a1) ′ and a structural unit (a2) derived from a functional group-containing monomer (a2) ′, and a carboxyl group-containing monomer and A photochromic dye (C) composed of an acrylic copolymer (A), a crosslinking agent (B), and an oxazine compound each containing 3.0% by mass or less of a constituent unit derived from a primary amino group-containing monomer. ), And the blending amount of the photochromic dye (C) is 0.40 to 8.00 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A).
The inventors of the present invention have used an acrylic copolymer (A) in which the content of structural units derived from a carboxyl group-containing monomer and a primary amino group-containing monomer is 3.0% by mass or less, with a specific amount of oxazine It has been found that the pressure-sensitive adhesive composition contained together with the photochromic dye (C) made of a compound can suppress the above-described deterioration in weather resistance while expressing the excellent adhesive strength of the acrylic copolymer (A), The present invention has been completed.
なお、本発明の粘着剤組成物は、必要に応じて、さらに酸化防止剤や、紫外線吸収剤等のその他の配合剤を含有することができる。
以下、本発明の粘着剤組成物に含まれる、アクリル系共重合体（Ａ）、架橋剤（Ｂ）、フォトクロミック性染料（Ｃ）、及びその他の配合剤について詳述する。なお、本発明において、例えば「（メタ）アクリレート」とは、アクリレート及びメタクリレートの両方を意味し、他の類似用語も同様である。
In addition, the adhesive composition of this invention can contain other compounding agents, such as antioxidant and a ultraviolet absorber, as needed.
Hereinafter, the acrylic copolymer (A), the crosslinking agent (B), the photochromic dye (C), and other compounding agents included in the pressure-sensitive adhesive composition of the present invention will be described in detail. In the present invention, for example, “(meth) acrylate” means both acrylate and methacrylate, and the same applies to other similar terms.
〔アクリル系共重合体（Ａ）〕
本発明で用いるアクリル系共重合体（Ａ）は、アルキル（メタ）アクリレート（ａ１）’（以下、「モノマー（ａ１）’」ともいう）由来の構成単位（ａ１）及び官能基含有モノマー（ａ２）’（以下、「モノマー（ａ２）’」ともいう）由来の構成単位（ａ２）を有し、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位の含有量がそれぞれ３．０質量％以下の共重合体である。また、アクリル系共重合体（Ａ）は、モノマー（ａ１）’及び（ａ２）’以外のその他のモノマー由来の構成単位を有していてもよい。
以下、アクリル系共重合体（Ａ）の各構成単位について説明する。
[Acrylic copolymer (A)]
The acrylic copolymer (A) used in the present invention comprises a structural unit (a1) derived from an alkyl (meth) acrylate (a1) ′ (hereinafter also referred to as “monomer (a1) ′”) and a functional group-containing monomer (a2). ) ′ (Hereinafter also referred to as “monomer (a2) ′”), and the content of the structural unit derived from the carboxyl group-containing monomer and the primary amino group-containing monomer is 3.0, respectively. It is a copolymer of mass% or less. Moreover, the acrylic copolymer (A) may have a structural unit derived from another monomer other than the monomers (a1) ′ and (a2) ′.
Hereinafter, each structural unit of the acrylic copolymer (A) will be described.
（構成単位（ａ１））
本発明で用いるアクリル系共重合体（Ａ）は、粘着力向上の観点から、アルキル（メタ）アクリレート（ａ１）’由来の構成単位（ａ１）を含有する。
(Structural unit (a1))
The acrylic copolymer (A) used in the present invention contains the structural unit (a1) derived from the alkyl (meth) acrylate (a1) ′ from the viewpoint of improving the adhesive strength.
モノマー（ａ１）’としては、粘着力向上の観点から、炭素数４〜２０のアルキル基を有するアルキル（メタ）アクリレートが好ましく、炭素数４〜１２のアルキル基を有するアルキル（メタ）アクリレートがより好ましく、炭素数４〜８のアルキル基を有するアルキル（メタ）アクリレートが更に好ましい。 As the monomer (a1) ′, an alkyl (meth) acrylate having an alkyl group having 4 to 20 carbon atoms is preferable, and an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of improving adhesive strength. Preferably, the alkyl (meth) acrylate which has a C4-C8 alkyl group is still more preferable.
より具体的なモノマー（ａ１）’としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチルアクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ミリスチル（メタ）アクリレート、パルミチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。
これらのモノマー（ａ１）’は、単独で又は２種以上組み合わせて用いてもよい。
More specific monomers (a1) ′ include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, pentyl (meth) acrylate, hexyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylate and the like.
These monomers (a1) ′ may be used alone or in combination of two or more.
これらの中でも、粘着力向上の観点から、ブチル（メタ）アクリレートが好ましい。
なお、上述のモノマーを２種以上組み合わせて用いる場合、粘着剤層を薄膜化しても十分な粘着力を得る観点から、ブチル（メタ）アクリレート由来の構成単位を、モノマー（ａ１）’由来の構成単位中、好ましくは５０〜１００質量％、より好ましくは７０〜１００質量％、更に好ましくは８０〜１００質量％含有することが好ましい。
Among these, butyl (meth) acrylate is preferable from the viewpoint of improving adhesive strength.
In the case of using two or more of the above-mentioned monomers in combination, from the viewpoint of obtaining sufficient adhesive strength even if the pressure-sensitive adhesive layer is thinned, the structural unit derived from the monomer (a1) ′ is used as the structural unit derived from butyl (meth) acrylate. In a unit, Preferably it is 50-100 mass%, More preferably, it is 70-100 mass%, More preferably, it is preferable to contain 80-100 mass%.
構成単位（ａ１）の含有量は、十分な粘着力を得る観点から、アクリル系共重合体（Ａ）の全構成単位に対して、好ましくは５５〜９９．９９質量％、より好ましくは６５〜９９．９７質量％、更に好ましくは６８〜９９．９質量％、より更に好ましくは７５〜９９．９質量％である。 The content of the structural unit (a1) is preferably 55 to 99.99% by mass, more preferably 65% to all structural units of the acrylic copolymer (A) from the viewpoint of obtaining sufficient adhesive strength. It is 99.97 mass%, More preferably, it is 68-99.9 mass%, More preferably, it is 75-99.9 mass%.
（構成単位（ａ２））
本発明で用いるアクリル系共重合体（Ａ）は、粘着力向上の観点から、官能基含有モノマー（ａ２）’由来の構成単位（ａ２）を含有する。
本発明において、「官能基含有モノマー」の「官能基」とは、後述の架橋剤（Ｂ）と反応し、架橋起点となり得る官能基又は架橋促進効果を有する官能基を示す。
このような官能基としては、例えば、ヒドロキシ基、エポキシ基、シアノ基、ケト基、窒素元素含有環等が挙げられる。
(Structural unit (a2))
The acrylic copolymer (A) used in the present invention contains the structural unit (a2) derived from the functional group-containing monomer (a2) ′ from the viewpoint of improving the adhesive strength.
In the present invention, the “functional group” of the “functional group-containing monomer” refers to a functional group capable of reacting with a crosslinking agent (B) described later and serving as a crosslinking starting point or a functional group having a crosslinking promoting effect.
Examples of such a functional group include a hydroxy group, an epoxy group, a cyano group, a keto group, and a nitrogen element-containing ring.
なお、本発明において、カルボキシル基含有モノマー及び第１級アミノ基含有モノマーは、官能基含有モノマー（ａ２）’に該当する。ただし、本発明で用いるアクリル系共重合体（Ａ）は、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位の含有量がそれぞれ３．０質量％以下に調整されていることを特徴とする。これらのモノマー由来の構成単位の含有量がそれぞれ３．０質量％を超えると、得られる粘着剤組成物の耐候性が低下し、特に、長時間使用された後、フォトクロミック性能の低下や、紫外線非照射の環境下でも変色した状態が恒常化してしまうという弊害が生じる。 In the present invention, the carboxyl group-containing monomer and the primary amino group-containing monomer correspond to the functional group-containing monomer (a2) ′. However, in the acrylic copolymer (A) used in the present invention, the content of the structural unit derived from the carboxyl group-containing monomer and the primary amino group-containing monomer is adjusted to 3.0% by mass or less, respectively. Features. When the content of the structural units derived from these monomers exceeds 3.0% by mass, the weather resistance of the resulting pressure-sensitive adhesive composition is lowered. In particular, after being used for a long time, the photochromic performance is lowered or ultraviolet rays are reduced. There is an adverse effect that the discolored state becomes permanent even in a non-irradiation environment.
ここで、カルボキシル基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸等のエチレン性不飽和モノカルボン酸；フマル酸、イタコン酸、マレイン酸、シトラコン酸等のエチレン性不飽和ジカルボン酸及びその無水物、２−カルボキシエチルメタクリレート等が挙げられる。 Here, examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; The anhydride, 2-carboxyethyl methacrylate, etc. are mentioned.
一方、第１級アミノ基含有モノマーとしては、例えば、（メタ）アクリルアミド、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸アミノプロピル等が挙げられる。 On the other hand, examples of the primary amino group-containing monomer include (meth) acrylamide, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, and the like.
カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位のそれぞれの含有量は、アクリル系共重合体（Ａ）の全構成単位に対して、３．０質量％以下であるが、長時間使用された後でも、フォトクロミック性能の低下を抑制しつつ、紫外線非照射の環境下での変色が恒常化することを防ぎ得る、優れた耐候性を有する粘着剤組成物とする観点から、好ましくは２．５質量％以下、より好ましくは１．７質量％以下、より好ましくは１．２質量％以下、更に好ましくは０．５質量％以下、より更に好ましくは実質０質量％である。本発明において「実質０質量％」とは、意図的に含有しないことを意味する。 The content of each of the structural units derived from the carboxyl group-containing monomer and the primary amino group-containing monomer is 3.0% by mass or less based on the total structural units of the acrylic copolymer (A). From the viewpoint of an adhesive composition having excellent weather resistance, which can prevent the discoloration in the environment without UV irradiation, while suppressing deterioration of the photochromic performance even after being used for a long time. Is 2.5% by mass or less, more preferably 1.7% by mass or less, more preferably 1.2% by mass or less, still more preferably 0.5% by mass or less, and still more preferably substantially 0% by mass. In the present invention, “substantially 0% by mass” means that it is not intentionally contained.
なお、得られる粘着剤組成物の粘着力を向上させる観点から、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位を含有してもよい。
粘着力を向上させる観点から、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位のそれぞれの含有量は、アクリル系共重合体（Ａ）の全構成単位に対して、好ましくは０．０１質量％以上、より好ましくは０．０４質量％以上、更に好ましくは０．０８質量％以上である。
In addition, you may contain the structural unit derived from a carboxyl group-containing monomer and a primary amino group-containing monomer from a viewpoint of improving the adhesive force of the obtained adhesive composition.
From the viewpoint of improving the adhesive strength, the content of each of the structural units derived from the carboxyl group-containing monomer and the primary amino group-containing monomer is preferably 0 with respect to all the structural units of the acrylic copolymer (A). 0.01% by mass or more, more preferably 0.04% by mass or more, and further preferably 0.08% by mass or more.
以上より、得られる粘着剤組成物の耐候性及び粘着力をバランスよく向上させる観点から、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位の含有量は、アクリル系共重合体（Ａ）の全構成単位に対して、好ましくは０．０１〜３．０質量％、より好ましくは０．０４〜２．５質量％、更に好ましくは０．０８〜１．７質量％である。 From the above, from the viewpoint of improving the weather resistance and adhesive strength of the obtained pressure-sensitive adhesive composition in a well-balanced manner, the content of the structural unit derived from the carboxyl group-containing monomer and the primary amino group-containing monomer is the acrylic copolymer ( Preferably it is 0.01-3.0 mass% with respect to all the structural units of A), More preferably, it is 0.04-2.5 mass%, More preferably, it is 0.08-1.7 mass%.
カルボキシル基含有モノマー及び第１級アミノ基含有モノマー以外のモノマー（ａ２）’としては、例えば、ヒドロキシ基含有モノマー、エポキシ基含有モノマー、シアノ基含有モノマー、ケト基含有モノマー、窒素原子含有環を有するモノマー等が挙げられる。 Examples of the monomer (a2) ′ other than the carboxyl group-containing monomer and the primary amino group-containing monomer include a hydroxy group-containing monomer, an epoxy group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and a nitrogen atom-containing ring. And monomers.
ヒドロキシ基含有モノマーとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；ビニルアルコール、アリルアルコール等の不飽和アルコール類等が挙げられる。 Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
エポキシ基を有するモノマーとしては、例えば、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。 Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
シアノ基含有モノマーとしては、例えば、（メタ）アクリロニトリル等が挙げられる。 Examples of the cyano group-containing monomer include (meth) acrylonitrile.
ケト基含有モノマーとしては、ジアセトン（メタ）アクリルアミド、アセトン（メタ）アクリレート、ビニルメチルケトン、ビニルエチルケトン、アリルアセトアセテート、ビニルアセトアセテート、アセトアセチル（メタ）アクリレート等が挙げられる。 Examples of the keto group-containing monomer include diacetone (meth) acrylamide, acetone (meth) acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, vinyl acetoacetate, and acetoacetyl (meth) acrylate.
窒素原子含有環を有するモノマーとしては、例えば、Ｎ−ビニル−２−ピロリドン、Ｎ−メチルビニルピロリドン、Ｎ−ビニルピペリドン、Ｎ−ビニルピペラジン、Ｎ−ビニルピラジン、Ｎ−ビニルピロール、Ｎ−ビニルイミダゾール、Ｎ−ビニルモルホリン、Ｎ−ビニルカプロラクタム、Ｎ−（メタ）アクリロイルモルホリン等が挙げられる。 Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine and the like can be mentioned.
これらのモノマー（ａ２）’は、単独で又は２種以上組み合わせて用いてもよい。
これらの中でも、凝集力を維持し、粘着力を向上させる観点から、ヒドロキシ基含有モノマーが好ましく、ヒドロキシアルキル（メタ）アクリレート類がより好ましく、２−ヒドロキシエチル（メタ）アクリレート、又は４−ヒドロキシブチル（メタ）アクリレートが更に好ましい。
These monomers (a2) ′ may be used alone or in combination of two or more.
Among these, from the viewpoint of maintaining cohesion and improving adhesive strength, hydroxy group-containing monomers are preferred, hydroxyalkyl (meth) acrylates are more preferred, 2-hydroxyethyl (meth) acrylate, or 4-hydroxybutyl More preferred is (meth) acrylate.
構成単位（ａ２）の含有量は、十分な粘着力を発現させる観点から、アクリル系共重合体（Ａ）の全構成単位に対して、好ましくは０．０１〜３５質量％、より好ましくは０．０３〜３２質量％、更に好ましくは０．１〜１２質量％である。
なお、上記構成単位（ａ２）の含有量には、カルボキシル基含有モノマー及び第１級アミノ基含有モノマー由来の構成単位の含有量も含まれるが、これらモノマー由来の構成単位の含有量の上限値は、上述のとおり、３．０質量％を超えることはない。
The content of the structural unit (a2) is preferably 0.01 to 35% by mass, more preferably 0, based on all the structural units of the acrylic copolymer (A), from the viewpoint of developing sufficient adhesive strength. 0.03 to 32 mass%, more preferably 0.1 to 12 mass%.
In addition, although content of the structural unit derived from a carboxyl group-containing monomer and a primary amino group-containing monomer is also included in the content of the structural unit (a2), the upper limit value of the content of the structural unit derived from these monomers As described above, does not exceed 3.0 mass%.
（その他の構成単位）
なお、アクリル系共重合体（Ａ）は、構成単位として、上記モノマー（ａ１）’及び（ａ２）’以外のその他のモノマー由来の構成単位を含んでもよい。
その他のモノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、エチレン、プロピレン、イソブチレン等のオレフィン類、塩化ビニル、ビニリデンクロリド等のハロゲン化オレフィン類、スチレン、メチルスチレン、ビニルトルエン等の芳香族ビニルモノマー、ブタジエン、イソプレン、クロロプレン等のジエン系モノマー等が挙げられる。
これらのモノマーは、単独で又は２種以上を組み合わせて用いてもよい。
(Other structural units)
The acrylic copolymer (A) may contain a structural unit derived from another monomer other than the monomers (a1) ′ and (a2) ′ as a structural unit.
Other monomers include, for example, vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene, and isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, styrene, methylstyrene, vinyltoluene, and the like. And aromatic vinyl monomers, diene monomers such as butadiene, isoprene and chloroprene.
These monomers may be used alone or in combination of two or more.
以上のモノマーからアクリル系共重合体（Ａ）を合成する方法としては、特に限定されず、溶媒の存在下又は不存在下で、公知の重合方法により合成することができる。
用いる溶媒としては、例えば、酢酸エチル、トルエン等を挙げられる。
なお、重合反応に際し、重合開始剤を用いてもよい。重合開始剤としては、例えば、アゾビスイソブチロニトリル、ベンゾイルパーオキサイド等を挙げられる。
また、重合条件としては、特に限定されないが、重合温度５０〜９０℃で、反応時間２〜３０時間の条件で行われることが好ましい。
The method for synthesizing the acrylic copolymer (A) from the above monomers is not particularly limited, and can be synthesized by a known polymerization method in the presence or absence of a solvent.
Examples of the solvent to be used include ethyl acetate and toluene.
In the polymerization reaction, a polymerization initiator may be used. Examples of the polymerization initiator include azobisisobutyronitrile and benzoyl peroxide.
Moreover, it does not specifically limit as polymerization conditions, However, It is preferable to carry out on the conditions for polymerization temperature 50-90 degreeC and reaction time 2-30 hours.
アクリル系共重合体（Ａ）の重量平均分子量としては、粘着力向上の観点から、好ましくは１８万〜１５０万、より好ましくは２０万〜１２０万、更に好ましくは２５万〜１０５万である。１８万以上であれば、粘着剤組成物の凝集力が向上し、十分な粘着力が得られる。また、１５０万以下であれば、形成した粘着シートの粘着剤層の弾性率が高くなりすぎず、粘着力の低下を抑えることができる。
なお、本発明において、重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した標準ポリスチレン換算の値を意味する。
The weight average molecular weight of the acrylic copolymer (A) is preferably 180,000 to 1,500,000, more preferably 200,000 to 1,200,000, and even more preferably 250,000 to 1,50,000, from the viewpoint of improving the adhesive strength. If it is 180,000 or more, the cohesive force of the pressure-sensitive adhesive composition is improved, and sufficient adhesive force is obtained. Moreover, if it is 1.5 million or less, the elasticity modulus of the adhesive layer of the formed adhesive sheet will not become high too much, and the fall of adhesive force can be suppressed.
In addition, in this invention, a weight average molecular weight (Mw) means the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
なお、アクリル系共重合体（Ａ）の共重合形態については、特に制限はなく、ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。
また、本発明において、上記のアクリル系共重合体（Ａ）は、単独で又は２種以上を組み合わせて用いてもよい。
In addition, there is no restriction | limiting in particular about the copolymerization form of an acryl-type copolymer (A), Any of a random copolymer, a block copolymer, and a graft copolymer may be sufficient.
Moreover, in this invention, you may use said acrylic copolymer (A) individually or in combination of 2 or more types.
上記アクリル系共重合体（Ａ）の含有量は、粘着剤組成物の総量に対して、好ましくは７０〜９９．５質量％、より好ましくは８５〜９９．０質量％、更に好ましくは９０〜９８．０質量％である。７０質量％以上であれば、優れた粘着力を有する粘着剤組成物とすることができる。 The content of the acrylic copolymer (A) is preferably 70 to 99.5% by mass, more preferably 85 to 99.0% by mass, and still more preferably 90 to 90% by mass with respect to the total amount of the pressure-sensitive adhesive composition. It is 98.0 mass%. If it is 70 mass% or more, it can be set as the adhesive composition which has the outstanding adhesive force.
〔架橋剤（Ｂ）〕
本発明の粘着剤組成物は、凝集力を高めて所望の粘着力を得る観点から、アクリル系共重合体（Ａ）が有する官能基と反応する架橋剤（Ｂ）を含有する。
架橋剤（Ｂ）としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、及び金属キレート系架橋剤等が挙げられる。
[Crosslinking agent (B)]
The pressure-sensitive adhesive composition of the present invention contains a crosslinking agent (B) that reacts with the functional group of the acrylic copolymer (A) from the viewpoint of increasing the cohesive force and obtaining a desired pressure-sensitive adhesive force.
Examples of the crosslinking agent (B) include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.
イソシアネート系架橋剤としては、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、１，３−キシリレンジイソシアネート、１，４−キシリレンジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、ジフェニルメタン−２，４’−ジイソシアネート、３−メチルジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、ジシクロヘキシルメタン−２，４’−ジイソシアネート、リジンイソシアネート等の多価イソシアネート化合物、これらの化合物のトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、イソシアヌレート環を含むイソシアヌレート型変性体等の変性体が挙げられる。 Examples of the isocyanate crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanate compounds such as diphenylmethane-2,4′-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, lysine isocyanate , Trimethylolpropane adduct modified products of these compounds, burette modified products reacted with water, isocyanurate modified products containing isocyanurate rings Modified products of the body, and the like.
エポキシ系架橋剤としては、分子中に２個以上のエポキシ基又はグリシジル基を有する化合物であれば、特に限定されないが、分子中に２個以上のグリシジル基を有する多官能性エポキシ化合物が好ましい。
上記の多官能性エポキシ化合物としては、例えば、ビスフェノールＡのジグリシジルエーテル及びそのオリゴマー、水素化ビスフェノールＡのジグリシジルエーテル及びそのオリゴマー、オルソフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、ｐ−オキシ安息香酸グリシジルエステル、テトラハイドロフタル酸ジグリシジルエステル、ヘキサハイドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４−ブタンジオールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル及びポリアルキレングリコールジグリシジルエーテル類、トリメリット酸トリグリシジルエステル、トリグリシジルイソシアヌレート、１，４−ジグリシジルオキシベンゼン、ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールプロパンジ又はトリグリシジルエーテル、ペンタエリスリトールジ又はトリグリシジルエーテル、グリセロールアルキレンオキサイド付加物のトリグリシジルエーテル、ジグリシジルアニリン等のジグリシジルアミン等が挙げられる。
Although it will not specifically limit if it is a compound which has a 2 or more epoxy group or glycidyl group in a molecule | numerator as an epoxy type crosslinking agent, The polyfunctional epoxy compound which has a 2 or more glycidyl group in a molecule | numerator is preferable.
Examples of the polyfunctional epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester. Ester, p-oxybenzoic acid glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and Realkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane di or triglycidyl ether, pentaerythritol Examples thereof include diglycidyl amines such as di- or triglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and diglycidyl aniline.
アジリジン系架橋剤としては、例えば、１，１’−（メチレン−ジ−ｐ−フェニレン）ビス−３，３−アジリジニル尿素、１，１’−（ヘキサメチレン）ビス−３，３−アジリジニル尿素、２，４，６−トリアジリジニル−１，３，５−トリアジン、トリメチロールプロパン−トリス−（２−アジリジニルプロピオネート）等が挙げられる。 Examples of the aziridine-based crosslinking agent include 1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridinyl urea, 1,1 ′-(hexamethylene) bis-3,3-aziridinyl urea, 2,4,6-triaziridinyl-1,3,5-triazine, trimethylolpropane-tris- (2-aziridinylpropionate) and the like.
金属キレート系架橋剤としては、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロム、ジルコニウム等の多価金属にアセチルアセトン、アセト酢酸エチル等が配位した化合物等が挙げられる。 Examples of the metal chelate-based crosslinking agent include compounds in which acetylacetone, ethyl acetoacetate, and the like are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Etc.
これらの架橋剤（Ｂ）は、単独で又は２種以上組み合わせて用いてもよい。
これらの中でも、高い粘着力を発現させる観点から、イソシアネート系架橋剤が好ましい。
These crosslinking agents (B) may be used alone or in combination of two or more.
Among these, an isocyanate-based crosslinking agent is preferable from the viewpoint of developing high adhesive force.
架橋剤（Ｂ）の配合量は、高い粘着力を発現させる観点から、アクリル系共重合体（Ａ）１００質量部に対して、好ましくは０．０１〜８質量部、より好ましくは０．０５〜５質量部、更に好ましくは０．１〜３質量部である。 The blending amount of the crosslinking agent (B) is preferably 0.01 to 8 parts by mass, more preferably 0.05 with respect to 100 parts by mass of the acrylic copolymer (A), from the viewpoint of developing high adhesive strength. -5 parts by mass, more preferably 0.1-3 parts by mass.
〔フォトクロミック性染料（Ｃ）〕
本発明で用いるフォトクロミック性染料（Ｃ）は、フォトクロミック性能を有するものであり、オキサジン系化合物からなる。本発明の粘着剤組成物は、フォトクロミック性染料（Ｃ）として、オキサジン系化合物を含有することで、長時間使用された後でも、フォトクロミック性能の低下を抑制しつつ、紫外線非照射の環境下での変色が恒常化することを防ぎ得る、優れた耐候性を発現させることができる。また、有色から無色への色調変化の速度が速い粘着剤組成物とすることができる。
本発明において、オキサジン系化合物とは、酸素原子、窒素原子をそれぞれ１原子ずつ含む６員環複素環を少なくとも含む化合物を意味する。
[Photochromic dye (C)]
The photochromic dye (C) used in the present invention has photochromic performance and is composed of an oxazine compound. The pressure-sensitive adhesive composition of the present invention contains an oxazine-based compound as a photochromic dye (C), so that even after being used for a long time, the deterioration of photochromic performance is suppressed, and in an environment without ultraviolet irradiation. It is possible to develop excellent weather resistance that can prevent the discoloration of the water from becoming constant. Moreover, it can be set as the adhesive composition with the quick speed | rate of color tone change from colored to colorless.
In the present invention, the oxazine-based compound means a compound containing at least a 6-membered heterocyclic ring containing one oxygen atom and one nitrogen atom.
オキサジン系化合物としては、例えば、ナフトスピロオキサジン等が挙げられる。
ナフトスピロオキサジンとしては、例えば、１，３，３−トリメチルスピロ［インドリン−２，３’−（３Ｈ）−ナフト−（２，１−ｂ）（１，４）−オキサジン］、６’−インドリノ−１，３，３−トリメチルスピロ［インドリン−２，３’−（３Ｈ）−ナフト−（２，１−ｂ）（１，４）−オキサジン］、５−クロル−１，３，３−トリメチルスピロ［インドリン−２，３’−（３Ｈ）−ナフト−（２，１−ｂ）（１，４）−オキサジン］、６’−ピペリジノ−１，３，３−トリメチルスピロ［インドリン−２，３’−（３Ｈ）−ナフト−（２，１−ｂ）（１，４）−オキサジン］、１−ベンジル−３，３−ジメチルスピロ［インドリン−２，３’−（３Ｈ）−ナフト−（２，１−ｂ）（１，４）−オキサジン］、１，３，５，６−テトラメチル−３−エチルスピロ［インドリン−２，３’−（３Ｈ）−ナフト−（２，１−ｂ）（１，４）−オキサジン］、１，３，３，５，６−ペンタメチルスピロ［インドリン−２，３’−（３Ｈ）−ナフト−（２，１−ｂ）（１，４）−オキサジン］、１，３，５，６−テトラメチル−３−エチルスピロ［インドリン−２，３’−（３Ｈ）−ピリド−（３，２−ｆ）（１，４）−ベンゾオキサジン］等が挙げられる。
また、市販品としては、例えば、「Ｔ１２５９（製品名、東京化成工業社製）」等が挙げられる。
これらのオキサジン系化合物は、単独で又は２種以上組み合わせて用いてもよい。
Examples of the oxazine-based compound include naphthospiroxazine.
Examples of naphthospiroxazine include 1,3,3-trimethylspiro [indoline-2,3 ′-(3H) -naphtho (2,1-b) (1,4) -oxazine], 6′-indolino. -1,3,3-trimethylspiro [indoline-2,3 ′-(3H) -naphtho- (2,1-b) (1,4) -oxazine], 5-chloro-1,3,3-trimethyl Spiro [indoline-2,3 ′-(3H) -naphtho- (2,1-b) (1,4) -oxazine], 6′-piperidino-1,3,3-trimethylspiro [indoline-2,3 '-(3H) -naphtho- (2,1-b) (1,4) -oxazine], 1-benzyl-3,3-dimethylspiro [indoline-2,3'-(3H) -naphtho- (2 , 1-b) (1,4) -oxazine], 1,3,5,6-tetramethyl- 3-ethylspiro [indoline-2,3 ′-(3H) -naphtho- (2,1-b) (1,4) -oxazine], 1,3,3,5,6-pentamethylspiro [indoline-2 , 3 ′-(3H) -naphtho- (2,1-b) (1,4) -oxazine], 1,3,5,6-tetramethyl-3-ethylspiro [indoline-2,3 ′-(3H ) -Pyrido- (3,2-f) (1,4) -benzoxazine] and the like.
Moreover, as a commercial item, "T1259 (product name, Tokyo Chemical Industry Co., Ltd. product)" etc. are mentioned, for example.
These oxazine compounds may be used alone or in combination of two or more.
本発明の粘着剤組成物におけるフォトクロミック性染料（Ｃ）の配合量は、アクリル系共重合体（Ａ）１００質量部に対して、０．４０〜８．００質量部である。０．４０質量部未満であると、得られる粘着剤組成物に対して、十分なフォトクロミック性能を発現させることができない。また、８．００質量部を超えると、得られる粘着剤組成物の耐候性が低下し、特に、長時間使用された後において、フォトクロミック性能の低下や、紫外線非照射の環境下でも変色した状態が恒常化してしまうという弊害が生じる。
フォトクロミック性染料（Ｃ）の配合量は、上記観点から、アクリル系共重合体（Ａ）１００質量部に対して、好ましくは０．５０〜６．００質量部、より好ましくは０．５５〜４．８０質量部、より好ましくは０．６０〜４．２０質量部、更に好ましくは０．６５〜３．４０質量部、より更に好ましくは０．７２〜３．００質量部である。
The compounding amount of the photochromic dye (C) in the pressure-sensitive adhesive composition of the present invention is 0.40 to 8.00 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). When the amount is less than 0.40 parts by mass, sufficient photochromic performance cannot be expressed with respect to the obtained pressure-sensitive adhesive composition. In addition, when it exceeds 8.00 parts by mass, the weather resistance of the resulting pressure-sensitive adhesive composition is lowered, and particularly after being used for a long time, the photochromic performance is deteriorated, or the color is changed even in an environment not irradiated with ultraviolet rays. The detrimental effect of becoming permanent.
From the above viewpoint, the blending amount of the photochromic dye (C) is preferably 0.50 to 6.00 parts by mass, more preferably 0.55 to 4 parts per 100 parts by mass of the acrylic copolymer (A). .80 parts by mass, more preferably 0.60 to 4.20 parts by mass, still more preferably 0.65 to 3.40 parts by mass, and even more preferably 0.72 to 3.00 parts by mass.
加えて、粘着剤組成物中に含まれるアクリル系共重合体（Ａ）の構成単位中に第１級アミノ基含有モノマー由来の構成単位を含む場合、当該フォトクロミック性染料（Ｃ）の配合量は、得られる粘着剤組成物の上述の耐候性を向上させる観点から、アクリル系共重合体（Ａ）１００質量部に対して、より好ましくは２．５０質量部以下、より好ましくは１．８０質量部以下、更に好ましくは１．３０質量部以下にすることが好ましい。 In addition, when the structural unit derived from the primary amino group-containing monomer is included in the structural unit of the acrylic copolymer (A) included in the pressure-sensitive adhesive composition, the blending amount of the photochromic dye (C) is From the viewpoint of improving the weather resistance of the obtained pressure-sensitive adhesive composition, the amount is more preferably 2.50 parts by mass or less, more preferably 1.80 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). Or less, more preferably 1.30 parts by mass or less.
なお、本発明の効果を損なわない範囲において、本発明の粘着剤組成物は、オキサジン系化合物以外のフォトクロミック性染料を含有してもよい。 In addition, in the range which does not impair the effect of this invention, the adhesive composition of this invention may contain photochromic dyes other than an oxazine type compound.
〔その他の配合剤〕
本発明の粘着剤組成物は、本発明の効果を損なわず、粘着力等の特性を阻害しない範囲で、さらにその他の配合剤を含有してもよい。
その他の配合剤としては、例えば、粘着付与剤、酸化防止剤、紫外線吸収剤、光安定剤、樹脂安定剤、充填剤、顔料、増量剤、赤外線／近赤外線吸収剤、防腐・防かび剤、防錆剤、可塑剤、高沸点溶剤等が挙げられる。これらの添加剤は、単独で又は２種以上を組み合わせて用いてもよい。
[Other ingredients]
The pressure-sensitive adhesive composition of the present invention may further contain other compounding agents as long as the effects of the present invention are not impaired and the properties such as adhesive strength are not impaired.
Other compounding agents include, for example, tackifiers, antioxidants, ultraviolet absorbers, light stabilizers, resin stabilizers, fillers, pigments, extenders, infrared / near infrared absorbers, antiseptic / antifungal agents, Examples include rust preventives, plasticizers, and high-boiling solvents. These additives may be used alone or in combination of two or more.
（粘着付与剤）
本発明で用いる粘着剤組成物には、得られる粘着剤組成物の粘着力を更に向上させる観点から、さらに粘着付与剤を含有してもよい。
粘着付与剤としては、公知の粘着付与剤が挙げられるが、粘着剤組成物の耐候性を良好とし、フォトクロミック性能を維持する観点から、水素化石油樹脂が好ましい。
本発明において、水素化石油樹脂とは、水素化触媒を使用して、脂肪族系石油樹脂、芳香族系石油樹脂、シクロペンタジエン系石油樹脂等の石油樹脂を水素化したものを意味する。
(Tackifier)
The pressure-sensitive adhesive composition used in the present invention may further contain a tackifier from the viewpoint of further improving the adhesive strength of the obtained pressure-sensitive adhesive composition.
Examples of the tackifier include known tackifiers, and hydrogenated petroleum resins are preferred from the viewpoint of improving the weather resistance of the pressure-sensitive adhesive composition and maintaining photochromic performance.
In the present invention, the hydrogenated petroleum resin means a hydrogenated petroleum resin such as an aliphatic petroleum resin, an aromatic petroleum resin or a cyclopentadiene petroleum resin using a hydrogenation catalyst.
水素化石油樹脂としては、例えば、水添テルペン系樹脂、水添ロジン及び水添ロジンエステル系樹脂、不均化ロジン、不均化ロジンエステル系樹脂、石油ナフサの熱分解で生成するペンテン、イソプレン、ピペリン、１．３−ペンタジエン等のＣ５留分を共重合して得られるＣ５系石油樹脂の水添加樹脂である水添ジシクロペンタジエン系樹脂、部分水添芳香族変性ジシクロペンタジエン系樹脂、石油ナフサの熱分解で生成するインデン、ビニルトルエン、α−又はβ−メチルスチレン等のＣ９留分を共重合して得られるＣ９系石油樹脂を水添した樹脂、上記したＣ５留分とＣ９留分の共重合石油樹脂を水添した樹脂等が挙げられる。 Examples of hydrogenated petroleum resins include hydrogenated terpene resins, hydrogenated rosins and hydrogenated rosin ester resins, disproportionated rosins, disproportionated rosin ester resins, pentenes generated by thermal decomposition of petroleum naphtha, and isoprene. Hydrogenated dicyclopentadiene resin which is a hydrogenated resin of C5 petroleum resin obtained by copolymerizing C5 fractions such as piperine and 1.3-pentadiene, partially hydrogenated aromatic modified dicyclopentadiene resin, Resin obtained by hydrogenation of C9 petroleum resin obtained by copolymerizing C9 fraction such as indene, vinyltoluene, α- or β-methylstyrene produced by thermal decomposition of petroleum naphtha, C5 fraction and C9 fraction described above For example, a resin obtained by hydrogenation of a copolymerized petroleum resin.
粘着付与剤を含有する場合、粘着付与剤の配合量としては、アクリル系共重合体（Ａ）１００質量部に対して、好ましくは５〜６０質量部、より好ましくは１０〜４０質量部、更に好ましくは１５〜２５質量部である。５質量部以上であれば、得られる粘着剤組成物に対して、更に粘着力を向上させることができる。また、６０質量部以下であれば、得られる粘着剤組成物から形成される粘着シートの粘着剤層に十分な柔軟性を付与することができ、ジッピングの発生を抑制することができる。 When the tackifier is contained, the blending amount of the tackifier is preferably 5 to 60 parts by mass, more preferably 10 to 40 parts by mass, more preferably 100 parts by mass of the acrylic copolymer (A). Preferably it is 15-25 mass parts. If it is 5 mass parts or more, adhesive force can be improved further with respect to the obtained adhesive composition. Moreover, if it is 60 mass parts or less, sufficient softness | flexibility can be provided to the adhesive layer of the adhesive sheet formed from the adhesive composition obtained, and generation | occurrence | production of zipping can be suppressed.
（酸化防止剤）
本発明の粘着剤組成物は、さらに酸化防止剤を配合することができる。本発明の粘着剤組成物は、酸化防止剤を配合しても、フォトクロミック性能等を損なうことがない。同時に、酸化防止剤を配合することにより、高湿熱に対する耐久性に優れた粘着剤組成物とすることができる。
(Antioxidant)
The pressure-sensitive adhesive composition of the present invention can further contain an antioxidant. The pressure-sensitive adhesive composition of the present invention does not impair photochromic performance or the like even when an antioxidant is blended. At the same time, by adding an antioxidant, a pressure-sensitive adhesive composition having excellent durability against high heat and humidity can be obtained.
酸化防止剤としては、粘着剤組成物の高湿熱に対する耐久性を向上させる観点から、ヒンダードフェノール系酸化防止剤が好ましく、分岐状のアルキル基を有するヒンダードフェノール系酸化防止剤がより好ましく、ヒンダードフェノール基のベータ位が２つともｔ−ブチル基であるヒンダードフェノール系酸化防止剤が更に好ましい。
ヒンダードフェノール基のベータ位が２つともｔ−ブチル基であるヒンダードフェノール系酸化防止剤は、長時間の駆動や屋外での駆動環境下で用いる場合において、特に耐久性の向上という酸化防止剤としての性能に優れている。
As the antioxidant, from the viewpoint of improving durability against high-humidity heat of the pressure-sensitive adhesive composition, a hindered phenol-based antioxidant is preferable, and a hindered phenol-based antioxidant having a branched alkyl group is more preferable. More preferred are hindered phenol antioxidants in which both of the beta positions of the hindered phenol groups are t-butyl groups.
Hindered phenolic antioxidants in which both of the hindered phenol groups are t-butyl groups are antioxidants that improve durability, especially when used in long-term driving or outdoor driving environments. Excellent performance as an agent.
本発明の粘着剤組成物において酸化防止剤を配合する場合、酸化防止剤の配合量としては、粘着剤組成物の高湿熱に対する耐久性を向上させる観点から、アクリル系共重合体（Ａ）１００質量部に対して、好ましくは０．０１〜１．０質量部、より好ましくは０．０３〜０．５質量部、更に好ましくは０．０４〜０．３質量部である。０．０１質量部以上であれば、得られる粘着剤組成物の耐久性を十分に向上させることができる。一方、１．０質量部以下であれば、他の成分と分離して析出することを抑制することができる。 When the antioxidant is blended in the pressure-sensitive adhesive composition of the present invention, the amount of the antioxidant is from the viewpoint of improving the durability of the pressure-sensitive adhesive composition to high-humidity heat from the acrylic copolymer (A) 100. Preferably it is 0.01-1.0 mass part with respect to a mass part, More preferably, it is 0.03-0.5 mass part, More preferably, it is 0.04-0.3 mass part. If it is 0.01 mass part or more, durability of the obtained adhesive composition can fully be improved. On the other hand, if it is 1.0 mass part or less, it can suppress that it isolate | separates from other components and precipitates.
（紫外線吸収剤）
紫外線吸収剤としては、例えば、ヒンダードアミン系化合物、ベンゾトリアゾール系化合物、オキサゾリアックアシッドアミド化合物、ベンゾフェノン系化合物等が挙げられる。市販品としては、Ｔｉｎｕｖｉｎ７６５（ＢＡＳＳ社製、ヒンダードアミン系化合物）等が挙げられる。
本発明の粘着剤組成物において紫外線吸収剤を配合する場合、紫外線吸収剤の配合量としては、アクリル系共重合体（Ａ）１００質量部に対して、好ましくは０．０１〜３．０質量部、より好ましくは０．０３〜２．０質量部、更に好ましくは０．０４〜１．０質量部である。
(UV absorber)
Examples of the ultraviolet absorber include hindered amine compounds, benzotriazole compounds, oxazolyac acid amide compounds, benzophenone compounds, and the like. Examples of commercially available products include Tinuvin 765 (manufactured by BASS, hindered amine compounds).
When mix | blending a ultraviolet absorber in the adhesive composition of this invention, as a compounding quantity of a ultraviolet absorber, Preferably it is 0.01-3.0 mass with respect to 100 mass parts of acrylic copolymers (A). Part, more preferably 0.03 to 2.0 parts by weight, still more preferably 0.04 to 1.0 parts by weight.
（光安定剤）
光安定剤としては、例えば、ヒンダードアミン系光安定剤、ベンゾフェノン系光安定剤、ベンゾトリアゾール系光安定剤等が挙げられる。
本発明の粘着剤組成物において光安定剤を配合する場合、光安定剤の配合量としては、アクリル系共重合体（Ａ）１００質量部に対して、好ましくは０．０１〜２質量部である。
(Light stabilizer)
Examples of the light stabilizer include hindered amine light stabilizers, benzophenone light stabilizers, and benzotriazole light stabilizers.
When mix | blending a light stabilizer in the adhesive composition of this invention, as a compounding quantity of a light stabilizer, Preferably it is 0.01-2 mass parts with respect to 100 mass parts of acrylic type copolymers (A). is there.
（樹脂安定剤）
樹脂安定剤としては、例えば、イミダゾール系樹脂安定剤、ジチオカルバミン酸塩系樹脂安定剤、リン系樹脂安定剤、硫黄エステル系樹脂安定剤等が挙げられる。
本発明の粘着剤組成物において樹脂安定剤を配合する場合、樹脂安定剤の配合量としては、アクリル系共重合体（Ａ）１００質量部に対して、好ましくは０．０１〜３質量部である。
(Resin stabilizer)
Examples of the resin stabilizer include an imidazole resin stabilizer, a dithiocarbamate resin stabilizer, a phosphorus resin stabilizer, and a sulfur ester resin stabilizer.
When the resin stabilizer is blended in the pressure-sensitive adhesive composition of the present invention, the blending amount of the resin stabilizer is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). is there.
［粘着シート］
本発明の粘着シートは、上述の本発明の粘着剤組成物からなる粘着剤層を有するものであり、基材や剥離材上に当該粘着剤層を有する粘着シートが好ましい。本発明の粘着シートの構成は、特に限定されず、図１（ａ）に示された粘着シート１ａのように、基材１１上に粘着剤層１２を形成した粘着シートに限られない。
例えば、図１（ｂ）示された粘着シート１ｂのように、基材１１上に形成した粘着剤層１２上に、更に別の基材１１’が形成された粘着シートや、図１（ｃ）に示された粘着シート１ｃのように、基材１１上に形成した粘着剤層１２上に、剥離可能な剥離材１３を形成した粘着シート等が挙げられる。
また、図１（ｄ）に示された粘着シート１ｄのように、基材を用いずに、粘着剤層１２を、剥離材１３と別の剥離材１３’とで挟持した粘着シートとしてもよい。なお、粘着シート１ｄにおいて、剥離材１３と剥離材１３’とは、同じ種類の剥離材を用いてもよく、互いに異なる種類の剥離材を用いてもよいが、剥離材１３と剥離材１３’との剥離力差が異なるように調整することが好ましい。
[Adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer comprising the above-mentioned pressure-sensitive adhesive composition of the present invention, and a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer on a substrate or a release material is preferable. The structure of the adhesive sheet of this invention is not specifically limited, It is not restricted to the adhesive sheet which formed the adhesive layer 12 on the base material 11 like the adhesive sheet 1a shown by Fig.1 (a).
For example, as in the pressure-sensitive adhesive sheet 1b shown in FIG. 1B, a pressure-sensitive adhesive sheet in which another base material 11 ′ is formed on the pressure-sensitive adhesive layer 12 formed on the base material 11, or FIG. Like the pressure-sensitive adhesive sheet 1c shown in FIG. 5), a pressure-sensitive adhesive sheet or the like in which a peelable release material 13 is formed on the pressure-sensitive adhesive layer 12 formed on the substrate 11 can be used.
Moreover, it is good also as an adhesive sheet which clamped the adhesive layer 12 with the peeling material 13 and another peeling material 13 'without using a base material like the adhesive sheet 1d shown by FIG.1 (d). . In the pressure-sensitive adhesive sheet 1d, the release material 13 and the release material 13 ′ may use the same type of release material, or may use different types of release materials, but the release material 13 and the release material 13 ′. It is preferable to adjust so that the difference in the peel strength between the two is different.
粘着シートの粘着剤層の厚さとしては、用途等に応じて適宜選定されるが、好ましくは０．５〜１００μｍ、より好ましくは１〜６０μｍ、更に好ましくは３〜４０μｍである。粘着剤層の厚さが０．５μｍ以上であれば、被着体に対し良好な粘着力が得られる。一方、１００μｍ以下であれば、生産性の面で有利であり、取り扱い易い粘着シートとなり得る。 The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is appropriately selected depending on the use and the like, but is preferably 0.5 to 100 μm, more preferably 1 to 60 μm, and still more preferably 3 to 40 μm. When the thickness of the pressure-sensitive adhesive layer is 0.5 μm or more, good adhesive force can be obtained for the adherend. On the other hand, if it is 100 micrometers or less, it is advantageous in terms of productivity and can be an easy-to-handle pressure-sensitive adhesive sheet.
（基材）
基材としては、特に限定されず、粘着シートの使用目的に応じて適宜選定される。
基材としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂等のポリオレフィン樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂等のポリエステル樹脂、アセテート樹脂、ＡＢＳ樹脂、ポリスチレン樹脂、塩化ビニル樹脂等の樹脂、これらの混合物又は積層物からなるプラスチックフィルム又はプラスチックシート；上質紙、アート紙、コート紙、グラシン紙等の紙基材、これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙等の各種紙類；各種合成紙；アルミニウム箔、銅箔、鉄箔等の金属箔；不織布等の多孔質材料からなる基材等が挙げられる。なお、プラスチックフィルム及びプラスチックシート等は、未延伸でもよいし、縦又は横等の一軸方向あるいは二軸方向に延伸されていてもよい。
用いる基材の着色の有無については問わないが、紫外線を十分に透過する基材が好ましく、可視光領域においても無色透明である基材がより好ましい。
(Base material)
It does not specifically limit as a base material, According to the intended purpose of an adhesive sheet, it selects suitably.
Examples of the base material include polyolefin resins such as polyethylene resins and polypropylene resins, polyester resins such as polybutylene terephthalate resins and polyethylene terephthalate resins, resins such as acetate resins, ABS resins, polystyrene resins and vinyl chloride resins, mixtures thereof, or Laminated plastic film or plastic sheet; paper substrates such as fine paper, art paper, coated paper, glassine paper, and various papers such as laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates; Various synthetic papers; metal foils such as aluminum foil, copper foil, and iron foil; and substrates made of porous materials such as nonwoven fabrics. In addition, the plastic film, the plastic sheet, and the like may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as longitudinal or lateral.
Although the base material used is not colored, a base material that sufficiently transmits ultraviolet rays is preferable, and a base material that is colorless and transparent in the visible light region is more preferable.
なお、基材には、更に、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、スリップ剤、アンチブロッキング剤、着色剤等が含有されていてもよい。
また、基材の表面又は裏面には、印刷、印字等を施してもよい。そのために、基材には、感熱記録層、熱転写、インクジェット、レーザー印字等が可能な印字受像層、印刷性向上層等が設けられてもよい。なお、不透明な基材に印刷・印字等された基材を用いた粘着シートは、該粘着シートの粘着剤層越しに印刷面を観察するような用途に使ってもよい。
The base material may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant and the like.
Moreover, you may give printing, printing, etc. to the surface or back surface of a base material. For this purpose, the substrate may be provided with a heat-sensitive recording layer, a print image receiving layer capable of performing thermal transfer, ink jetting, laser printing, and the like, a printability improving layer, and the like. In addition, you may use the adhesive sheet using the base material printed / printed on the opaque base material for the use which observes a printing surface through the adhesive layer of this adhesive sheet.
基材としてプラスチック系材料を用いる場合、基材と粘着剤層との密着性を向上させるために、必要に応じて、基材表面に対し酸化法や凹凸化法等の表面処理を施すことが好ましい。
酸化法としては、特に限定されず、例えば、コロナ放電処理法、プラズマ処理法、クロム酸酸化（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理等が挙げられる。
また、凹凸化法としては、特には限定されず、例えば、サンドブラスト法、溶剤処理法等が挙げられる。
これらの表面処理は、基材の種類に応じて適宜選定されるが、粘着剤層との密着性の向上効果や操作性の観点から、コロナ放電処理法が好ましい。また、プライマー処理を施すこともできる。
When a plastic material is used as the base material, surface treatment such as an oxidation method or a roughening method may be applied to the base material surface as necessary in order to improve the adhesion between the base material and the pressure-sensitive adhesive layer. preferable.
The oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
Moreover, it does not specifically limit as an uneven | corrugated method, For example, a sandblasting method, a solvent processing method, etc. are mentioned.
These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the pressure-sensitive adhesive layer and operability. Moreover, primer treatment can also be performed.
基材の厚さは、特に制限はないが、取り扱い易さの観点から、通常１０〜２５０μｍ、好ましくは１５〜２００μｍ、より好ましくは２０〜１５０μｍである。 Although the thickness of a base material does not have a restriction | limiting in particular, From a viewpoint of the ease of handling, it is 10-250 micrometers normally, Preferably it is 15-200 micrometers, More preferably, it is 20-150 micrometers.
（剥離材）
剥離材としては、基材上に剥離剤を塗布して製造したものが挙げられ、両面剥離処理をされた剥離シートや、片面剥離処理された剥離シート等を用いることができる。
基材としては、例えば、グラシン紙、コート紙、上質紙等の紙基材；これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙；ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂等のポリエステル樹脂フィルム、ポリプロピレン樹脂、ポリエチレン樹脂等のポリオレフィン樹脂フィルム等のプラスチックフィルム等が挙げられる。
剥離剤としては、例えば、シリコーン系樹脂、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂等が挙げられる。
(Peeling material)
Examples of the release material include those manufactured by applying a release agent on a substrate, and a release sheet subjected to double-sided release processing, a release sheet subjected to single-sided release processing, and the like can be used.
Examples of the base material include paper base materials such as glassine paper, coated paper, and high-quality paper; laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials; polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate. Examples thereof include a polyester resin film such as a phthalate resin, and a plastic film such as a polyolefin resin film such as a polypropylene resin and a polyethylene resin.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
剥離材の厚さは、特に制限ないが、通常２０〜２００μｍ、好ましくは２５〜１５０μｍである。 The thickness of the release material is not particularly limited, but is usually 20 to 200 μm, preferably 25 to 150 μm.
（粘着シートの製造方法）
本発明の粘着シートの製造方法としては、特に制限は無く、例えば、本発明の粘着剤組成物に対して、トルエン、酢酸エチル、メチルエチルケトン等の有機溶媒を配合して、粘着剤組成物の溶液を調整し、基材上又は剥離材の剥離処理面上に、公知の塗布方法により、当該溶液を塗布及び乾燥し、粘着剤層を形成させて、粘着シートを得る方法等が挙げられる。
また、基材上に上記の方法で形成した粘着剤層と、別の基材とを貼り合わせれば、図１（ｂ）に示された粘着シート１ｂを作製することができる。他に、基材又は剥離材上に上記の方法で形成した粘着剤層と、上述の剥離材の剥離処理面とを貼り合わせれば、図１（ｃ）に示された粘着シート１ｃや、図１（ｄ）に示された粘着シート１ｄとすることができる。
(Method for producing adhesive sheet)
The method for producing the pressure-sensitive adhesive sheet of the present invention is not particularly limited. For example, a solution of the pressure-sensitive adhesive composition by blending an organic solvent such as toluene, ethyl acetate or methyl ethyl ketone with the pressure-sensitive adhesive composition of the present invention. And a method of obtaining a pressure-sensitive adhesive sheet by applying and drying the solution on a substrate or a release treatment surface of a release material to form a pressure-sensitive adhesive layer.
Moreover, if the adhesive layer formed by said method on the base material and another base material are bonded together, the adhesive sheet 1b shown by FIG.1 (b) can be produced. In addition, if the adhesive layer formed by the above method on the base material or the release material and the release treatment surface of the release material are bonded together, the adhesive sheet 1c shown in FIG. The pressure-sensitive adhesive sheet 1d shown in 1 (d) can be obtained.
粘着剤組成物の溶液の固形分濃度としては、好ましくは１０〜６０質量％、より好ましくは１０〜４５質量％、更に好ましくは１５〜３０質量％である。当該固形分濃度が１０質量％以上であれば、塗布性が良好となる。一方、６０質量％以下であれば、適度な粘度となり、優れた塗布作業性を有する粘着剤組成物の溶液とすることができる。 As solid content concentration of the solution of an adhesive composition, Preferably it is 10-60 mass%, More preferably, it is 10-45 mass%, More preferably, it is 15-30 mass%. If the said solid content concentration is 10 mass% or more, applicability | paintability will become favorable. On the other hand, if it is 60 mass% or less, it will become a moderate viscosity and can be set as the solution of the adhesive composition which has the outstanding workability | operativity.
塗布方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等の公知の方法が挙げられる。また、基材や剥離材の剥離層面に粘着剤組成物を有機溶媒に溶解した溶液を塗布した後、形成される粘着剤層中に溶媒や低沸点成分が残留することを防ぐために、８０〜１５０℃の温度で３０秒〜５分間加熱し乾燥させることが好ましい。 Examples of the coating method include known methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating. Moreover, in order to prevent that a solvent and a low boiling point component remain in the adhesive layer formed, after apply | coating the solution which melt | dissolved the adhesive composition in the organic solvent on the peeling layer surface of a base material or a peeling material, 80- It is preferable to heat and dry at 150 ° C. for 30 seconds to 5 minutes.
［実施例１］
（１）粘着剤組成物の調製
アクリル系共重合体として、ブチルアクリレート（ＢＡ）及びアクリル酸（ＡＡ）からなるアクリル系共重合体（ＢＡ／ＡＡ＝９９．０／１．０（質量％）、重量平均分子量２９万、固形分濃度４８質量％）を用い、該アクリル系共重合体の固形分１００質量部に対し、架橋剤として、トリレンジイソシアネート系架橋剤（日本ポリウレタン社製、製品名「コロネートＬ」、固形分濃度７５質量％）を２．２１質量部（固形分比）、及びフォトクロミック性染料として、下記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）を０．９６質量部（固形分比）添加して混合し、メチルエチルケトンで希釈して、固形分濃度２５質量％の粘着剤組成物の溶液を調製した。
（２）粘着シートの作製
基材として厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東レ株式会社製、製品名「ルミラー」）を用い、当該ＰＥＴフィルム上に、上記の粘着剤組成物の溶液を乾燥後の厚さが２０μｍになるように塗布し、１２０℃で２分間加熱し、厚さ２０μｍの粘着剤層を形成した。次いで、この粘着剤層の表面に、剥離シート（剥離材）として、剥離処理したポリエチレンテレフタレートフィルム（リンテック社製、製品名「ＳＰ−ＰＥＴ３８０１０１」）の剥離処理面を貼付して、粘着シートを作製した。
[Example 1]
(1) Preparation of pressure-sensitive adhesive composition As an acrylic copolymer, an acrylic copolymer composed of butyl acrylate (BA) and acrylic acid (AA) (BA / AA = 99.0 / 1.0 (mass%)) , A weight average molecular weight of 290,000 and a solid content concentration of 48% by mass), a tolylene diisocyanate-based crosslinking agent (product name, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent with respect to 100 parts by mass of the solid content of the acrylic copolymer. As "Coronate L", solid content concentration of 75% by mass, 2.21 parts by mass (solid content ratio) and photochromic dye, an oxazine compound represented by the following formula (1) (product of Tokyo Chemical Industry Co., Ltd., product) 0.96 parts by mass (solid content ratio) was added and mixed, and diluted with methyl ethyl ketone to prepare a pressure-sensitive adhesive composition solution having a solid content concentration of 25% by mass.
(2) Preparation of pressure-sensitive adhesive sheet Using a polyethylene terephthalate (PET) film (product name “Lumirror” manufactured by Toray Industries, Inc.) having a thickness of 100 μm as a base material, a solution of the pressure-sensitive adhesive composition is placed on the PET film. It was applied so that the thickness after drying was 20 μm, and heated at 120 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Next, a release sheet of a polyethylene terephthalate film (product name “SP-PET380101”, manufactured by Lintec Co., Ltd.), which has been subjected to a release treatment, is attached to the surface of the pressure-sensitive adhesive layer as a release sheet (release material) to produce an adhesive sheet. did.
［実施例２］
実施例１の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系染料（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 2]
In the pressure-sensitive adhesive composition of Example 1, the addition amount of the oxazine dye represented by the above formula (1) used as a photochromic dye (Tokyo Chemical Industry Co., Ltd., product name “T1259”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［実施例３］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）及びアクリル酸（ＡＡ）からなるアクリル系共重合体（ＢＡ／ＡＡ＝９９．９／０．１（質量％）、重量平均分子量２２万、固形分濃度４７質量％）を用いた以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 3]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer composed of butyl acrylate (BA) and acrylic acid (AA) (BA / AA = 99.9 / 0.1 (mass%) as the acrylic copolymer. ), A weight average molecular weight of 220,000, and a solid content concentration of 47% by mass) were prepared in the same manner as in Example 1 to prepare a pressure-sensitive adhesive composition solution, and the pressure-sensitive adhesive sheet was prepared using the composition solution. Produced.
［実施例４］
実施例３の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、実施例３と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 4]
In the pressure-sensitive adhesive composition of Example 3, the amount of the oxazine compound represented by the above formula (1) used as a photochromic dye (Tokyo Chemical Industry Co., Ltd., product name “T1259”) was added to 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 3 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［実施例５］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）、メチルアクリレート（ＭＡ）、及び４−ヒドロキシブチルアクリレート（４ＨＢＡ）からなるアクリル系共重合体（ＢＡ／ＭＡ／４ＨＢＡ＝７９．０／２０．０／１．０（質量％）、重量平均分子量９０万、固形分濃度３０質量％）を用い、該アクリル系共重合体の固形分１００質量部に対し、架橋剤として、キシレンジイソシアネート系架橋剤（綜研化学社製、製品名「ＴＤ−７５」、固形分濃度３０質量％）を０．１３質量部、及びフォトクロミック性染料として、上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）を０．９６質量部（固形分比）添加した以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 5]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer (BA / MA /) comprising butyl acrylate (BA), methyl acrylate (MA), and 4-hydroxybutyl acrylate (4HBA) as the acrylic copolymer. 4HBA = 79.0 / 20.0 / 1.0 (mass%), weight average molecular weight 900,000, solid content concentration of 30 mass%), and crosslinking with respect to 100 mass parts of the solid content of the acrylic copolymer. As an agent, xylene diisocyanate-based crosslinking agent (manufactured by Soken Chemical Co., Ltd., product name “TD-75”, solid content concentration: 30% by mass) is expressed by the above formula (1) as 0.13 parts by mass and a photochromic dye. PSA composition in the same manner as in Example 1 except that 0.96 parts by mass (solid content ratio) of an oxazine compound (manufactured by Tokyo Chemical Industry Co., Ltd., product name “T1259”) was added. The solution was prepared, a pressure-sensitive adhesive sheet was prepared using a solution of the composition.
［実施例６］
実施例５の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、実施例５と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 6]
In the pressure-sensitive adhesive composition of Example 5, the amount of the oxazine-based compound represented by the above formula (1) used as a photochromic dye (manufactured by Tokyo Chemical Industry Co., Ltd., product name “T1259”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 5 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［実施例７］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）及び２−ヒドロキシエチルアクリレート（ＨＥＡ）からなるアクリル系共重合体（ＢＡ／ＨＥＡ＝７０．０／３０．０（質量％）、重量平均分子量９０万、固形分濃度３０質量％）を用い、該アクリル系共重合体の固形分１００質量部に対し、架橋剤として、トリレンジイソシアネート系架橋剤（日本ポリウレタン社製、製品名「コロネートＬ」、固形分濃度７５質量％）を４．２５質量部（固形分比）、及びフォトクロミック性染料として、上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）を０．９６質量部（固形分比）添加した以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 7]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer (BA / HEA = 70.0 / 30.0) composed of butyl acrylate (BA) and 2-hydroxyethyl acrylate (HEA) was used as the acrylic copolymer. (Mass%), weight average molecular weight 900,000, solid content concentration 30 mass%), and 100 parts by mass of the solid content of the acrylic copolymer, a tolylene diisocyanate crosslinking agent (Nippon Polyurethane Co., Ltd.) Oxazine compound (Tokyo Kasei Kogyo Co., Ltd.) represented by the above formula (1) as a product, product name “Coronate L”, solid concentration 75% by mass) 4.25 parts by mass (solid content ratio) and photochromic dye A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.96 parts by mass (solid content ratio) was added (product name “T1259”), and the composition was prepared. The solution to prepare a pressure-sensitive adhesive sheet used.
［実施例８］
実施例７の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、実施例７と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 8]
In the pressure-sensitive adhesive composition of Example 7, the amount of the oxazine compound represented by the above formula (1) used as a photochromic dye (Tokyo Chemical Industry Co., Ltd., product name “T1259”) added was 2.88 parts by mass. Except having set it as (solid content ratio), it carried out similarly to Example 7, the solution of the adhesive composition was prepared, and the adhesive sheet was produced using the solution of this composition.
［実施例９］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）、イソブチルアクリレート（ｉＢＡ）、酢酸ビニル（ＶＡｃ）、２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）、及びメタクリル酸（ＭＡＡ）からなるアクリル系共重合体（ＢＡ／ｉＢＡ／ＶＡｃ／ＨＥＭＡ／ＭＡＡ＝４４．０／４４．０／５．７６／６．２０／０．０４（質量％）、重量平均分子量８０万、固形分濃度３７質量％）を用い、該アクリル系共重合体の固形分１００質量部に対し、架橋剤として、ヘキサメチレンジイソシアネート系架橋剤（日本ポリウレタン社製、製品名「コロネートＨＬ」、固形分濃度７５質量％）を０．３９質量部（固形分比）、及びフォトクロミック性染料として、上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）を０．９６質量部（固形分比）添加した以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 9]
In the pressure-sensitive adhesive composition of Example 1, acrylic copolymers include butyl acrylate (BA), isobutyl acrylate (iBA), vinyl acetate (VAc), 2-hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA). An acrylic copolymer (BA / iBA / VAc / HEMA / MAA = 44.0 / 44.0 / 5.76 / 6.20 / 0.04 (mass%), weight average molecular weight 800,000, solid content A concentration of 37% by mass), and 100 parts by mass of the solid content of the acrylic copolymer, as a cross-linking agent, a hexamethylene diisocyanate cross-linking agent (manufactured by Nippon Polyurethane Co., Ltd., product name “Coronate HL”, solid content concentration 75). % By mass) is 0.39 parts by mass (solid content ratio), and a photochromic dye, which is an oxazine system represented by the above formula (1) A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.96 parts by mass (solid content ratio) of the compound (manufactured by Tokyo Chemical Industry Co., Ltd., product name “T1259”) was added. An adhesive sheet was prepared using the solution of the composition.
［実施例１０］
実施例９の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、実施例９と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 10]
In the pressure-sensitive adhesive composition of Example 9, the amount added of the oxazine compound represented by the above formula (1) used as a photochromic dye (Tokyo Chemical Industry Co., Ltd., product name “T1259”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 9 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［実施例１１］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）、エチルアクリレート（ＥＡ）、酢酸ビニル（ＶＡｃ）、及びアクリルアミド（ＡＡｍ）からなるアクリル系共重合体（ＢＡ／ＥＡ／ＶＡｃ／ＡＡｍ＝５４．０／２７．０／１７．０／２．０（質量％）、重量平均分子量１００万、固形分濃度２４．６質量％）を用い、該アクリル系共重合体の固形分１００質量部に対し、架橋剤として、トリレンジイソシアネート系架橋剤（日本ポリウレタン社製、製品名「コロネートＬ」、固形分濃度７５質量％）を３．０５質量部（固形分比）、及びフォトクロミック性染料として、上記式（１）で表されるオキサジン系染料（東京化成工業社製、製品名「Ｔ１２５９」）を０．９６質量部（固形分比）添加した以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 11]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer (BA / A) composed of butyl acrylate (BA), ethyl acrylate (EA), vinyl acetate (VAc), and acrylamide (AAm) was used as the acrylic copolymer. EA / VAc / AAm = 54.0 / 27.0 / 17.0 / 2.0 (mass%), weight average molecular weight 1 million, solid content concentration 24.6 mass%), and the acrylic copolymer As a crosslinking agent, 1005 parts by mass of the solid content of Tolylene diisocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., product name “Coronate L”, solid content concentration: 75% by mass) is 3.05 parts by mass (solid content ratio). And 0.96 parts by mass (solid content ratio) of an oxazine dye represented by the above formula (1) (product name “T1259” manufactured by Tokyo Chemical Industry Co., Ltd.) as a photochromic dye Other than the can, in the same manner as in Example 1, a solution of a pressure-sensitive adhesive composition was prepared, a pressure-sensitive adhesive sheet was prepared using a solution of the composition.
［実施例１２］
実施例１１の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、実施例１１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Example 12]
In the pressure-sensitive adhesive composition of Example 11, the addition amount of the oxazine compound represented by the above formula (1) used as a photochromic dye (Tokyo Chemical Industry Co., Ltd., product name “T1259”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 11 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［比較例１］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）及びアクリル酸（ＡＡ）からなるアクリル系共重合体（ＢＡ／ＡＡ＝９１．０／９．０（質量％）、重量平均分子量８０万、固形分濃度３４質量％）を用いた以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 1]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer composed of butyl acrylate (BA) and acrylic acid (AA) (BA / AA = 91.0 / 9.0 (mass%) was used as the acrylic copolymer. ), A weight average molecular weight of 800,000, and a solid content concentration of 34% by mass) were prepared in the same manner as in Example 1 to prepare a solution of the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive sheet was prepared using the solution of the composition. Produced.
［比較例２］
比較例１の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、比較例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 2]
In the pressure-sensitive adhesive composition of Comparative Example 1, the amount of the oxazine-based compound represented by the above formula (1) used as a photochromic dye (manufactured by Tokyo Chemical Industry Co., Ltd., product name “T1259”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 1 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［比較例３］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）及びアクリル酸（ＡＡ）からなるアクリル系共重合体（ＢＡ／ＡＡ＝９４．０／６．０（質量％）、重量平均分子量８０万、固形分濃度３４質量％）を用いた以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 3]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer (BA / AA = 94.0 / 6.0 (mass%) composed of butyl acrylate (BA) and acrylic acid (AA) was used as the acrylic copolymer. ), A weight average molecular weight of 800,000, and a solid content concentration of 34% by mass) were prepared in the same manner as in Example 1 to prepare a solution of the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive sheet was prepared using the solution of the composition. Produced.
［比較例４］
比較例３の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、比較例３と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 4]
In the pressure-sensitive adhesive composition of Comparative Example 3, the amount of the oxazine-based compound represented by the above formula (1) used as a photochromic dye (manufactured by Tokyo Chemical Industry Co., Ltd., product name “T1259”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 3 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［比較例５］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）及びアクリル酸（ＡＡ）からなるアクリル系共重合体（ＢＡ／ＡＡ＝９６．０／４．０（質量％）、重量平均分子量１４５万、固形分濃度１７質量％）を用いた以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 5]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer composed of butyl acrylate (BA) and acrylic acid (AA) (BA / AA = 96.0 / 4.0 (mass%) was used as the acrylic copolymer. ), A weight average molecular weight of 1,450,000, and a solid content concentration of 17% by mass), a solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition. Produced.
［比較例６］
比較例５の粘着剤組成物において、フォトクロミック性染料として用いた上記式（１）で表されるオキサジン系化合物（東京化成工業社製、製品名「Ｔ１２５９」）の添加量を２．８８質量部（固形分比）とした以外は、比較例５と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 6]
In the pressure-sensitive adhesive composition of Comparative Example 5, the amount of the oxazine compound represented by the above formula (1) used as a photochromic dye (manufactured by Tokyo Chemical Industry Co., Ltd., product name “T1259”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 5 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［比較例７］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）、イソブチルアクリレート（ｉＢＡ）、酢酸ビニル（ＶＡｃ）、２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）、及びメタクリル酸（ＭＡＡ）からなるアクリル系共重合体（ＢＡ／ｉＢＡ／ＶＡｃ／ＨＥＭＡ／ＭＡＡ＝４４．０／４４．０／５．７６／６．２０／０．０４（質量％）、重量平均分子量８０万、固形分濃度３７質量％）を用い、該アクリル系共重合体の固形分１００質量部に対し、架橋剤として、ヘキサメチレンジイソシアネート系架橋剤（日本ポリウレタン社製、製品名「コロネートＨＬ」、固形分濃度７５質量％）を０．３９質量部（固形分比）、及びフォトクロミック性染料として、下記式（２）で表されるスピロピラン系化合物（東京化成工業社製、製品名「Ｔ０３６６」）を０．９６質量部（固形分比）添加した以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 7]
In the pressure-sensitive adhesive composition of Example 1, acrylic copolymers include butyl acrylate (BA), isobutyl acrylate (iBA), vinyl acetate (VAc), 2-hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA). An acrylic copolymer (BA / iBA / VAc / HEMA / MAA = 44.0 / 44.0 / 5.76 / 6.20 / 0.04 (mass%), weight average molecular weight 800,000, solid content A concentration of 37% by mass), and 100 parts by mass of the solid content of the acrylic copolymer, as a cross-linking agent, a hexamethylene diisocyanate cross-linking agent (manufactured by Nippon Polyurethane Co., Ltd., product name “Coronate HL”, solid content concentration 75). % By mass) 0.39 parts by mass (solid content ratio) and a photochromic dye, spiropyran represented by the following formula (2) A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that 0.96 parts by mass (solid content ratio) of the compound (manufactured by Tokyo Chemical Industry Co., Ltd., product name “T0366”) was added. A pressure-sensitive adhesive sheet was prepared using the product solution.
［比較例８］
比較例７の粘着剤組成物において、フォトクロミック性染料として用いた上記式（２）で表されるスピロピラン系化合物（東京化成工業社製、製品名「Ｔ０３６６」）の添加量を２．８８質量部（固形分比）とした以外は、比較例７と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 8]
In the pressure-sensitive adhesive composition of Comparative Example 7, the addition amount of the spiropyran compound represented by the above formula (2) used as a photochromic dye (Tokyo Chemical Industry Co., Ltd., product name “T0366”) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 7 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
［比較例９］
実施例１の粘着剤組成物において、アクリル系共重合体として、ブチルアクリレート（ＢＡ）、エチルアクリレート（ＥＡ）、酢酸ビニル（ＶＡｃ）、及びアクリルアミド（ＡＡｍ）からなるアクリル系共重合体（ＢＡ／ＥＡ／ＶＡｃ／ＡＡｍ＝５４．０／２７．０／１７．０／２．０（質量％）、重量平均分子量１００万、固形分濃度２４．６質量％）を用い、該アクリル系共重合体の固形分１００質量部に対し、架橋剤として、トリレンジイソシアネート系架橋剤（日本ポリウレタン社製、製品名「コロネートＬ」、固形分濃度７５質量％）を３．０５質量部（固形分比）、及びフォトクロミック性染料として、上記式（２）で表されるスピロピラン系化合物（東京化成工業社製、製品名「Ｔ０３６６」）を０．９６質量部（固形分比）添加した以外は、実施例１と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 9]
In the pressure-sensitive adhesive composition of Example 1, an acrylic copolymer (BA / A) composed of butyl acrylate (BA), ethyl acrylate (EA), vinyl acetate (VAc), and acrylamide (AAm) was used as the acrylic copolymer. EA / VAc / AAm = 54.0 / 27.0 / 17.0 / 2.0 (mass%), weight average molecular weight 1 million, solid content concentration 24.6 mass%), and the acrylic copolymer As a crosslinking agent, 1005 parts by mass of the solid content of Tolylene diisocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., product name “Coronate L”, solid content concentration 75% by mass) is 3.05 parts by mass (solid content ratio). As a photochromic dye, 0.96 parts by mass (solid content ratio) of a spiropyran compound represented by the above formula (2) (product name “T0366” manufactured by Tokyo Chemical Industry Co., Ltd.) Except where pressure, in the same manner as in Example 1, a solution of a pressure-sensitive adhesive composition was prepared, a pressure-sensitive adhesive sheet was prepared using a solution of the composition.
［比較例１０］
比較例９の粘着剤組成物において、フォトクロミック性染料として用いた上記式（２）で表されるスピロピラン系染料（東京化成工業社製、製品名「Ｔ０３６６」）の添加量を２．８８質量部（固形分比）とした以外は、比較例９と同様にして、粘着剤組成物の溶液を調製し、該組成物の溶液を用いて粘着シートを作製した。
[Comparative Example 10]
In the pressure-sensitive adhesive composition of Comparative Example 9, the added amount of the spiropyran dye represented by the above formula (2) used as a photochromic dye (product name “T0366” manufactured by Tokyo Chemical Industry Co., Ltd.) was 2.88 parts by mass. A solution of the pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 9 except that (solid content ratio) was used, and a pressure-sensitive adhesive sheet was prepared using the solution of the composition.
上記のようにして作製した粘着シートの評価方法は以下の通りである。これらの評価結果を表１に示す。
（１）紫外線非照射の環境下での着色の有無の評価
実施例及び比較例で作製した粘着シートを２０ｍｍ×２０ｍｍの大きさに裁断し、剥離シートを除去し、表出した粘着剤層面とガラス板（エヌ・エス・ジー・プレシジョン社製、製品名「コーニングガラス イーグルＸＧ」、１５０ｍｍ×７０ｍｍ×２ｍｍ）とをスキージーを用いて貼り合わせ、評価用サンプルを作製した。
初めに、紫外線を照射していない環境下にて、上記評価用サンプルを目視で観察し、下記基準に基づき、着色されているか否かの評価を行った。なお、当該評価結果は、表１中の「作製直後」の欄に記載している。
さらに耐候性試験機（スガ試験機社製、製品名「紫外線フェードメーターＵ４８」、光源：カーボンアークランプ（以下、「ＦＯＭ」ともいう））を用いて、当該評価用サンプルを７５時間及び１５０時間照射した。その後、紫外線が照射されていない環境下にて、当該評価用サンプルを目視で観察し、下記基準に基づき、着色されているか否かの評価を行った。なお、当該評価結果は、表１中の「ＦＯＭ７５ｈ」及び「ＦＯＭ１５０ｈ」の欄に記載している。
（紫外線非照射の環境下での着色の有無の評価基準）
Ａ＋：着色が認められず、無色である。
Ａ：凝視すればわずかな着色が認められるが、ほぼ無色に近い。
Ｂ：淡黄、淡赤、淡茶等の淡色の着色が認められる。
Ｃ：黄、赤、茶等の着色がはっきりと認められる。
The evaluation method of the pressure-sensitive adhesive sheet produced as described above is as follows. These evaluation results are shown in Table 1.
(1) Evaluation of presence / absence of coloring under non-ultraviolet irradiation environment The adhesive sheets prepared in Examples and Comparative Examples were cut into a size of 20 mm × 20 mm, the release sheet was removed, and the exposed adhesive layer surface A glass plate (manufactured by NSG Precision Co., Ltd., product name “Corning Glass Eagle XG”, 150 mm × 70 mm × 2 mm) was bonded using a squeegee to prepare a sample for evaluation.
First, the sample for evaluation was visually observed in an environment not irradiated with ultraviolet rays, and whether or not it was colored was evaluated based on the following criteria. The evaluation results are listed in the “immediately after production” column of Table 1.
Furthermore, using a weather resistance tester (manufactured by Suga Test Instruments Co., Ltd., product name “UV Fade Meter U48”, light source: carbon arc lamp (hereinafter also referred to as “FOM”)), the sample for evaluation was subjected to 75 hours and 150 hours. Irradiated. Thereafter, the sample for evaluation was visually observed in an environment where no ultraviolet rays were irradiated, and an evaluation was made as to whether or not the sample was colored based on the following criteria. The evaluation results are described in the columns of “FOM75h” and “FOM150h” in Table 1.
(Evaluation criteria for the presence or absence of coloring in an environment without UV irradiation)
A +: Coloring is not recognized and is colorless.
A: Slight coloring is observed when staring, but it is almost colorless.
B: Light coloration such as light yellow, light red, and light brown is observed.
C: Coloring of yellow, red, brown, etc. is clearly recognized.
（２）フォトクロミック性能の評価
上述のとおり作製した評価用サンプルに対して、紫外線照射装置（アズワン社製、製品名「Ｈａｎｄｙ ＵＶ Ｌａｍｐ ＳＬＵＶ−４」）を用いて、紫外線（波長３６５ｎｍ）を５秒間照射し、当該評価用サンプルを目視で観察し、下記基準に基づき、発色するか否かの評価を行った。なお、当該評価結果は、表１中の「作製直後」の欄に記載している。
さらに耐候性試験機（スガ試験機社製、製品名「フェードメーターＵ４８」、光源：カーボンアークランプ）を用いて、当該評価用サンプルを２５時間、５０時間照射した。その後、評価用サンプルに、上述の紫外線照射装置を用いて、紫外線（波長３６５ｎｍ）を５秒間照射し、当該評価用サンプルを目視で観察し、上記と同様に評価した。なお、当該評価結果は、それぞれ表１中の「ＦＯＭ２５ｈ」及び「ＦＯＭ５０ｈ」の欄に記載している。
（長時間の耐候性の評価基準）
Ａ：十分に発色する。
Ｂ：発色する。
Ｃ：発色しない（変化なし）。
(2) Evaluation of photochromic performance The sample for evaluation produced as described above was irradiated with ultraviolet rays (wavelength 365 nm) for 5 seconds using an ultraviolet irradiation device (manufactured by ASONE, product name “Handy UV Lamp SLUV-4”). Irradiation was conducted, and the sample for evaluation was visually observed, and whether or not color was developed was evaluated based on the following criteria. The evaluation results are listed in the “immediately after production” column of Table 1.
Further, the sample for evaluation was irradiated for 25 hours and 50 hours using a weather resistance tester (manufactured by Suga Test Instruments Co., Ltd., product name “Fade Meter U48”, light source: carbon arc lamp). Thereafter, the evaluation sample was irradiated with ultraviolet rays (wavelength 365 nm) for 5 seconds using the above-described ultraviolet irradiation apparatus, and the evaluation sample was visually observed and evaluated in the same manner as described above. The evaluation results are described in the columns “FOM25h” and “FOM50h” in Table 1, respectively.
(Evaluation criteria for long-term weather resistance)
A: Full color is developed.
B: Color develops.
C: No color development (no change)
（３）消色時間の評価
上述のとおり作製した評価用サンプルに対して、紫外線照射装置（アズワン社製、製品名「Ｈａｎｄｙ ＵＶ Ｌａｍｐ ＳＬＵＶ−４」）を用いて、紫外線（波長３６５ｎｍ）を５秒間照射し、当該評価用サンプルが、紫外線照射前の状態まで色が戻るのに要した時間を測定し、測定時間に応じて、以下の通り評価をした。
Ａ：１０秒未満で消色する。
Ｆ：１０秒以上経っても消色しない。
(3) Evaluation of decoloring time Using an ultraviolet irradiation device (manufactured by ASONE, product name “Handy UV Lamp SLUV-4”), 5 ultraviolet rays (wavelength 365 nm) were applied to the evaluation sample prepared as described above. Irradiation was performed for 2 seconds, and the time required for the sample for evaluation to return to the state before the ultraviolet irradiation was measured, and evaluation was performed as follows according to the measurement time.
A: Discolor in less than 10 seconds.
F: Does not fade even after 10 seconds.
実施例１〜１２の粘着シートは、フェードメーターに７５時間投入した後でも着色が抑えられており、紫外線非照射の環境下でも変色が恒常化することを防ぎうる結果であった。
また、フェードメーターに５０時間投入した後においても、紫外線照射により発色が確認され、フォトクロミック性能が維持され、優れた耐候性を有していることが分かる。
さらに、消色時間も短く、有色から無色への色調変化の速度が速いことも分かる。
一方、比較例１〜１０の粘着シートは、上記の評価のいずれかの点で劣る結果となった。
In the pressure-sensitive adhesive sheets of Examples 1 to 12, coloring was suppressed even after being put into a fade meter for 75 hours, and it was possible to prevent the discoloration from becoming permanent even in an environment without ultraviolet irradiation.
Moreover, even after putting it in a fade meter for 50 hours, it can be seen that color development is confirmed by ultraviolet irradiation, photochromic performance is maintained, and excellent weather resistance is obtained.
Further, it can be seen that the decoloring time is short and the speed of color change from colored to colorless is fast.
On the other hand, the adhesive sheets of Comparative Examples 1 to 10 were inferior in any of the above evaluations.
本発明の粘着剤組成物、及び粘着シートは、長時間使用された後でも、フォトクロミック性能の低下を抑制しつつ、紫外線非照射の環境下での変色が恒常化することを防ぎ得る、優れた耐候性を有し、また、有色から無色への色調変化の速度も速い。
そのため、本発明の粘着シートは、窓ガラスや壁面、間仕切り用のガラスや透明樹脂板、ブラックライトが照射される空間内で使用されるイルミネーション用のガラスや透明樹脂板、自動車、バス、電車等の車輌、サングラス、眼鏡等のレンズ等において、光の透過性を調節する目的で貼付され、屋外もしくは屋内で使用される着色シートの用途として好適である。
The pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention are excellent in that they can prevent the discoloration in an environment not irradiated with ultraviolet rays from becoming permanent, while suppressing a decrease in photochromic performance even after being used for a long time. It has weather resistance and also has a fast rate of color change from colored to colorless.
Therefore, the pressure-sensitive adhesive sheet of the present invention includes window glass and wall surfaces, partition glass and transparent resin plates, illumination glass and transparent resin plates used in the space irradiated with black light, automobiles, buses, trains, etc. In a vehicle, a lens such as sunglasses, glasses, etc., it is affixed for the purpose of adjusting the light transmission property, and is suitable for use as a coloring sheet used outdoors or indoors.
１ａ、１ｂ、１ｃ 粘着シート
１１、１１’ 基材
１２ 粘着剤層
１３、１３’ 剥離材
1a, 1b, 1c Adhesive sheet 11, 11 'Base material 12 Adhesive layer 13, 13' Release material
Claims (7)
フォトクロミック性染料（Ｃ）の配合量が、アクリル系共重合体（Ａ）１００質量部に対して、０．４０〜８．００質量部であり、
光の透過性を調節する目的で貼付され、屋外もしくは屋内で使用される着色シートに用いられる、粘着剤組成物。 It has a structural unit (a1) derived from an alkyl (meth) acrylate (a1) ′ and a structural unit (a2) derived from a functional group-containing monomer (a2) ′, and is derived from a carboxyl group-containing monomer and a primary amino group-containing monomer. A pressure-sensitive adhesive composition containing a photochromic dye (C) comprising an acrylic copolymer (A), a crosslinking agent (B), and an oxazine compound each having a constituent unit content of 3.0% by mass or less. There,
The amount of the photochromic dye (C) is an acrylic copolymer (A) with respect to 100 parts by weight, Ri 0.40 to 8.00 parts by mass der,
A pressure-sensitive adhesive composition that is applied to a colored sheet that is affixed for the purpose of adjusting light permeability and used outdoors or indoors .
The adhesive sheet which has an adhesive layer which consists of an adhesive composition in any one of Claims 1-6 .
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| CN201380017431.2A CN104204127B (en) | 2012-03-30 | 2013-03-26 | Adhesive composition and bonding sheet |
| PCT/JP2013/058854 WO2013146813A1 (en) | 2012-03-30 | 2013-03-26 | Adhesive composition and adhesive sheet |
| US14/387,605 US20150031785A1 (en) | 2012-03-30 | 2013-03-26 | Adhesive composition and adhesive sheet |
| TW102111321A TWI579362B (en) | 2012-03-30 | 2013-03-29 | Adhesive composition and adhesive sheet |
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