JP4498057B2 - Photopolymerizable acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or tape using the composition - Google Patents
Photopolymerizable acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or tape using the composition Download PDFInfo
- Publication number
- JP4498057B2 JP4498057B2 JP2004232497A JP2004232497A JP4498057B2 JP 4498057 B2 JP4498057 B2 JP 4498057B2 JP 2004232497 A JP2004232497 A JP 2004232497A JP 2004232497 A JP2004232497 A JP 2004232497A JP 4498057 B2 JP4498057 B2 JP 4498057B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- weight
- pressure
- parts
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims description 66
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 46
- 229920005989 resin Polymers 0.000 claims description 70
- 239000011347 resin Substances 0.000 claims description 70
- 239000000178 monomer Substances 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 26
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- -1 alkyl acrylate ester Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 9
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 8
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229920000058 polyacrylate Polymers 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 5
- 238000012662 bulk polymerization Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 4
- 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 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- SUAYFRHPQLERMW-UHFFFAOYSA-N 2-methyl-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(C)(C)C(=O)C1=CC=CC=C1 SUAYFRHPQLERMW-UHFFFAOYSA-N 0.000 description 2
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-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
- 229920001342 Bakelite® Polymers 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 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 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- ZWVXMGIAPJZXCO-UHFFFAOYSA-N 2-cyclohexyl-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1CCCCC1 ZWVXMGIAPJZXCO-UHFFFAOYSA-N 0.000 description 1
- DDMXJSKEBBVELP-UHFFFAOYSA-N 2-ethyl-2-(2-methylpentan-2-ylperoxy)hexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)CCC DDMXJSKEBBVELP-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical group CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- ORTNTAAZJSNACP-UHFFFAOYSA-N 6-(oxiran-2-ylmethoxy)hexan-1-ol Chemical compound OCCCCCCOCC1CO1 ORTNTAAZJSNACP-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- MAMABHFMIUQTIY-UHFFFAOYSA-N CC1=CC=CC=C1.N=C=O.N=C=O.N=C=O Chemical compound CC1=CC=CC=C1.N=C=O.N=C=O.N=C=O MAMABHFMIUQTIY-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- BWLKKFSDKDJGDZ-UHFFFAOYSA-N [isocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)C1=CC=CC=C1 BWLKKFSDKDJGDZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical class C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 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
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GOZDOXXUTWHSKU-UHFFFAOYSA-N pentadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C=C GOZDOXXUTWHSKU-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、長鎖アルキル基を有し、ポリオレフィンや塗装鋼板などの低エネルギー表面の被着体に対しても優れた接着力を示す光重合性アクリル系粘着剤組成物に関する。またこのアクリル系粘着剤を支持体の片面または両面に設けてシート状やテープ状などの形態とした粘着シート又はテープに関する。 The present invention relates to a photopolymerizable acrylic pressure-sensitive adhesive composition having a long-chain alkyl group and exhibiting excellent adhesion even to adherends having a low energy surface such as polyolefin and coated steel sheet. The present invention also relates to a pressure-sensitive adhesive sheet or tape in which the acrylic pressure-sensitive adhesive is provided on one side or both sides of a support to form a sheet or tape.
従来、（メタ）アクリルポリマーは、それ自身に粘着性があり、耐熱性及び耐候性の良好な感圧接着剤となり得るが、常温での接着性や、ポリオレフィン、自動車塗料面などの低エネルギー表面への接着性に劣っている。この欠点を解消し、感圧性接着剤に有効な特性を付与するために、通常ロジン系樹脂、変性ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、Ｃ５およびＣ９系石油樹脂、クマロン樹脂などの粘着付与樹脂が配合されている。しかしながら、アクリル系感圧接着剤に対して、ロジン酸誘導体に代表されるような一般的な粘着付与樹脂を添加すると、透明性や耐候性が低下することがあり、これにより経日での粘着特性低下を招くおそれがある。さらに、シートに塗布した光重合性組成物を紫外線の照射により硬化して得られるアクリル系感圧接着剤の製造において、このような粘着付与樹脂が重合反応時に存在する場合には、その構造により連鎖移動剤や反応停止剤として作用し、重合反応の阻害もしくは遅延を招く恐れもある。 Conventionally, (meth) acrylic polymers have pressure-sensitive adhesives themselves and can be pressure-sensitive adhesives with good heat resistance and weather resistance, but low-energy surfaces such as adhesion at room temperature and polyolefins, automotive paint surfaces, etc. Inferior to the adhesive. In order to eliminate this drawback and to give effective properties to the pressure-sensitive adhesive, usually rosin resin, modified rosin resin, terpene resin, terpene phenol resin, C5 and C9 petroleum resin, coumarone resin, etc. A tackifying resin is blended. However, when a general tackifying resin represented by a rosin acid derivative is added to an acrylic pressure-sensitive adhesive, transparency and weather resistance may be lowered. There is a risk of deterioration of characteristics. Furthermore, in the production of an acrylic pressure-sensitive adhesive obtained by curing a photopolymerizable composition applied to a sheet by irradiation with ultraviolet rays, if such a tackifying resin is present during the polymerization reaction, It may act as a chain transfer agent or a reaction terminator, leading to inhibition or delay of the polymerization reaction.
これに対して、上記のような従来の粘着付与樹脂の欠点を改善すべく、アクリル系ポリマー粘着付与樹脂など、新規な粘着付与樹脂を配合した感圧接着剤が開示されている。アクリルポリマーに、粘着付与剤として（メタ）アクリル酸アルキルエステルとビニル芳香族系化合物とを共重合して得られ、数平均分子量５００〜３５００、軟化点４０℃以下であるオリゴマーを配合した感圧接着剤（特許文献１参照）、炭素数４〜１２個のアクリル酸アルキルエステルと極性共重合性モノマーを共重合して得られたポリマーに、粘着付与樹脂として数平均分子量が約３００〜２５００であり、多分散指数が約５未満であり、ガラス転移温度（Ｔｇ）が約４０〜１２０℃であり、溶解パラメーターが約７〜９．５（ｃａｌ／ｃｃ）0.5である脂肪族ポリマー樹脂を配合した感圧接着剤（特許文献２参照）、各種粘着剤組成物に、炭素数１〜２０のアクリル酸アルキルエステルまたはアクリル酸シクロアルキルエステルと遊離基重合性オレフィン酸とを重合して得られた数平均分子量約３５０００以下、軟化点約４０℃以上のポリマー型添加物を含有する粘着剤組成物（特許文献３参照）などである。 On the other hand, a pressure-sensitive adhesive containing a novel tackifying resin such as an acrylic polymer tackifying resin has been disclosed in order to improve the drawbacks of the conventional tackifying resin as described above. Pressure sensitivity obtained by copolymerizing an acrylic polymer with a (meth) acrylic acid alkyl ester and a vinyl aromatic compound as a tackifier and having a number average molecular weight of 500 to 3500 and a softening point of 40 ° C. or lower. A polymer obtained by copolymerizing an adhesive (see Patent Document 1), an alkyl acrylate ester having 4 to 12 carbon atoms and a polar copolymerizable monomer, has a number average molecular weight of about 300 to 2500 as a tackifier resin. Contains an aliphatic polymer resin having a polydispersity index of less than about 5, a glass transition temperature (Tg) of about 40-120 ° C., and a solubility parameter of about 7-9.5 (cal / cc) 0.5 Pressure-sensitive adhesive (see Patent Document 2), various pressure-sensitive adhesive compositions, and C 1-20 alkyl acrylate or cycloalkyl acrylate and free A pressure-sensitive adhesive composition containing a polymer-type additive having a number average molecular weight of about 35,000 or less and a softening point of about 40 ° C. or more obtained by polymerizing a group-polymerizable olefinic acid (see Patent Document 3).
一方、アルキル基の炭素数が２〜１４のアクリル系アルキルエステルと、アルキル基の炭素数が１５〜２０のアクリル系長鎖アルキルエステルとを共重合して、感圧接着剤の表面エネルギーを低下させ、被着体の表面エネルギーに近づけることにより低エネルギー表面に対する接着力を高める感圧性接着剤（特許文献４参照）や、一価アルコールのアクリル酸エステル（但し、そのホモポリマーは０℃より低いＴｇを有する）と、非極性エチレン性不飽和モノマー（但し、そのホモポリマーは、１０．５０より大きくない溶解パラメーター、及び１５℃より高いＴｇを有する）と、極性エチレン性不飽和モノマー（但し、そのホモポリマーは１０．５０より大きな溶解パラメーター、及び１５℃より高いＴｇを有する）との重合生成物である感圧接着剤（特許文献５参照）などが開示されている。 On the other hand, the surface energy of the pressure-sensitive adhesive is reduced by copolymerizing an acrylic alkyl ester having 2 to 14 carbon atoms in the alkyl group and an acrylic long-chain alkyl ester having 15 to 20 carbon atoms in the alkyl group. Pressure sensitive adhesive (see Patent Document 4) that increases the adhesion to the low energy surface by bringing it close to the surface energy of the adherend, and acrylic acid ester of monohydric alcohol (however, its homopolymer is lower than 0 ° C.) Having a Tg), a non-polar ethylenically unsaturated monomer (where the homopolymer has a solubility parameter not greater than 10.50, and a Tg greater than 15 ° C.), and a polar ethylenically unsaturated monomer (provided that The homopolymer is a polymerization product with a solubility parameter greater than 10.50 and a Tg greater than 15 ° C.) Such as adhesives (see Patent Document 5) are disclosed.
これらの粘着剤組成物は、ポリマーと粘着付与樹脂との相溶性が充分でない、表面エネルギーの低い被着体に対する接着力が充分でないなどの欠点を完全に解消できていない。さらに、これらの粘着付与樹脂或いは粘着剤を重合する際は、通常、溶液重合法やバルク重合法、乳化重合法などの方法で重合を行うのが一般的である。この際、長鎖アルキル基を有するアクリル系モノマーの含有量が増加するに従い、重合中にゲル化が起こり易くなる。また、これらの粘着剤組成物を用いて粘着シート類を製造する際、有機溶剤を用いて粘着剤組成物の粘度調整を行い、基材に塗布するのに適した粘着剤溶液を得る。有機溶媒を含有した粘着剤溶液を用いる場合には基材に塗布または含浸した粘着剤溶液を高温で乾燥するのに多大なエネルギーを消費され、また、溶剤による大気汚染を防止するために、膨大な回収装置が必要である。しかも、有機溶剤は引火し易いため、安全保持のために充分な安全装置を必要とする。エマルジョンを用いる場合、水を蒸発させるには溶剤を蒸発させるよりもさらに大きなエネルギーが必要となる。また、重合時に混入する乳化剤により耐水性が低下する。しかも、水溶性モノマーが使用できないため、モノマー種が限定され、粘着剤に要求される多種多様なニーズへの対応が乏しいという欠点がある。 These pressure-sensitive adhesive compositions cannot completely eliminate the drawbacks such as insufficient compatibility between the polymer and the tackifying resin and insufficient adhesion to an adherend having a low surface energy. Furthermore, when polymerizing these tackifier resins or pressure-sensitive adhesives, the polymerization is generally carried out by a method such as a solution polymerization method, a bulk polymerization method or an emulsion polymerization method. At this time, as the content of the acrylic monomer having a long-chain alkyl group increases, gelation easily occurs during polymerization. Moreover, when manufacturing an adhesive sheet using these adhesive compositions, the viscosity of an adhesive composition is adjusted using an organic solvent, and the adhesive solution suitable for apply | coating to a base material is obtained. When an adhesive solution containing an organic solvent is used, a great deal of energy is consumed to dry the adhesive solution applied or impregnated on the substrate at a high temperature, and in order to prevent air pollution by the solvent, Recovery equipment is required. Moreover, since organic solvents are flammable, a sufficient safety device is required to maintain safety. When using an emulsion, evaporating water requires more energy than evaporating the solvent. Moreover, water resistance falls by the emulsifier mixed at the time of superposition | polymerization. In addition, since a water-soluble monomer cannot be used, there are disadvantages that the types of monomers are limited and the response to various needs required for pressure-sensitive adhesives is poor.
これに対して、（メタ）アクリル酸エステル成分単位を主構成単位とし、重量平均分子量が５００００以上である粘着性ポリマーと、（メタ）アクリル酸エステル成分単位を主構成単位とし、重量平均分子量が２００００以下である粘着付与樹脂と、（メタ）アクリル酸エステルを主成分とするモノマーから成り、実質的に溶剤を含有していない粘着剤組成物が開示されている（特許文献６参照）。しかし、低エネルギー表面に対する接着力は充分でない。 On the other hand, a (meth) acrylic acid ester component unit as a main constituent unit, an adhesive polymer having a weight average molecular weight of 50000 or more, and a (meth) acrylic acid ester component unit as a main constituent unit, the weight average molecular weight is A pressure-sensitive adhesive composition comprising a tackifier resin of 20000 or less and a monomer mainly composed of (meth) acrylic acid ester and containing substantially no solvent is disclosed (see Patent Document 6). However, adhesion to low energy surfaces is not sufficient.
本発明は、上記問題に鑑み、表面エネルギーの低い被着体に対しても充分な接着力を発揮し、溶剤を用いることなく製造できる光重合性アクリル系粘着剤組成物を提供することを目的としている。本発明は又、上記光重合性アクリル系粘着剤組成物を用いた、表面エネルギーの低い被着体に対しても良好な接着力を発揮する粘着シートを提供することを目的としている。 In view of the above problems, an object of the present invention is to provide a photopolymerizable acrylic pressure-sensitive adhesive composition that exhibits sufficient adhesive force even on an adherend having a low surface energy and can be produced without using a solvent. It is said. Another object of the present invention is to provide a pressure-sensitive adhesive sheet that uses the above-mentioned photopolymerizable acrylic pressure-sensitive adhesive composition and exhibits good adhesion even to an adherend having a low surface energy.
このような課題を解決するために鋭意検討した結果、アクリル系モノマー混合物の組成並びに粘着付与樹脂の組成や物性値などを調節することにより、アクリル系モノマー混合物又はその部分重合物と粘着付与樹脂との相溶性が向上することを見出した。また同時に、特定のアクリル系モノマー成分と粘着付与樹脂の組み合わせにより、表面エネルギーの低い被着体に対する接着力が良好な粘着剤組成物が得られることを見出した。さらにこのようなアクリル系粘着剤組成物は溶剤を用いることなく製造でき、塗工性にも優れたものである。本発明はこれらの知見に基づき完成されたものである。 As a result of intensive studies to solve such problems, by adjusting the composition of the acrylic monomer mixture and the composition and physical properties of the tackifier resin, the acrylic monomer mixture or a partial polymer thereof and the tackifier resin It has been found that the compatibility is improved. At the same time, it has been found that a pressure-sensitive adhesive composition having a good adhesion to an adherend having a low surface energy can be obtained by a combination of a specific acrylic monomer component and a tackifying resin. Furthermore, such an acrylic pressure-sensitive adhesive composition can be produced without using a solvent, and has excellent coatability. The present invention has been completed based on these findings.
すなわち本発明は、（ａ）アルキル基の炭素数が１２〜２０であり、かつそのホモポリマーのガラス転移温度が１５℃以下であるアクリル酸アルキルエステル；１０〜７０重量％、および（ｂ）アルキル基の炭素数が２〜９であるアクリル酸アルキルエステル；９０〜３０重量％からなるアクリル酸アルキルエステルと、（ｃ）前記（ａ）及び（ｂ）のアクリル酸アルキルエステルと共重合可能な不飽和カルボン酸；前記（ａ）及び（ｂ）の総和１００重量部に対して１〜１０重量部とから成るモノマー成分又はその部分重合物と、（ｄ）光重合開始剤；前記（ａ）、（ｂ）、（ｃ）の総和１００重量部に対して０．０１〜５重量部と、（ｅ）（メタ）アクリル酸エステルを主構成単位とし、重量平均分子量が１００００未満であり、溶解性パラメータが２０．０（ＭＰａ）0.5以下であり、ガラス転移温度が４０℃以上である粘着付与樹脂；（ａ）、（ｂ）、（ｃ）の総和１００重量部に対して５〜４０重量部とを含むことを特徴とする光重合性アクリル系粘着剤組成物に係わるものである。 That is, the present invention relates to (a) an acrylic acid alkyl ester in which the alkyl group has 12 to 20 carbon atoms and the homopolymer has a glass transition temperature of 15 ° C. or lower; 10 to 70% by weight, and (b) alkyl An acrylic acid alkyl ester having 2 to 9 carbon atoms; an acrylic acid alkyl ester comprising 90 to 30% by weight; and (c) a copolymerizable copolymer of (a) and (b) with the acrylic acid alkyl ester. A saturated carboxylic acid; a monomer component consisting of 1 to 10 parts by weight based on 100 parts by weight of the sum of (a) and (b) or a partial polymer thereof; (d) a photopolymerization initiator; (B), 0.01 to 5 parts by weight with respect to 100 parts by weight of the total of (c), (e) (meth) acrylic acid ester as the main structural unit, the weight average molecular weight is less than 10,000, and solubility Parameter is at 20.0 (MPa) 0.5 or less, a tackifier resin having a glass transition temperature of 40 ° C. or higher; (a), (b) , 5~40 parts by weight per total 100 parts by weight of (c) And a photopolymerizable acrylic pressure-sensitive adhesive composition.
本発明の光重合性アクリル系粘着剤組成物において、アクリル酸アルキルエステル（ａ）のアルキル基の炭素数が１４〜１８であることが好ましい。 In the photopolymerizable acrylic pressure-sensitive adhesive composition of the present invention, the alkyl group of the acrylic acid alkyl ester (a) preferably has 14 to 18 carbon atoms.
粘着付与樹脂（ｅ）は、（ａ）、（ｂ）、（ｃ）からなるモノマー成分の部分重合物に可溶であることが望ましい。 The tackifier resin (e) is desirably soluble in the partial polymer of the monomer component consisting of (a), (b), and (c).
本発明の光重合性アクリル系粘着剤組成物は、架橋剤を（ａ）、（ｂ）、（ｃ）の総和１００重量部に対して０．０１〜５重量部含有していることが好ましい。 The photopolymerizable acrylic pressure-sensitive adhesive composition of the present invention preferably contains a crosslinking agent in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the total of (a), (b) and (c). .
本発明は又、上記（ａ）、（ｂ）、（ｃ）、（ｄ）及び（ｅ）からなる光重合性アクリル系粘着剤組成物を支持体上に塗布した後、紫外線を照射して重合させることにより粘着剤層を形成して得られる粘着シート又はテープに係わるものである。該粘着剤層を構成する粘着剤中には、架橋構造が形成されていることが好ましい。 In the present invention, the photopolymerizable acrylic pressure-sensitive adhesive composition comprising the above (a), (b), (c), (d) and (e) is applied on a support and then irradiated with ultraviolet rays. The present invention relates to a pressure-sensitive adhesive sheet or tape obtained by forming a pressure-sensitive adhesive layer by polymerization. A cross-linked structure is preferably formed in the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer.
本発明において、アクリル酸アルキルエステルを主成分とするモノマー成分、又はその部分重合物と粘着付与樹脂とは相溶性に優れており、これらの混合物である粘着剤組成物を支持体に塗布した後紫外線を照射し、重合して得られる粘着シート又はテープは、非常に高い接着力を示す。特に、従来接着が困難であったポリオレフィンや塗装鋼板など低エネルギー表面に対する接着性にも優れている。また、本発明の光重合性アクリル系粘着剤組成物は、溶剤を用いる必要がないので、粘着剤を製造する際に溶剤除去工程が不要である。 In the present invention, the monomer component mainly composed of an alkyl acrylate ester, or a partially polymerized product thereof, and a tackifier resin are excellent in compatibility, and after a pressure-sensitive adhesive composition, which is a mixture thereof, is applied to a support The pressure-sensitive adhesive sheet or tape obtained by irradiating with ultraviolet rays and polymerizing exhibits very high adhesive strength. In particular, it has excellent adhesion to low energy surfaces such as polyolefins and coated steel sheets, which have been difficult to bond. Moreover, since the photopolymerizable acrylic pressure-sensitive adhesive composition of the present invention does not require the use of a solvent, a solvent removal step is not necessary when producing the pressure-sensitive adhesive.
本発明の粘着剤組成物は、（ａ）アルキル基の炭素数が１２〜２０であり、かつそのホモポリマーのガラス転移温度が１５℃以下であるアクリル酸アルキルエステル、及び（ｂ）アルキル基の炭素数が２〜９であるアクリル酸アルキルエステルと、（ｃ）前記（ａ）及び（ｂ）のアクリル酸アルキルエステルと共重合可能な不飽和カルボン酸とからなるモノマー成分又はその部分重合物、（ｄ）光重合開始剤及び、（ｅ）（メタ）アクリル酸エステルを主構成単位とし、重量平均分子量が１００００未満であり、溶解性パラメーターが２０．０（ＭＰａ）0.5以下であり、ガラス転移温度が４０℃以上である粘着付与樹脂を含む。 The pressure-sensitive adhesive composition of the present invention comprises (a) an alkyl group having 12 to 20 carbon atoms and an alkyl acrylate ester whose homopolymer has a glass transition temperature of 15 ° C. or lower, and (b) an alkyl group. A monomer component consisting of an acrylic acid alkyl ester having 2 to 9 carbon atoms and (c) an unsaturated carboxylic acid copolymerizable with the acrylic acid alkyl ester of (a) and (b) above, or a partial polymer thereof. (D) a photopolymerization initiator and (e) a (meth) acrylic acid ester as a main constituent unit, a weight average molecular weight of less than 10,000, a solubility parameter of 20.0 (MPa) 0.5 or less, and a glass transition A tackifying resin having a temperature of 40 ° C. or higher is included.
上記アクリル酸アルキルエステル（ａ）は、アルキル基の炭素数が１２〜２０であり、かつそのホモポリマーのガラス転移温度が１５℃以下であれば特に制限されないが、好ましくはアルキル基の炭素数は１４〜１８である。これらのアクリル酸アルキルエステルの例として、例えば、ｎ−テトラデシルアクリレート、ｎ−ペンタデシルアクリレート、ｎ−ヘキサデシルアクリレート、イソミリスチルアクリレート、イソステアリルアクリレートなどが挙げられる。これらのアクリル酸アルキルエステルの中から１種または２種以上を選択して用いることができる。これらの中でイソミリスチルアクリレートまたは、イソステアリルアクリレートが特に好適に用いられる。 The acrylic acid alkyl ester (a) is not particularly limited as long as the alkyl group has 12 to 20 carbon atoms and the homopolymer has a glass transition temperature of 15 ° C. or lower, but preferably the alkyl group has carbon atoms. 14-18. Examples of these alkyl acrylates include n-tetradecyl acrylate, n-pentadecyl acrylate, n-hexadecyl acrylate, isomyristyl acrylate, isostearyl acrylate, and the like. One or more of these acrylic acid alkyl esters can be selected and used. Of these, isomyristyl acrylate or isostearyl acrylate is particularly preferably used.
アクリル酸アルキルエステル（ａ）の含有量は、（ａ）と（ｂ）との総和の１０〜７０重量％、好ましくは２０〜４０重量％である。その含有量が１０重量％未満では、低エネルギー表面の被着体に対する接着力に乏しく、７０重量％を超えると、低エネルギー表面以外の被着体に対する接着性やタックが乏しい。 The content of the alkyl acrylate ester (a) is 10 to 70% by weight, preferably 20 to 40% by weight, based on the sum of (a) and (b). If the content is less than 10% by weight, the adhesion to the adherend on the low energy surface is poor, and if it exceeds 70% by weight, the adhesion and tack to the adherend other than the low energy surface are poor.
上記アクリル酸アルキルエステル（ｂ）は、アルキル基の炭素数が２〜９であれば特に制限されない。これらのアクリル酸アルキルエステルとしては、例えば、ブチルアクリレート、イソノニルアクリレート、イソオクチルアクリレート、２−エチルヘキシルアクリレート、などが挙げられる。これらのアクリル酸アルキルエステルの中から１種または２種以上を選択して用いることができる。アクリル酸アルキルエステル（ｂ）は、（ａ）と（ｂ）との総和の９０〜３０重量％、好ましくは８０〜６０重量％配合される。 The acrylic acid alkyl ester (b) is not particularly limited as long as the alkyl group has 2 to 9 carbon atoms. Examples of these alkyl acrylates include butyl acrylate, isononyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, and the like. One or more of these acrylic acid alkyl esters can be selected and used. The acrylic acid alkyl ester (b) is blended in an amount of 90 to 30% by weight, preferably 80 to 60% by weight, based on the total of (a) and (b).
（ｃ）の不飽和カルボン酸としては、例えば、（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸等が挙げられる。本発明においては、アクリル酸が好適に用いられる。不飽和カルボン酸（ｃ）は、（ａ）と（ｂ）との総和１００重量部に対して１〜１０重量部、好ましくは５〜１０重量部配合する。含有量が１重量部未満では粘着剤の凝集力に乏しくなり、１０重量部を超えると低エネルギー表面の被着体に対する接着性が乏しくなる。 Examples of the unsaturated carboxylic acid (c) include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid and the like. In the present invention, acrylic acid is preferably used. The unsaturated carboxylic acid (c) is blended in an amount of 1 to 10 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the sum of (a) and (b). When the content is less than 1 part by weight, the cohesive force of the pressure-sensitive adhesive is poor, and when it exceeds 10 parts by weight, the adhesion to the adherend on the low energy surface becomes poor.
光重合開始剤（ｄ）は、光ラジカル重合開始剤が好適に用いられる。これらの例としては、４−（２−ヒドロキシエトキシ）フェニル（２−ヒドロキシ−２−プロピル）ケトン（例として、チバガイギー社製、商品名「ダロキュアー２９５９」）、α−ヒドロキシ−α，α′−ジメチルアセトフェノン（例として、チバガイギー社製、商品名「ダロキュアー１１７３」）、メトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン（例として、チバガイギー社製、商品名「イルガキュア６５１」）、２−ヒドロキシ−２−シクロヘキシルアセトフェノン（例として、チバガイギー社製、商品名「イルガキュアー１８４」）などのアセトフェノン系光重合開始剤、ベンジルジメチルケタールなどのケタール系光重合開始剤、その他のハロゲン化ケトン、アシルフォスフィンオキサイド（例として、チバガイギー社製、商品名「イルガキュアー８１９」）などを挙げることができる。 As the photopolymerization initiator (d), a radical photopolymerization initiator is preferably used. Examples of these include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (for example, Ciba Geigy, trade name “Darocur 2959”), α-hydroxy-α, α′- Dimethylacetophenone (for example, Ciba Geigy, trade name “Darocur 1173”), methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone (for example, Ciba Geigy, trade name “Irgacure 651”), 2-hydroxy Acetophenone photopolymerization initiators such as 2-cyclohexylacetophenone (for example, trade name “Irgacure 184” manufactured by Ciba Geigy), ketal photopolymerization initiators such as benzyldimethyl ketal, other halogenated ketones, acylphossine Fin oxide (as an example Ciba-Geigy Co., Ltd. under the trade name "Irgacure 819"), and the like.
本発明で使用される光重合開始剤は、（ａ）、（ｂ）、（ｃ）の総和１００重量部に対して、０．０１〜５重量部、好ましくは０．０５〜３重量部の範囲内の量で配合される。その添加量が０．０１未満では重合反応が不十分となり、５重量部を超えるとポリマーの低分子量化を招く。また、本発明において必要であれば熱重合開始剤を併用してもよい。このような熱重合開始剤としては、例えばベンゾイルパーオキサイド、ｔｅｒｔ−ヘキシルパーオキシ−２−エチルヘキサノエイト（例として、日本油脂（株）製、商品名「パーヘキシルＯ」）などの有機過酸化物やアゾビスイソブチロニトリル、ジメチル２−２′−アゾビス（２−メチルプロピオネート）などのアゾ系開始剤が挙げられる The photopolymerization initiator used in the present invention is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the sum of (a), (b) and (c). It is blended in an amount within the range. If the addition amount is less than 0.01, the polymerization reaction is insufficient, and if it exceeds 5 parts by weight, the polymer has a low molecular weight. Further, if necessary in the present invention, a thermal polymerization initiator may be used in combination. Examples of such a thermal polymerization initiator include organic peroxidation such as benzoyl peroxide and tert-hexylperoxy-2-ethylhexanoate (for example, trade name “Perhexyl O” manufactured by NOF Corporation). And azo initiators such as azobisisobutyronitrile and dimethyl 2-2'-azobis (2-methylpropionate).
粘着付与樹脂（ｅ）は、（メタ）アクリル酸エステルを主成分とするモノマーを重合させることにより形成される。このような（メタ）アクリル酸エステルとしては、炭素数１〜１６のアルキル基を有する（メタ）アクリル酸アルキルエステル、炭素数３〜１４の脂環式基（シクロアルキル基、橋かけ環式基等）を有するアルコールと、（メタ）アクリル酸とのエステル、炭素数６〜１４のアリール基又はアラルキル基を有するアルコールと（メタ）アクリル酸とのエステルなどを用いることができる。具体的には例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピルアクリレート、イソブチルアクリレート、ｔ−ブチルアクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレートなどが挙げられるが、本発明においてはこれらの中で特にイソボルニルアクリレートなどの橋かけ環式を有するアルコールと（メタ）アクリル酸とのエステル、ｔ−ブチルメタクリレートなどの第３級アルコールと（メタ）アクリル酸とのエステルが好適に用いられる。このような（メタ）アクリル酸エステルは、単独であるいは組み合わせて使用することができる。本発明の粘着付与樹脂中、このような（メタ）アクリル酸エステルから誘導される繰り返し単位（（メタ）アクリル酸エステル成分単位）を単量体換算で一般に７０重量％以上、好ましくは９０重量％以上の割合で有している。 The tackifier resin (e) is formed by polymerizing a monomer mainly composed of (meth) acrylic acid ester. As such (meth) acrylic acid ester, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 16 carbon atoms, alicyclic group having 3 to 14 carbon atoms (cycloalkyl group, bridged cyclic group) Etc.) and ester of (meth) acrylic acid, ester of alcohol having 6 to 14 carbon atoms of aryl group or aralkyl group and (meth) acrylic acid, and the like can be used. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (Meth) acrylates and the like can be mentioned, but in the present invention, among them, particularly, an ester of an alcohol having a bridged cyclic structure such as isobornyl acrylate and (meth) acrylic acid, a third such as t-butyl methacrylate, etc. An ester of a secondary alcohol and (meth) acrylic acid is preferably used. Such (meth) acrylic acid esters can be used alone or in combination. In the tackifier resin of the present invention, such a repeating unit derived from (meth) acrylic acid ester ((meth) acrylic acid ester component unit) is generally 70% by weight or more, preferably 90% by weight in terms of monomer. It has in the above ratio.
粘着付与樹脂（ｅ）は、上記（メタ）アクリル酸エステル成分単位の他に、（メタ）アクリル酸エステルと共重合可能な単量体から誘導される繰り返し単位を有していてもよい。このような単量体の例としては、（メタ）アクリル酸グリシジルのようなエポキシ基含有ビニル単量体；（メタ）アクリル酸−２−ヒドロキシエチル、アクリル酸−２−ヒドロキシプロピルなどのヒドロキシル基含有ビニル化合物；イタコン酸、クロトン酸、マレイン酸、フマル酸のような不飽和カルボン酸；メタクリルアミドのようなアミド基含有ビニル単量体などを挙げることができる。このような単量体は単独で或いは組み合わせて上記（メタ）アクリル酸エステルと共重合させることができる。 The tackifier resin (e) may have a repeating unit derived from a monomer copolymerizable with the (meth) acrylic acid ester in addition to the above (meth) acrylic acid ester component unit. Examples of such monomers include epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; hydroxyl groups such as (meth) acrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, etc. Examples thereof include vinyl compounds containing; unsaturated carboxylic acids such as itaconic acid, crotonic acid, maleic acid and fumaric acid; amide group-containing vinyl monomers such as methacrylamide. Such monomers can be copolymerized with the (meth) acrylic acid ester alone or in combination.
粘着付与樹脂（ｅ）は、例えば溶液重合、懸濁重合、乳化重合、バルク重合などの種々の方法により製造することができるが、分散剤や乳化剤など不純物の混入がなく、溶剤除去が不要である塊状重合法が望ましい。さらにこの塊状重合において、比較的低温（例えば５０〜１００℃）で重合反応を行う第１段階と、高温（例えば１５０〜２００℃）でさらに重合を行う第２段階とを設けて重合を行い、残存モノマーを５重量％以下とすることが望ましい。 The tackifier resin (e) can be produced by various methods such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, etc., but there is no mixing of impurities such as dispersants and emulsifiers, and solvent removal is unnecessary. Some bulk polymerization is desirable. Furthermore, in this bulk polymerization, polymerization is performed by providing a first stage in which the polymerization reaction is performed at a relatively low temperature (for example, 50 to 100 ° C.) and a second stage in which the polymerization is further performed at a high temperature (for example, 150 to 200 ° C.), It is desirable that the residual monomer is 5% by weight or less.
粘着付与樹脂（ｅ）の製造に際しては適宜な重合開始剤を使用してもよい。重合開始剤としては慣用のものがいずれも使用でき、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、ジ−ｔｅｒｔ−ブチルパーオキサイド、クメンハイドロパーオキサイドなどが挙げられる。その使用量は、通常モノマー総量に対して０．０１〜１０重量％とすればよく、得られる粘着付与樹脂の分子量が所望の範囲内となるように調節して使用すればよい。 An appropriate polymerization initiator may be used in the production of the tackifier resin (e). Any conventional polymerization initiator can be used, and examples thereof include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, and the like. The amount used may be usually 0.01 to 10% by weight based on the total amount of monomers, and may be used by adjusting the molecular weight of the resulting tackifier resin within a desired range.
また粘着付与樹脂（ｅ）の分子量を調整するためには、重合する際に連鎖移動剤を使用することができる。連鎖移動剤としては慣用のものがいずれも使用でき、例えば、チオグリコール酸、２−メルカプトエタノール、α−チオグリセロールなどが挙げられる。その使用量は、通常モノマー総量に対して０．０１〜１０重量％とすればよく、得られる粘着付与樹脂の分子量が所望の範囲内となるように調節して使用すればよい Moreover, in order to adjust the molecular weight of tackifying resin (e), a chain transfer agent can be used at the time of superposition | polymerization. Any conventional chain transfer agent can be used, and examples thereof include thioglycolic acid, 2-mercaptoethanol, α-thioglycerol and the like. The amount used may be usually 0.01 to 10% by weight based on the total amount of monomers, and may be used by adjusting the molecular weight of the resulting tackifier resin to be within a desired range.
粘着付与樹脂（ｅ）の重量平均分子量は１００００未満、好ましくは３０００〜７０００の範囲内である。この粘着付与樹脂の重量平均分子量が１００００以上になると本発明の組成物を用いて得られる粘着剤における粘着性能の向上効果が十分には発現しない。 The weight average molecular weight of the tackifier resin (e) is less than 10,000, preferably in the range of 3000 to 7000. When the weight average molecular weight of the tackifier resin is 10,000 or more, the effect of improving the adhesive performance in the adhesive obtained using the composition of the present invention is not sufficiently exhibited.
さらに、粘着付与樹脂（ｅ）の溶解性パラメーターは２０．０（ＭＰａ）0.5以下（例えば１５〜２０（ＭＰａ）0.5）であり、ガラス転移温度は４０℃以上（例えば４０〜１８０℃）である。溶解性パラメーターが高すぎると、粘着剤層のベースポリマーとの相溶性が低下して、粘着付与樹脂とベースポリマーが相分離してしまい、接着性が向上せず、透明性も失われる。ガラス転移温度が低すぎると、接着性能が劣る。粘着付与樹脂（ｅ）の溶解性パラメーターやガラス転移温度は、構成モノマーの種類及び割合を選択することにより調整できる。 Further, the solubility parameter of the tackifier resin (e) is 20.0 (MPa) 0.5 or less (for example, 15 to 20 (MPa) 0.5 ), and the glass transition temperature is 40 ° C. or more (for example, 40 to 180 ° C.). . If the solubility parameter is too high, the compatibility of the pressure-sensitive adhesive layer with the base polymer is lowered, the tackifier resin and the base polymer are phase-separated, the adhesiveness is not improved, and the transparency is lost. If the glass transition temperature is too low, the adhesion performance is poor. The solubility parameter and glass transition temperature of the tackifier resin (e) can be adjusted by selecting the type and ratio of the constituent monomers.
粘着付与樹脂（ｅ）は、（ａ）、（ｂ）、（ｃ）の総和１００重量部に対して、５〜４０重量部配合される。５重量部未満では表面エネルギーの低い被着体に対する接着力が充分でなく、４０重量部より多いと、保持力や透明性が劣る。 The tackifying resin (e) is blended in an amount of 5 to 40 parts by weight based on 100 parts by weight of the sum of (a), (b) and (c). If it is less than 5 parts by weight, the adhesive force to the adherend having a low surface energy is not sufficient, and if it is more than 40 parts by weight, the holding power and transparency are inferior.
本発明のアクリル系粘着剤組成物は、（ａ）、（ｂ）、（ｃ）からなるモノマー成分又はその部分重合物、光重合開始剤（ｄ）、および粘着付与樹脂（ｅ）を個別に調製し、これらを混合して調製することができる。この際、（ａ）、（ｂ）、（ｃ）を部分重合したポリマーシロップを調製し、これに光重合開始剤（ｄ）及び別途調製した粘着付与樹脂（ｅ）を添加して混合することにより製造することが好ましい。 The acrylic pressure-sensitive adhesive composition of the present invention comprises a monomer component consisting of (a), (b), and (c) or a partial polymer thereof, a photopolymerization initiator (d), and a tackifier resin (e) individually. They can be prepared and mixed. At this time, a polymer syrup in which (a), (b), and (c) are partially polymerized is prepared, and a photopolymerization initiator (d) and a separately prepared tackifying resin (e) are added thereto and mixed. It is preferable to manufacture by.
（ａ）、（ｂ）及び（ｃ）からなるモノマー成分の部分重合は、熱重合、光重合等の何れの方法で行っても良い。何れの場合も、塊状重合により調製するのが好ましい。光重合で行う場合には、前記光重合開始剤（ｄ）の一部又は全部を用い、（ａ）、（ｂ）及び（ｃ）のモノマー混合物に、不活性雰囲気下で紫外線を照射して部分重合することができる。このときこの部分重合体は、支持体上に塗布可能な粘度（通常室温で１０００〜１０００００センチポイズ）を有する粘稠な液体となることが望ましい。このときの転化率は通常５〜１０％程度である。このポリマーシロップの粘度や転化率は、紫外線の照度や照射時間を調節することにより調整すればよい。 The partial polymerization of the monomer component consisting of (a), (b) and (c) may be performed by any method such as thermal polymerization or photopolymerization. In any case, it is preferable to prepare by bulk polymerization. When carrying out by photopolymerization, a part or all of the photopolymerization initiator (d) is used, and the monomer mixture of (a), (b) and (c) is irradiated with ultraviolet rays under an inert atmosphere. Partial polymerization is possible. At this time, the partial polymer is desirably a viscous liquid having a viscosity (usually 1000 to 100,000 centipoise at room temperature) that can be applied on the support. The conversion at this time is usually about 5 to 10%. What is necessary is just to adjust the viscosity and conversion rate of this polymer syrup by adjusting the illumination intensity and irradiation time of an ultraviolet-ray.
また、本発明の粘着剤組成物には、耐熱性や高温での凝集力を増加させるために架橋剤を配合することが好ましい。この架橋剤は、前記（ａ）、（ｂ）、（ｃ）の総和１００重量部に対して、通常０．０１〜５重量部、好ましくは０．０１〜３重量部の範囲内の量で配合される。 Moreover, it is preferable to mix | blend a crosslinking agent with the adhesive composition of this invention in order to increase heat resistance and the cohesion force in high temperature. This crosslinking agent is usually in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, with respect to 100 parts by weight of the total of (a), (b) and (c). Blended.
架橋剤の例としては、例えば、トリメチロールプロパントリアクリレート、ヘキサンジオールジアクリレート、ポリエチレンジオールジアクリレート、ポリプロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、ペンタエリスリトールジアクリレート、ジペンタエリスリトールヘキサアクリレートなどの多官能ビニル化合物、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラグリシジル−ｍ−キシリレンジアミン、１，３−ビス（Ｎ，Ｎ′−ジアミングリシジルアミノメチル）シクロヘキサンなどのエポキシ基を有する化合物、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタリンジイソシアネート、トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルイソシアネートなどのイソシアネート基を有する化合物を挙げることができる。このような架橋剤として、日本ポリウレタン（株）製、商品名「コロネートＬ」などを挙げることができる。 Examples of cross-linking agents include, for example, polyfunctionality such as trimethylolpropane triacrylate, hexanediol diacrylate, polyethylenediol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate, etc. Vinyl compounds, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N , N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis N, N'-diamine glycidylaminomethyl) cyclohexane and other compounds having an epoxy group, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane isocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate Examples thereof include compounds having an isocyanate group such as phenylmethane triisocyanate and polymethylene polyphenyl isocyanate. As such a crosslinking agent, a product name "Coronate L" manufactured by Nippon Polyurethane Co., Ltd. can be exemplified.
なお、上記重合開始剤、架橋剤を使用する場合、これらは実質的に溶媒を含有していないものであることが好ましい。本発明のアクリル系粘着剤組成物には、さらに、充填剤として、炭酸カルシウム、水酸化アルミニウム、シリカ、クレー、タルク、酸化チタンなどの無機物、ガラスバルーン、シラスバルーン、セラミックバルーンなどの無機中空体、塩化ビニリデンバルーン、アクリルバルーンなどの有機中空体、発泡剤、染料、顔料など通常粘着剤に配合される添加剤が配合されてもよい。 In addition, when using the said polymerization initiator and a crosslinking agent, it is preferable that these do not contain a solvent substantially. The acrylic pressure-sensitive adhesive composition of the present invention further includes, as a filler, inorganic materials such as calcium carbonate, aluminum hydroxide, silica, clay, talc, and titanium oxide, and inorganic hollow bodies such as glass balloons, shirasu balloons, and ceramic balloons. Additives that are usually blended in adhesives such as organic hollow bodies such as vinylidene chloride balloons and acrylic balloons, foaming agents, dyes, and pigments may be blended.
本発明のアクリル系粘着剤組成物（塗布液）を支持体表面に塗布して、紫外線等を照射して重合させることにより、表面エネルギーの低い被着体に対しても良好な接着力を発揮する粘着シート類を製造することができる。 By applying the acrylic pressure-sensitive adhesive composition (coating liquid) of the present invention to the surface of a support and irradiating it with ultraviolet rays or the like to polymerize it, it exhibits good adhesion even to adherends with low surface energy. It is possible to manufacture pressure-sensitive adhesive sheets.
本発明に用いられる支持体は特に制限されず、例えば、紙などの紙系基材；布、不織布、ネットなどの繊維系基材；金属箔、金属板などの金属系基材、プラスチックのフィルムやシートなどのプラスチック系基材；ゴムシートなどのゴム系基材；発泡シートなどの発泡体や、これらの積層体（特に、プラスチック系基材と他の基材との積層体や、プラスチックフィルム（又はシート）同士の積層体など）等の適宜な薄葉体を用いることができる。基材としては、プラスチックのフィルムやシートなど、プラスチック系基材を好適に用いることができる。このようなプラスチックのフィルムやシートにおける素材としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体（ＥＶＡ）等のα−オレフィンをモノマー成分とするオレフィン系樹脂；ポリエチレンテレフタラート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンテレフタラート（ＰＢＴ）等のポリエステル系樹脂；ポリ塩化ビニル（ＰＶＣ）；酢酸ビニル系樹脂；ポリフェニレンスルフィド（ＰＰＳ）；ポリアミド（ナイロン）、全芳香族ポリアミド（アラミド）等のアミド系樹脂；ポリイミド系樹脂、ポリエーテルエーテルケトン（ＰＥＥＫ）などが挙げられる。これらの素材は単独で又は２種以上組み合わせて使用することができる。 The support used in the present invention is not particularly limited. For example, a paper-based substrate such as paper; a fiber-based substrate such as cloth, nonwoven fabric, or net; a metal-based substrate such as metal foil or metal plate; a plastic film Plastic base materials such as rubber sheets; Rubber base materials such as rubber sheets; Foams such as foam sheets and laminates thereof (particularly, laminates of plastic base materials and other base materials, plastic films) A suitable thin leaf body such as a laminate of (or sheets) can be used. As the substrate, a plastic substrate such as a plastic film or sheet can be suitably used. As a material in such a plastic film or sheet, for example, an α-olefin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) or the like is used as a monomer component. Olefin resins: Polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); Polyvinyl chloride (PVC); Vinyl acetate resin; Polyphenylene sulfide (PPS) Amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); polyimide resins, polyether ether ketone (PEEK) and the like. These materials can be used alone or in combination of two or more.
なお、支持体としてプラスチック系素材が用いられている場合には、延伸処理等により伸び率などの変形性を制御していてもよい。また、支持体としては、紫外線の透過を阻害しないものを使用することが好ましい。 When a plastic material is used as the support, the deformability such as the elongation may be controlled by a stretching process or the like. In addition, it is preferable to use a support that does not inhibit the transmission of ultraviolet rays.
支持体の厚さは、強度や柔軟性、使用目的などに応じて適宜に選択でき、例えば、一般的には１０００μｍ以下（例えば１〜１０００μｍ）、好ましくは１〜５００μｍ、更に好ましくは３〜３００μｍ程度であるが、これらに限定されない。なお、支持体は単層の形態を有していてもよく、積層された形態を有していてもよい。 The thickness of the support can be appropriately selected depending on the strength, flexibility, purpose of use, and the like. For example, it is generally 1000 μm or less (for example, 1 to 1000 μm), preferably 1 to 500 μm, more preferably 3 to 300 μm. However, it is not limited to these. In addition, the support body may have a single layer form or may have a laminated form.
支持体の表面は、光重合性粘着剤組成物との密着性を高めるため、慣用の表面処理、例えばコロナ処理、クロム処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理等の化学的又は物理的方法による酸化処理等が施されていてもよく、下塗り剤や剥離剤等によるコーティング処理等が施されていてもよい。 The surface of the support is chemically treated by conventional surface treatments such as corona treatment, chrome treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc., in order to enhance adhesion with the photopolymerizable pressure-sensitive adhesive composition. Alternatively, oxidation treatment or the like by a physical method may be performed, or coating treatment or the like by an undercoat agent or a release agent may be performed.
本発明の光重合性アクリル系粘着シートは、支持体の両面に粘着剤層が設けられた両面粘着シートの形態を有していてもよく、支持体の片面のみに粘着剤層が設けられた片面粘着シートの形態を有していてもよい。 The photopolymerizable acrylic pressure-sensitive adhesive sheet of the present invention may have a form of a double-sided pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is provided on both sides of the support, and the pressure-sensitive adhesive layer is provided only on one side of the support. You may have the form of a single-sided adhesive sheet.
本発明において、光重合性粘着剤組成物を支持体上に塗布する方法は特に制限されず、慣用の塗布法を採用できる。例えばロールコーター、ダイコーター、バーコーター、ナイフコーター、グラビアコーター、メイヤーバーコーター等を用いて塗布すればよい。塗布厚は特に制限されないが、通常０．０１〜１．０ｍｍ程度である。 In this invention, the method in particular of apply | coating a photopolymerizable adhesive composition on a support body is not restrict | limited, A usual application method can be employ | adopted. For example, a roll coater, a die coater, a bar coater, a knife coater, a gravure coater, a Mayer bar coater or the like may be used. The coating thickness is not particularly limited, but is usually about 0.01 to 1.0 mm.
このようにして支持体上に塗布した光重合性粘着剤組成物に対して紫外線を照射することにより重合反応が進行し、粘着剤層が形成される。紫外線の照度は、一般に０．１〜５００ｍＷ／ｃｍ2であり、好ましくは０．５〜３００ｍＷ／ｃｍ2、さらに好ましくは１〜１００ｍＷ／ｃｍ2である（測定装置；トプコン社製工業用ＵＶチェッカー、商品名「ＵＶＲ−Ｔ１」）。紫外線の照射時間は、塗布層の厚さや紫外線の照度によっても異なるが、通常０．５〜１０分間、好ましくは０．５〜５分間である。 By irradiating the photopolymerizable pressure-sensitive adhesive composition coated on the support in this way with ultraviolet rays, the polymerization reaction proceeds and a pressure-sensitive adhesive layer is formed. The illuminance of ultraviolet rays is generally 0.1 to 500 mW / cm 2 , preferably 0.5 to 300 mW / cm 2 , more preferably 1 to 100 mW / cm 2 (measuring device; industrial UV checker manufactured by Topcon Corporation). , Trade name "UVR-T1"). The irradiation time of ultraviolet rays varies depending on the thickness of the coating layer and the illuminance of ultraviolet rays, but is usually 0.5 to 10 minutes, preferably 0.5 to 5 minutes.
本発明のアクリル酸アルキルエステルを主成分とするモノマー成分又はその部分重合物と粘着付与樹脂とは相溶性に優れており、これらの混合物である粘着剤組成物を支持体に塗布して紫外線を照射して重合させて得られる粘着テープは、非常に高い接着力を示す。特に、従来接着が困難であったポリオレフィンなど低エネルギー表面に対する接着性にも優れている。また、本発明の光重合性アクリル系粘着剤組成物は、溶剤を用いる必要が無いので、粘着剤を製造する際に溶剤除去工程が不要である。 The monomer component comprising the alkyl acrylate ester of the present invention as a main component or a partial polymer thereof and the tackifier resin are excellent in compatibility. The pressure-sensitive adhesive tape obtained by polymerization by irradiation exhibits a very high adhesive force. In particular, it is excellent in adhesion to low energy surfaces such as polyolefin, which has been difficult to bond. Moreover, since the photopolymerizable acrylic pressure-sensitive adhesive composition of the present invention does not require the use of a solvent, a solvent removal step is not necessary when producing the pressure-sensitive adhesive.
以下、本発明の実施例を記載してより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。なお、以下において、部は特に断らない限り重量部を意味する。 Examples of the present invention will be described below in more detail. However, the present invention is not limited to these examples. In the following, “parts” means “parts by weight” unless otherwise specified.
（粘着付与樹脂の調製１）
撹拌機、還流冷却機、温度計および窒素導入管を備えた装置にイソボルニルアクリレート（大阪有機化学工業（株）製、商品名「ＩＢＸＡ」）１００部、チオグリコール酸（堺化学工業（株）製、メルカプト酢酸）３部、ジ−ｔｅｒｔ−ヘキシルパーオキサイド（日本油脂（株）製、商品名「パーヘキシルＤ」）０．０５部を仕込み、室温で撹拌しながら１時間窒素パージした。次いでこの混合物に緩やかに窒素ガスを吹き込みながら撹拌し、７０℃になるまで昇温し、重合反応を開始させた。発生する反応熱によって上昇する装置内温度を７０℃〜８０℃に保つように第１段階目の重合反応を約２時間行なった。ここにジ−ｔｅｒｔ−ヘキシルパーオキサイド０．０５部を添加して、自己発生熱により生じる反応系内の温度上昇が緩やかになった後、反応系内温度を１７０℃にまで緩やかに昇温させ、第２段階目の重合反応を４〜６時間行ない、転化率が約９８％、重量平均分子量（Ｍｗ）が３５００のイソボルニルアクリレートポリマーを得た。
(Preparation of tackifying resin 1)
A device equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube is 100 parts of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “IBXA”), thioglycolic acid (Sakai Chemical Industry Co., Ltd.) ), 3 parts of mercaptoacetic acid) and 0.05 part of di-tert-hexyl peroxide (manufactured by NOF Corporation, trade name “Perhexyl D”) were purged with nitrogen for 1 hour while stirring at room temperature. Next, this mixture was stirred while gently blowing nitrogen gas, and the temperature was raised to 70 ° C. to initiate the polymerization reaction. The polymerization reaction in the first stage was carried out for about 2 hours so that the temperature inside the apparatus, which was raised by the generated heat of reaction, was maintained at 70 to 80 ° C. Here, 0.05 part of di-tert-hexyl peroxide was added, and after the temperature rise in the reaction system caused by self-generated heat became moderate, the temperature in the reaction system was gradually raised to 170 ° C. The second stage polymerization reaction was performed for 4 to 6 hours to obtain an isobornyl acrylate polymer having a conversion rate of about 98% and a weight average molecular weight (Mw) of 3500.
（粘着付与樹脂の調製２）
チオグリコール酸（堺化学工業（株）製、メルカプト酢酸）の添加量を０．７重量部とした以外は粘着付与樹脂の調製１と同様の操作を行い、重量平均分子量が１５０００のイソボルニルアクリレートポリマーを得た。
(Preparation of tackifying resin 2)
Isobornyl having a weight average molecular weight of 15000 was performed in the same manner as in Preparation 1 of tackifying resin except that the amount of thioglycolic acid (manufactured by Sakai Chemical Industry Co., Ltd., mercaptoacetic acid) was 0.7 parts by weight. An acrylate polymer was obtained.
（粘着付与樹脂の調製３）
イソボルニルアクリレートの代わりに、ｔｅｒｔ−ブチルメタクリレート（共栄社製、商品名「ライトエステルＴＢ」）を主構成単位として用いた以外は、粘着付与樹脂の調製１と同様の操作を行い、重合平均分子量が３５００のｔｅｒｔ−ブチルメタクリレートポリマーを得た。
(Preparation of tackifying resin 3)
Polymerization average molecular weight was the same as in Preparation of tackifying resin 1 except that tert-butyl methacrylate (trade name “Light Ester TB”, manufactured by Kyoeisha, Ltd.) was used as the main structural unit instead of isobornyl acrylate. Gave 3500 tert-butyl methacrylate polymers.
（粘着付与樹脂の調製４）
イソボルニルアクリレートの代わりに、２−エチルヘキシルメタクリレート（２ＥＨＭＡ）（共栄社製、商品名「ライトエステルＥＨ」）を主構成単位として用い、チオグリコール酸の添加量を１部とした以外は、粘着付与樹脂の調製１と同様の操作を行い、重量平均分子量が９０００の２−エチルヘキシルメタクリレートポリマーを得た。
(Preparation of tackifying resin 4)
Tackifying except that 2-ethylhexyl methacrylate (2EHMA) (trade name “Light Ester EH”, manufactured by Kyoeisha) is used as the main structural unit instead of isobornyl acrylate, and the addition amount of thioglycolic acid is 1 part. The same operation as in Resin Preparation 1 was performed to obtain a 2-ethylhexyl methacrylate polymer having a weight average molecular weight of 9000.
（粘着付与樹脂の調製５）
イソボルニルアクリレートの代わりに、シクロヘキシルメタクリレート（三菱ガス化学社製、商品名「ＣＨＭＡ」）を主構成単位として用いた以外は、粘着付与樹脂の調製１と同様の操作を行い、重量平均分子量が３３００のシクロヘキシルメタクリレートポリマーを得た。
(Preparation of tackifying resin 5)
Except for using cyclohexyl methacrylate (trade name “CHMA”, manufactured by Mitsubishi Gas Chemical Co., Inc.) as the main structural unit instead of isobornyl acrylate, the same operation as in Preparation 1 of tackifying resin was performed, and the weight average molecular weight was 3300 cyclohexyl methacrylate polymers were obtained.
得られた粘着付与樹脂について、それぞれの溶解性パラメーター、ガラス転移温度、重量平均分子量を表１に示す。これらの数値は以下の方法により求められた。
（分子量）
ＧＰＣ（ゲル浸透クロマトグラフィー）により求めた重量平均分子量（ＭW）である。装置：東ソー（株）製、商品名「ＨＬＣ−８０２０」
カラム：東ソー（株）製、商品名「ＴＳＫｇｅｌＧＭＨHR−Ｈ（２０）」
溶媒：テトラヒドロフラン
標準物質：ポリスチレン
（溶解性パラメーター）
Ｆｅｄｏｒｓ，Ｐｏｌｙｍ．Ｅｎｇ．ａｎｄ Ｓｃｉ．，１４；１４７（１９７４）に記載されている方法により算出される。
（ガラス転移温度）
粘着付与樹脂のガラス転移温度は、ＤＳＣ測定により確認した。
装置：セイコーインスツルメンツ（株）製、商品名「２００ＣＵ」
測定温度：−８０〜１６０℃（１０℃／ｍｉｎ）
測定環境：窒素雰囲気
Table 1 shows the solubility parameter, glass transition temperature, and weight average molecular weight of the resulting tackifier resin. These numerical values were obtained by the following method.
(Molecular weight)
It is the weight average molecular weight (M W ) determined by GPC (gel permeation chromatography). Apparatus: Product name “HLC-8020” manufactured by Tosoh Corporation
Column: manufactured by Tosoh Corporation, trade name “TSKgelGMH HR- H (20)”
Solvent: Tetrahydrofuran Standard: Polystyrene (solubility parameter)
Fedors, Polym. Eng. and Sci. , 14; 147 (1974).
(Glass-transition temperature)
The glass transition temperature of the tackifying resin was confirmed by DSC measurement.
Equipment: Seiko Instruments Inc., trade name “200CU”
Measurement temperature: -80 to 160 ° C. (10 ° C./min)
Measurement environment: nitrogen atmosphere
（実施例１）
撹拌機と温度計と窒素ガス導入管および冷却管を備えた四つ口フラスコに、重合性単量体として、イソオクチルアクリレート６６部、イソステアリルアクリレート（大阪有機化学工業（株）製、商品名「ＩＳＴＡ」）３４部、アクリル酸５部および２，２−ジメチル−２−フェニルアセトフェノン（チバガイギー社製、商品名「イルガキュア６５１」）０．０４部を投入し、均一に分散するまで撹拌混合しながら、窒素ガスをパージすることにより溶存酸素を除去した。次に、窒素雰囲気下、紫外線を数分間照射して部分重合を行い、転化率が約７．０％のポリマーシロップを得た。
このシロップ１００部にトリメチロールプロパントリアクリレート（大阪有機化学工業製、商品名「Ｖ♯２９５」）０．１５部、２，２−ジメチル−２−フェニルアセトフェノン（チバガイギー社製、商品名「イルガキュア６５１」）を０．１６部、粘着付与樹脂の調製１で得た粘着付与樹脂２０部を混合して本発明の無溶剤型アクリル系粘着剤組成物を調製した。
この混合物を厚さ２５μｍのポリエステルフィルム表面に、０．１ｍｍの厚さで塗布し、さらにカバーセパレーターとして表面が離型処理された３８μｍ厚みのポリエチレンテレフタレートフィルムを離型処理面が該塗工面に接するように被覆した。次に、ブラックライトを用いて照度３．６ｍＷ／ｃｍ2（照度測定装置；トプコン社製工業用ＵＶチェッカー、商品名「ＵＶＲ−Ｔｌ」）の紫外線を３分間照射することにより重合させて本発明の粘着シートを製造した。
Example 1
In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube, as a polymerizable monomer, 66 parts of isooctyl acrylate, isostearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name) "ISTA") 34 parts, acrylic acid 5 parts and 2,2-dimethyl-2-phenylacetophenone (product name "Irgacure 651" manufactured by Ciba Geigy Co., Ltd.) 0.04 parts are added and mixed with stirring until evenly dispersed. The dissolved oxygen was removed by purging with nitrogen gas. Next, partial polymerization was performed by irradiating ultraviolet rays for several minutes under a nitrogen atmosphere to obtain a polymer syrup having a conversion rate of about 7.0%.
To 100 parts of this syrup, 0.15 part of trimethylolpropane triacrylate (trade name “V # 295”, manufactured by Osaka Organic Chemical Industry), 2,2-dimethyl-2-phenylacetophenone (trade name “Irgacure 651, manufactured by Ciba Geigy Corporation) The solvent-free acrylic pressure-sensitive adhesive composition of the present invention was prepared by mixing 0.16 part of “)” and 20 parts of the tackifying resin obtained in Preparation 1 of tackifying resin.
This mixture is applied to the surface of a polyester film having a thickness of 25 μm to a thickness of 0.1 mm, and a 38 μm-thick polyethylene terephthalate film whose surface has been released as a cover separator is in contact with the coated surface. Was coated as follows. Next, the present invention is polymerized by irradiating with ultraviolet light having an illuminance of 3.6 mW / cm 2 (illuminance measuring device; industrial UV checker manufactured by Topcon, trade name “UVR-Tl”) for 3 minutes using a black light. A pressure-sensitive adhesive sheet was produced.
（実施例２）
イソオクチルアクリレートの使用量を３４部、イソステアリルアクリレートの使用量を６６部とした以外は実施例１と同様の操作を行った。
(Example 2)
The same operation as in Example 1 was performed except that the amount of isooctyl acrylate used was 34 parts and the amount of isostearyl acrylate used was 66 parts.
（実施例３）
粘着付与樹脂として粘着付与樹脂の調製１で得られたイソボルニルアクリレートポリマーの代わりに粘着付与樹脂の調製３で得られたｔｅｒｔ−ブチルメタクリレートポリマーを用いた以外は、実施例１と同様の操作を行った。
(Example 3)
The same operation as in Example 1 except that the tert-butyl methacrylate polymer obtained in Preparation 3 of the tackifying resin was used in place of the isobornyl acrylate polymer obtained in Preparation 1 of the tackifying resin as the tackifying resin. Went.
（実施例４）
イソステアリルアクリレートの代わりに、イソミリスチルアクリレート（共栄社製、商品名「ライトアクリレートＩＭ−Ａ」）を用いた以外は、実施例１と同様の操作を行った。
Example 4
The same operation as in Example 1 was performed except that isomyristyl acrylate (manufactured by Kyoeisha, trade name “Light Acrylate IM-A”) was used instead of isostearyl acrylate.
（実施例５）
粘着付与樹脂の添加量を４０部とした以外は、実施例１と同様の操作を行った
(Example 5)
The same operation as in Example 1 was performed except that the addition amount of the tackifying resin was 40 parts.
（実施例６）
イソオクチルアクリレートの代わりにｎ−ブチルアクリレートを用いた以外は、実施例１と同様の操作を行った。
(Example 6)
The same operation as in Example 1 was performed except that n-butyl acrylate was used instead of isooctyl acrylate.
（比較例１）
イソステアリルアクリレートを用いず、イソオクチルアクリレートの使用量を１００部とした以外は、実施例１と同様の操作を行った。
(Comparative Example 1)
The same operation as in Example 1 was performed except that isostearyl acrylate was not used and the amount of isooctyl acrylate used was 100 parts.
（比較例２）
イソステアリルアクリレートを用いず、イソオクチルアクリレートの使用量を１００部とし、粘着付与樹脂を配合しない以外は、実施例１と同様の操作を行った。
(Comparative Example 2)
The same operation as in Example 1 was performed except that isostearyl acrylate was not used, the amount of isooctyl acrylate used was 100 parts, and no tackifying resin was blended.
（比較例３）
イソオクチルアクリレートの代わりにｎ−ブチルアクリレートを用いた以外は、比較例１と同様の操作を行った。
(Comparative Example 3)
The same operation as in Comparative Example 1 was performed except that n-butyl acrylate was used instead of isooctyl acrylate.
（比較例４）
イソオクチルアクリレートの代わりにｎ−ブチルアクリレートを用いた以外は比較例２と同様の操作を行った。
(Comparative Example 4)
The same operation as Comparative Example 2 was performed except that n-butyl acrylate was used instead of isooctyl acrylate.
（比較例５）
粘着付与樹脂を配合しない以外は、実施例１と同様の操作を行った。
(Comparative Example 5)
The same operation as in Example 1 was performed except that no tackifying resin was blended.
（比較例６）
アクリル酸の使用量を０．５部とした以外は、実施例１と同様の操作を行った。
(Comparative Example 6)
The same operation as in Example 1 was performed except that the amount of acrylic acid used was 0.5 parts.
（比較例７）
イソステアリルアクリレートの代わりに、イソボルニルアクリレートを用い、アクリル酸の使用量を０．５部とした以外は、実施例１と同様の操作を行った。
(Comparative Example 7)
The same operation as in Example 1 was performed except that isobornyl acrylate was used instead of isostearyl acrylate and the amount of acrylic acid used was 0.5 parts.
（比較例８）
粘着付与樹脂の添加量を５０部とした以外は、実施例１と同様の操作を行った。
(Comparative Example 8)
The same operation as in Example 1 was performed except that the addition amount of the tackifying resin was 50 parts.
（比較例９）
粘着付与樹脂の調製２で得た重量平均分子量１５０００のイソボルニルアクリレートポリマーを粘着付与樹脂として用いた以外は、実施例１と同様の操作を行った。
(Comparative Example 9)
The same operation as in Example 1 was performed except that the isobornyl acrylate polymer having a weight average molecular weight of 15000 obtained in Preparation 2 of the tackifying resin was used as the tackifying resin.
（比較例１０）
粘着付与樹脂の調製４で得られた２−エチルヘキシルメタクリレートポリマーを粘着付与樹脂として用いた以外は、実施例１と同様の操作を行った。
(Comparative Example 10)
The same operation as in Example 1 was performed except that the 2-ethylhexyl methacrylate polymer obtained in Preparation 4 of the tackifier resin was used as the tackifier resin.
（比較例１１）
粘着付与樹脂の調製５で得られたシクロヘキシルメタクリレートポリマーを粘着付与樹脂として用いた以外は、実施例１と同様の操作を行った。
(Comparative Example 11)
The same operation as in Example 1 was performed except that the cyclohexyl methacrylate polymer obtained in Preparation 5 of the tackifying resin was used as the tackifying resin.
（比較例１２）
粘着付与樹脂として市販のフェノール系樹脂（住友ベークライト社製）を用いた以外は、実施例１と同様の操作を行ったが、粘着剤組成物の重合が進行せず、粘稠な液体のままで、粘着シートは得られなかった。
(Comparative Example 12)
The same operation as in Example 1 was performed except that a commercially available phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd.) was used as the tackifying resin, but the polymerization of the pressure-sensitive adhesive composition did not proceed and the liquid remained viscous. Thus, an adhesive sheet was not obtained.
（試験評価）
実施例及び比較例で得た粘着シートに対し、以下の試験を行った。結果を表２に示す。
（接着力）
２０±２℃、６５％Ｒ．Ｈ．下において、長さ１５０ｍｍ、幅２０ｍｍの切断粘着テープ片を表面が平滑で清浄な被着体に重さ２ｋｇのゴムローラーを１往復させる方法で圧着し、３０分間放置後にその接着力（１８０度ピール、引張り速度３００ｍｍ／分）を測定した。被着体には、ステンレス鋼板（ＳＵＳ板）、ポリプロピレン板（ＰＰ板）を用いた。接着力が１２（Ｎ／２０ｍｍ）未満の場合には接着力が不十分である。なお、実施例２において、被着体にステンレス鋼板を用いたときの破壊モードはスリップスティックである。
（保持力）
貼着面積が長さ２０ｍｍ、幅１０ｍｍとなるように切断粘着テープ片をベークライト板に圧着し、３０分間放置後に被着体の一端を固定すると共に、その粘着テープの自由端に５００ｇの荷重を負荷し荷重が負荷されてから１時間後のズレ距離を測定した。試験は８０℃の雰囲気で行った。ずれ距離の評価 ○；０．５ｍｍ未満 △；０．５ｍｍ以上、２ｍｍ以下 ×；落下
（外観）
透明であるか白濁しているか、白濁している場合はその程度を目視により評価した。評価 ○；透明 △；やや白濁 ×；白濁
(Test evaluation)
The following test was done with respect to the adhesive sheet obtained by the Example and the comparative example. The results are shown in Table 2.
(Adhesive strength)
20 ± 2 ° C., 65% R.D. H. Below, a piece of adhesive tape with a length of 150 mm and a width of 20 mm is pressure-bonded by a method of reciprocating a rubber roller with a weight of 2 kg on an adherend having a smooth surface, and the adhesive strength (180 degrees) after standing for 30 minutes. Peel, tensile speed 300 mm / min) was measured. For the adherend, a stainless steel plate (SUS plate) and a polypropylene plate (PP plate) were used. When the adhesive force is less than 12 (N / 20 mm), the adhesive force is insufficient. In Example 2, the failure mode when a stainless steel plate is used as the adherend is a slip stick.
(Holding power)
The cut adhesive tape piece is pressure-bonded to the bakelite plate so that the sticking area is 20 mm long and 10 mm wide, and after being left for 30 minutes, one end of the adherend is fixed, and a load of 500 g is applied to the free end of the adhesive tape. The displacement distance 1 hour after the load was applied was measured. The test was conducted in an atmosphere at 80 ° C. Evaluation of deviation distance ○: Less than 0.5 mm Δ: 0.5 mm or more, 2 mm or less ×: Dropping (appearance)
When it was transparent, cloudy, or cloudy, the degree was visually evaluated. Evaluation ○: Transparent △; Slightly cloudy ×: Cloudy
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004232497A JP4498057B2 (en) | 2004-08-09 | 2004-08-09 | Photopolymerizable acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or tape using the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004232497A JP4498057B2 (en) | 2004-08-09 | 2004-08-09 | Photopolymerizable acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or tape using the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006045474A JP2006045474A (en) | 2006-02-16 |
| JP4498057B2 true JP4498057B2 (en) | 2010-07-07 |
Family
ID=36024435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004232497A Expired - Fee Related JP4498057B2 (en) | 2004-08-09 | 2004-08-09 | Photopolymerizable acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or tape using the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4498057B2 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006096958A (en) * | 2004-09-30 | 2006-04-13 | Nippon Shokubai Co Ltd | Adhesive composition |
| JP5038770B2 (en) * | 2007-05-01 | 2012-10-03 | 日東電工株式会社 | Adhesive sheet adhesion method for vehicle paint film surface |
| JP5204937B2 (en) * | 2007-06-18 | 2013-06-05 | 日東電工株式会社 | Adhesive composition for optical members |
| JP5186142B2 (en) * | 2007-07-04 | 2013-04-17 | 日東電工株式会社 | Acrylic viscoelastic composition and pressure sensitive adhesive tape or sheet |
| JP5289747B2 (en) * | 2007-10-10 | 2013-09-11 | 日東電工株式会社 | Double-sided adhesive tape or sheet for printed circuit board and printed circuit board |
| JP5280034B2 (en) * | 2007-10-10 | 2013-09-04 | 日東電工株式会社 | Double-sided adhesive tape or sheet for printed circuit board and printed circuit board |
| JP5362291B2 (en) * | 2008-08-26 | 2013-12-11 | 日東電工株式会社 | Acrylic adhesive composition, acrylic adhesive layer and acrylic adhesive tape or sheet |
| JP2011236414A (en) * | 2010-04-13 | 2011-11-24 | Nitto Denko Corp | Acrylic pressure-sensitive adhesive tape |
| JP2011236413A (en) * | 2010-04-13 | 2011-11-24 | Nitto Denko Corp | Acrylic pressure-sensitive adhesive composition and acrylic pressure-sensitive adhesive tape |
| JP5932857B2 (en) * | 2011-05-02 | 2016-06-08 | 日東電工株式会社 | Adhesive, adhesive layer, and adhesive sheet |
| JP5469194B2 (en) * | 2011-05-02 | 2014-04-09 | 日東電工株式会社 | Adhesive, adhesive layer, and adhesive sheet |
| JP6051477B2 (en) * | 2011-07-19 | 2016-12-27 | エルジー・ケム・リミテッド | Touch panel |
| JP6067405B2 (en) | 2012-07-31 | 2017-01-25 | 日東電工株式会社 | Radiation curable adhesive, radiation curable adhesive layer, radiation curable adhesive sheet and laminate |
| JP6306679B2 (en) * | 2012-07-31 | 2018-04-04 | 日東電工株式会社 | Radiation curable adhesive, radiation curable adhesive layer, radiation curable adhesive sheet and laminate |
| JP2013216899A (en) * | 2013-06-04 | 2013-10-24 | Nitto Denko Corp | Double-sided pressure-sensitive adhesive tape or sheet for wiring circuit board and wiring circuit board |
| DE102013219495A1 (en) * | 2013-09-27 | 2015-04-02 | Tesa Se | Pressure-sensitive adhesive for low-energy or rough surfaces |
| JP6517150B2 (en) * | 2013-11-22 | 2019-05-22 | 綜研化学株式会社 | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive optical film and laminate |
| JP6512892B2 (en) * | 2015-03-26 | 2019-05-15 | 株式会社日本触媒 | Curable resin composition and cured product using the same |
| CN105647087B (en) | 2016-01-13 | 2017-11-10 | 3M创新有限公司 | Curable compositions, contact adhesive, adhesive tape, adhesive article |
| JP6868343B2 (en) * | 2016-04-20 | 2021-05-12 | 日東電工株式会社 | Polarizing film and its manufacturing method, optical film and image display device |
| JP6868344B2 (en) * | 2016-04-20 | 2021-05-12 | 日東電工株式会社 | Polarizing film and its manufacturing method, optical film and image display device |
| JP6976063B2 (en) * | 2017-02-17 | 2021-12-01 | 日東電工株式会社 | Laminated sheet |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04248820A (en) * | 1991-01-25 | 1992-09-04 | Sekisui Chem Co Ltd | Adhesive tape manufacturing method and adhesive tape |
| JPH0733832A (en) * | 1992-10-27 | 1995-02-03 | Sekisui Chem Co Ltd | Photopolymerizable composition and production of viscoelastic product |
| WO2001088052A1 (en) * | 2000-05-15 | 2001-11-22 | Toagosei Co., Ltd. | Tackifier and adhesive composition |
| JP2002145917A (en) * | 2000-08-28 | 2002-05-22 | Sekisui Chem Co Ltd | Photopolymerization method, photopolymerizable composition, photopolymerization product and adhesive tape |
| JP2002241709A (en) * | 2001-02-19 | 2002-08-28 | Soken Chem & Eng Co Ltd | Acrylic adhesive mass composition and method for producing pressure-sensitive adhesive tape using the same composition |
| JP2003193006A (en) * | 2001-12-26 | 2003-07-09 | Dainippon Ink & Chem Inc | Double-sided adhesive tape for recycled parts |
-
2004
- 2004-08-09 JP JP2004232497A patent/JP4498057B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04248820A (en) * | 1991-01-25 | 1992-09-04 | Sekisui Chem Co Ltd | Adhesive tape manufacturing method and adhesive tape |
| JPH0733832A (en) * | 1992-10-27 | 1995-02-03 | Sekisui Chem Co Ltd | Photopolymerizable composition and production of viscoelastic product |
| WO2001088052A1 (en) * | 2000-05-15 | 2001-11-22 | Toagosei Co., Ltd. | Tackifier and adhesive composition |
| JP2002145917A (en) * | 2000-08-28 | 2002-05-22 | Sekisui Chem Co Ltd | Photopolymerization method, photopolymerizable composition, photopolymerization product and adhesive tape |
| JP2002241709A (en) * | 2001-02-19 | 2002-08-28 | Soken Chem & Eng Co Ltd | Acrylic adhesive mass composition and method for producing pressure-sensitive adhesive tape using the same composition |
| JP2003193006A (en) * | 2001-12-26 | 2003-07-09 | Dainippon Ink & Chem Inc | Double-sided adhesive tape for recycled parts |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006045474A (en) | 2006-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4498057B2 (en) | Photopolymerizable acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or tape using the composition | |
| JP5186142B2 (en) | Acrylic viscoelastic composition and pressure sensitive adhesive tape or sheet | |
| JP4825992B2 (en) | Acrylic pressure-sensitive adhesive composition, method for producing pressure-sensitive adhesive tape using the composition, and pressure-sensitive adhesive tape | |
| TWI384044B (en) | Adhesive composition, double-coated adhesive sheet, adhesion method and portable electronic devices | |
| WO2009116504A1 (en) | Acrylic adhesive, acrylic adhesive layer, and acrylic adhesive tape or sheet | |
| US9605184B2 (en) | Pressure-sensitive adhesive sheet | |
| US10479058B2 (en) | Pressure-sensitive adhesive sheet | |
| WO2001046328A1 (en) | Acrylic polymer compositions, acrylic pressure-sensitive adhesion tapes and process for producing the same | |
| EP2652060B1 (en) | Pressure sensitive adhesives for low surface energy substrates | |
| KR20160030235A (en) | Adhesive-agent composition | |
| JP2008174658A (en) | Composition for adhesive, and adhesive sheet using the composition, and member with adhesive | |
| US20130323498A1 (en) | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet | |
| KR20160030236A (en) | Adhesive sheet and use thereof | |
| JP2009173695A (en) | Photocurable acrylic viscoelastic composition, acrylic viscoelastic material, acrylic viscoelastic layer tape or sheet, and method for manufacturing the same | |
| JP2012021053A (en) | Double-sided pressure-sensitive adhesive tape for fixing decorative sheet for speaker | |
| WO2018168678A1 (en) | Adhesive agent composition, adhesive agent, adhesive tape, and adhesive tape for airproofing and waterproofing | |
| US20230235199A1 (en) | Polymers derived from a poly(tetrahydrofuran)(meth)acrylate macromer, adhesive compositions, and articles | |
| JP2005239830A (en) | Thermosetting pressure-sensitive adhesive composition and thermosetting pressure-sensitive adhesive tape or sheet | |
| JP4115811B2 (en) | Double-sided adhesive tape and fixing method | |
| JPH11152457A (en) | Acrylic adhesive tape or sheet | |
| JP5002777B2 (en) | Acrylic adhesive tape manufacturing method and acrylic adhesive tape | |
| JPWO2013161759A1 (en) | Composition for transparent adhesive sheet, method for producing the same, and transparent adhesive sheet | |
| JP2008081564A (en) | Aqueous adhesive composition | |
| JP6317938B2 (en) | Adhesive sheet | |
| JP2002012629A (en) | Polymerizable composition, adhesive, adhesive tape and adhesive sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061106 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100413 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100413 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130423 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160423 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |