JP5357470B2 - Radiation-curing re-peelable adhesive sheet - Google Patents
Radiation-curing re-peelable adhesive sheet Download PDFInfo
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- JP5357470B2 JP5357470B2 JP2008227702A JP2008227702A JP5357470B2 JP 5357470 B2 JP5357470 B2 JP 5357470B2 JP 2008227702 A JP2008227702 A JP 2008227702A JP 2008227702 A JP2008227702 A JP 2008227702A JP 5357470 B2 JP5357470 B2 JP 5357470B2
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- 239000000853 adhesive Substances 0.000 title claims abstract description 50
- 230000001070 adhesive effect Effects 0.000 title claims description 44
- 238000003847 radiation curing Methods 0.000 title claims description 32
- 230000005855 radiation Effects 0.000 claims abstract description 70
- 229920001225 polyester resin Polymers 0.000 claims abstract description 42
- 239000004645 polyester resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 150000002009 diols Chemical class 0.000 claims abstract description 33
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 150
- 239000000539 dimer Substances 0.000 claims description 36
- 239000010410 layer Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 11
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 9
- 239000012790 adhesive layer Substances 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000003208 petroleum Substances 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 4
- 241000196324 Embryophyta Species 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- -1 fatty acid ester Chemical class 0.000 description 13
- 229920005601 base polymer Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000005510 radiation hardening Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 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 2
- 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
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-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
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-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
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- PTKHNBWCIHXVFS-UHFFFAOYSA-N 4-[2-methyl-1-(4-methylsulfanylphenyl)propan-2-yl]morpholine Chemical compound C1=CC(SC)=CC=C1CC(C)(C)N1CCOCC1 PTKHNBWCIHXVFS-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- BWPYBAJTDILQPY-UHFFFAOYSA-N Methoxyphenone Chemical compound C1=C(C)C(OC)=CC=C1C(=O)C1=CC=CC(C)=C1 BWPYBAJTDILQPY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Chemical class 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- OPECTNGATDYLSS-UHFFFAOYSA-N naphthalene-2-sulfonyl chloride Chemical compound C1=CC=CC2=CC(S(=O)(=O)Cl)=CC=C21 OPECTNGATDYLSS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229920000765 poly(2-oxazolines) Chemical class 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000580 poly(melamine) Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000582 polyisocyanurate Chemical class 0.000 description 1
- 239000011495 polyisocyanurate Chemical class 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、基材上に放射線硬化型の粘着剤層を有する再剥離型粘着シートに関し、より詳しくは上記粘着剤層のベースポリマーに地球環境にやさしい植物由来材料を原料成分としたポリエステル樹脂を使用した放射線硬化再剥離型粘着シートに関する。
The present invention relates to a re-peelable pressure-sensitive adhesive sheet having a radiation-curable pressure-sensitive adhesive layer on a substrate, and more specifically, a polyester resin containing a plant-derived material friendly to the global environment as a raw material component in the base polymer of the pressure-sensitive adhesive layer. The present invention relates to the radiation-curing re-peeling type adhesive sheet used.
放射線硬化再剥離型粘着シートは、被着体に貼り付けて使用されたのちは、放射線照射により粘着剤層を硬化させ、これにより粘着力を低下させて剥離され、廃棄処理される。この再剥離型粘着シートの放射線硬化型の粘着剤層にはベースポリマーとして石油由来であるアクリル系の材料が主に用いられてきた（特許文献１，２）。
上記従来の放射線硬化再剥離型粘着シートは、石油由来材料のため、石油桔渇のおそれがあり、また使用後の廃棄処理に二酸化炭素を排出していた。つまり、石油桔渇や産廃時の二酸化炭素排出の点より地球環境への配慮はなされていなかった。
昨今、化石資源の枯渇や地球の温暖化対策として環境への配慮が求められ、再生可能な材料である植物由来材料の使用が推奨され始めている。
Since the conventional radiation-curing re-peelable pressure-sensitive adhesive sheet is a petroleum-derived material, there is a risk of oil depletion, and carbon dioxide has been discharged during disposal after use. In other words, no consideration was given to the global environment in terms of oil depletion and carbon dioxide emissions during industrial waste.
In recent years, environmental considerations have been sought as a countermeasure against depletion of fossil resources and global warming, and the use of plant-derived materials, which are renewable materials, has begun to be recommended.
本発明は、上記の事情に照らして、放射線硬化型の粘着剤層のベースポリマーとして、化石資源（石油資源を含む）を用いず、化石資源の枯渇や二酸化炭素排出の問題のない、地球環境にやさしい植物由来材料を用いたバイオマス放射線硬化再剥離型粘着シートを提供すること、また放射線照射前は被着体の表面保護や固定などの目的を達成できる良好な粘着力（初期特性）を示し、放射線照射後はその粘着力が低下して容易に再剥離が可能となる上記再剥離型粘着シートを提供することを課題とする。
In light of the above circumstances, the present invention does not use fossil resources (including petroleum resources) as the base polymer of the radiation-curable pressure-sensitive adhesive layer, and has no problem of fossil resource depletion or carbon dioxide emission. Provide a biomass radiation-curing re-peelable adhesive sheet that uses plant-derived materials that are easy on the environment, and show good adhesive strength (initial characteristics) that can achieve the purpose of surface protection and fixation of the adherend before irradiation. It is an object of the present invention to provide the above-described re-peelable pressure-sensitive adhesive sheet that can be easily re-peeled after its irradiation with a reduced adhesive strength.
本発明者らは、上記の課題に対して、鋭意検討した結果、基材上に、化石資源の枯渇に影響されない植物由来材料を原料成分としたポリエステル樹脂をベースポリマーとして、これに特定量の放射線硬化型樹脂とさらに放射線反応開始剤を含ませ、架橋剤により架橋処理した粘着剤層を設けたことにより、放射線照射前は表面保護や固定などの目的を達成できる良好な粘着力を示し、放射線照射後はその粘着力が低下して容易に再剥離が可能であり、また被着体より剥離した上記粘着シートは、これを廃棄物として処理する際に上記植物由来材料により二酸化炭素排出の問題のない、地球環境にやさしいバイオマス放射線硬化再剥離型粘着シートとなることを知り、本発明を完成した。
As a result of intensive studies on the above problems, the inventors of the present invention have used, as a base polymer, a polyester resin whose raw material component is a plant-derived material that is not affected by the depletion of fossil resources. By including a radiation curable resin and a radiation reaction initiator, and by providing a pressure-sensitive adhesive layer that has been subjected to crosslinking treatment with a crosslinking agent, it exhibits a good adhesive force that can achieve the purpose of surface protection and fixation before irradiation, After the irradiation, the adhesive strength of the adhesive sheet decreases and can be easily removed, and the adhesive sheet released from the adherend emits carbon dioxide by the plant-derived material when it is treated as waste. Knowing that this would be a problem-free, environmentally friendly biomass radiation-curing re-peelable adhesive sheet, the present invention was completed.
すなわち、本発明は、基材上に、植物由来のジカルボン酸であるダイマー酸と植物由来のジオールであるダイマージオールとをジカルボン酸に含まれるカルボキシル基１．００モルに対しジオールに含まれる水酸基が１．０１〜１．７０モルとなる割合で縮合重合させて得られる、重量平均分子量が１．１万〜８．５万のポリエステル樹脂と、このポリエステル樹脂１００重量部あたり３０〜７０重量部となる量の、官能基１個あたりの重量平均分子量が８，０００以下である放射線硬化型樹脂と、この放射線硬化型樹脂に対し２〜１０重量％となる量の放射線反応開始剤とを含有し、架橋剤により架橋処理された、ゲル分率が２０〜８０重量％である粘着剤層を有し、放射線照射前の粘着力が１．４Ｎ／２０mm以上で、放射線（４，８００ｍＪ／ｃｍ2 の紫外線）照射後の粘着力が０．９Ｎ／２０mm以下であることを特徴とする放射線硬化再剥離型粘着シートに係るものである。
また、本発明は、架橋剤がポリイソシアネート化合物である上記構成の放射線硬化再剥離型粘着シートに係るものである。
なお、本発明における「放射線硬化再剥離型粘着シート」には、通常幅広のシート状物だけでなく、通常幅狭のテープ状物も含まれ、その他、ラベル状物などの各種形態の再剥離型粘着製品が包含されるものである。
That is, in the present invention , a dimer acid that is a plant-derived dicarboxylic acid and a dimer diol that is a plant-derived diol are formed on a base material so that the hydroxyl group contained in the diol with respect to 1.00 mol of the carboxyl group contained in the dicarboxylic acid. A polyester resin having a weight average molecular weight of 11,000 to 85,000 obtained by condensation polymerization at a ratio of 1.01 to 1.70 mol, and 30 to 70 parts by weight per 100 parts by weight of the polyester resin; A radiation curable resin having a weight average molecular weight of 8,000 or less per functional group, and a radiation reaction initiator in an amount of 2 to 10% by weight based on the radiation curable resin. was cross-linked by a crosslinking agent, the gel fraction has a pressure-sensitive adhesive layer is 20 to 80 wt%, an adhesive force before irradiation is 1.4 N / 20 mm or more, radiation (4,800 Those of the radiation curable removable pressure-sensitive adhesive sheet, wherein J / cm 2 of ultraviolet) adhesive strength after irradiation is not more than 0.9N / 20 mm.
Further, the present invention, the crosslinking agent is related to the radiation curable removable pressure-sensitive adhesive sheet having the above structure is a polyisocyanate compound.
In addition, the “radiation curable re-peelable pressure-sensitive adhesive sheet” in the present invention includes not only a wide sheet-like material but also a usually narrow tape-like material, and other forms of re-peeling such as a label-like material Mold adhesive products are included.
このように、本発明は、基材上に、植物由来材料を原料成分としたポリエステル樹脂をベースポリマーとしこれに特定量の放射線硬化型樹脂と放射線反応開始剤を加えて架橋剤により架橋処理した粘着剤層を設けたことにより、化石資源の枯渇に影響されず、使用後廃棄処理する場合に植物由来材料を用いているため二酸化炭素を排出してもカーボンニュートラルを実現できる、地球環境にやさしいポリエステル系放射線硬化再剥離型粘着シートを提供できる。また、この粘着シートは、放射線照射前は表面保護や固定などの目的を達成できる良好な粘着力を示し、放射線照射後は粘着力が低下して容易に再剥離が可能であるという、再剥離型としてのすぐれた性能を発揮する。
Thus, in the present invention, on a base material, a polyester resin having a plant-derived material as a raw material component is used as a base polymer, and a specific amount of a radiation curable resin and a radiation reaction initiator are added to the base polymer, followed by crosslinking with a crosslinking agent. By providing an adhesive layer, it is not affected by the depletion of fossil resources, and because it uses plant-derived materials when it is disposed of after use, it can realize carbon neutral even if carbon dioxide is discharged. A polyester radiation curable re-peelable pressure-sensitive adhesive sheet can be provided. In addition, this pressure-sensitive adhesive sheet exhibits good adhesive strength that can achieve the purpose of surface protection and fixation before radiation irradiation, and after the radiation irradiation, the pressure-sensitive adhesive force decreases and can be easily removed again. Exhibits excellent performance as a mold.
本発明におけるポリエステル樹脂は、原料成分（モノマー成分）として植物由来のジカルボン酸と植物由来のジオールとを使用し、これらの原料成分を縮合重合させることにより得られるものである。
上記の縮合重合は、常法により、有機溶剤を使用して行ってもよいし、減圧下無溶剤で行ってもよい。縮合重合反応に際して、テトラ−ｎ−ブチルチタネート、テトライソプロピルチタネート、三酸化アンチモン、ブチルスズオキシドなどの金属化合物などの適宜の触媒を用いて行うことができる。
The polyester resin in the present invention is obtained by using a dicarboxylic acid derived from a plant and a diol derived from a plant as raw material components (monomer components) and subjecting these raw material components to condensation polymerization.
The above condensation polymerization may be performed by an ordinary method using an organic solvent, or may be performed without a solvent under reduced pressure. In the condensation polymerization reaction, an appropriate catalyst such as a metal compound such as tetra-n-butyl titanate, tetraisopropyl titanate, antimony trioxide, or butyltin oxide can be used.
植物由来のジカルボン酸としては、植物由来であれば特に限定されないが、ヒマシ油由来のセバシン酸やオレイン酸などからつくられるダイマー酸などが挙げられる。このようなジカルボン酸は２種以上を併用することもできる。
また、植物由来のジオールとしては、植物由来であれば特に限定されないが、ヒマシ油から誘導される脂肪酸エステルやオレイン酸などからつくられるダイマージオールなどが挙げられる。このようなジオールは２種以上を併用することもできる。
なお、植物由来のジカルボン酸と植物由来のジオールとは別に、植物由来でないジカルボン酸やジオールを併用することもできる。ただし、これら植物由来でないジカルボン酸やジオールは、原料成分全体の３０重量％以下、好ましくは２０重量％以下、さらに好ましくは１０重量％以下、最も好ましくは５重量％以下であるのがよい。
The plant-derived dicarboxylic acid is not particularly limited as long as it is plant-derived, and examples thereof include dimer acid produced from castor oil-derived sebacic acid and oleic acid. Two or more of these dicarboxylic acids can be used in combination.
In addition, the plant-derived diol is not particularly limited as long as it is derived from a plant, and examples thereof include a fatty acid ester derived from castor oil and a dimer diol produced from oleic acid. Two or more kinds of such diols can be used in combination.
Aside from plant-derived dicarboxylic acids and plant-derived diols, non-plant-derived dicarboxylic acids and diols can also be used in combination. However, these non-plant-derived dicarboxylic acids and diols may be 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and most preferably 5% by weight or less of the total raw material components.
ジカルボン酸とジオールとの縮合重合は、ジカルボン酸に含まれるカルボキシル基１．００モルに対して、ジオールに含まれる水酸基が１．０１〜１．７０モル、特に１．０５〜１．２０モルとなる割合で反応させるのが望ましい。
水酸基が１．０１モルより少ないと、縮合重合して得られるポリエステル樹脂の分子末端の水酸基が少なくなり、架橋剤による架橋処理が難しくなり、ゲル分率を適正範囲に調整しにくくなる。また、水酸基が１．７０モルより多くなると、分子量が低くなり、粘着剤層の塗工外観の低下などの支障をきたしやすい。
このような縮合重合により得られるポリエステル樹脂は、重量平均分子量（Ｍｗ）が、通常１万〜２０万の範囲にあるのが望ましい。
In the condensation polymerization of dicarboxylic acid and diol, the hydroxyl group contained in the diol is 1.01 to 1.70 mol, particularly 1.05 to 1.20 mol, relative to 1.00 mol of the carboxyl group contained in the dicarboxylic acid. It is desirable to make it react in the ratio.
When the number of hydroxyl groups is less than 1.01 mol, the number of hydroxyl groups at the molecular terminals of the polyester resin obtained by condensation polymerization is reduced, and crosslinking treatment with a crosslinking agent becomes difficult, making it difficult to adjust the gel fraction to an appropriate range. Moreover, when there are more hydroxyl groups than 1.70 mol, molecular weight will become low and it will be easy to cause troubles, such as a fall of the coating external appearance of an adhesive layer.
The polyester resin obtained by such condensation polymerization preferably has a weight average molecular weight (Mw) in the range of usually 10,000 to 200,000.
本発明においては、上記のポリエステル樹脂をベースポリマーとして、これに放射線硬化型樹脂と放射線反応開始剤と架橋剤を配合して、粘着剤を調製する。粘着剤の調製は、有機溶剤を用いて行ってもよいし、無溶剤下で行ってもよい。
なお、粘着剤の調製にあたり、必要により、従来公知の各種の添加剤、例えば、粘着付与剤、軟化剤、可塑剤、着色剤（染料、顔料）、老化防止剤、酸化防止剤、帯電防止剤、充填剤などを適量含ませることができる。
In the present invention, the above-mentioned polyester resin is used as a base polymer, and a radiation curable resin, a radiation reaction initiator, and a crosslinking agent are blended therein to prepare an adhesive. The pressure-sensitive adhesive may be prepared using an organic solvent or in the absence of a solvent.
In preparing the pressure-sensitive adhesive, various conventionally known additives such as tackifiers, softeners, plasticizers, colorants (dyes, pigments), anti-aging agents, antioxidants, and antistatic agents are used as necessary. An appropriate amount of a filler or the like can be included.
放射線硬化型樹脂は、放射線硬化性のオリゴマー成分として、ウレタン系、ポリエーテル系、ポリエステル系、ポリカーボネート系、ポリブタジエン系などの種々のオリゴマーが挙げられ、市販品をそのまま用いてもよい。粘着剤のバイオマス度を向上させるため、バイオマス材料を使用して合成したオリゴマーを使用してもよい。
この放射線硬化型樹脂は、官能基１個あたりの重量平均分子量が８，０００以下であるのが望ましく、より望ましくは５，０００以下、さらに望ましくは３，０００以下、最も望ましくは１，０００以下、とくに５００以下であるのがよい。
上記の重量平均分子量が大きすぎると、放射線照射による反応後も架橋間距離が長いために硬化が弱くなり、粘着力の低下に好結果が得られにくい。なお、放射線照射による反応後に粘着剤層が硬くなりすぎないように、官能基１個あたりの重量平均分子量は１００以上、とくに１５０以上であるのが望ましい。
The radiation curable resin includes various oligomers such as urethane, polyether, polyester, polycarbonate, and polybutadiene as radiation curable oligomer components, and commercially available products may be used as they are. In order to improve the biomass degree of the pressure-sensitive adhesive, an oligomer synthesized using a biomass material may be used.
The radiation curable resin preferably has a weight average molecular weight of 8,000 or less per functional group, more preferably 5,000 or less, more preferably 3,000 or less, and most preferably 1,000 or less. In particular, it should be 500 or less.
If the weight average molecular weight is too large, the distance between crosslinks is long even after the reaction by radiation irradiation, so that the curing becomes weak, and it is difficult to obtain a good result in reducing the adhesive force. In order to prevent the pressure-sensitive adhesive layer from becoming too hard after the reaction by irradiation, the weight average molecular weight per functional group is preferably 100 or more, particularly 150 or more.
ここで、上記の「官能基１個あたりの重量平均分子量」とは、（放射線硬化型樹脂の重量平均分子量）／（放射線硬化型樹脂に含まれる官能基数）として求められる値である。また、上記の官能基とは、放射線を照射することにより反応するビニル基などの二重結合（反応性不飽和結合）を指しており、さらに、その官能基数とは、放射線硬化型樹脂１分子中に含まれる上記官能基の数を指している。
Here, the above “weight average molecular weight per functional group” is a value obtained as (weight average molecular weight of radiation curable resin) / (number of functional groups contained in radiation curable resin). Moreover, said functional group points out double bonds (reactive unsaturated bond), such as a vinyl group which reacts by irradiating with radiation, Furthermore, the functional group number is one molecule of radiation curable resin. It refers to the number of the functional groups contained therein.
このような放射線硬化型樹脂の使用量は、ベースポリマーとなる前記ポリエステル樹脂１００重量部あたり、３０〜７０重量部となる割合とするのがよく、とくに望ましくは、４０〜６０重量部となる割合とするのがよい。
放射線硬化型樹脂が７０重量部より多くなると、とくに８０重量部以上となると、ポリエステル樹脂との混合が容易でなくなり、粘着剤層の塗工外観が悪くなるなどの支障をきたしやすい。また、３０重量部より少なくなると、とくに２０重量部以下となると、放射線照射後に粘着力の十分な低下効果が得られない。
The amount of such radiation curable resin used is preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight per 100 parts by weight of the polyester resin as the base polymer. It is good to do.
If the radiation curable resin is more than 70 parts by weight, particularly 80 parts by weight or more, mixing with the polyester resin is not easy, and troubles such as poor coating appearance of the pressure-sensitive adhesive layer are likely to occur. On the other hand, if the amount is less than 30 parts by weight, particularly 20 parts by weight or less, the effect of sufficiently reducing the adhesive strength after irradiation with radiation cannot be obtained.
放射線反応開始剤は、放射線硬化型樹脂を放射線の照射により硬化させるための反応開始剤であり、放射線の種類に応じた適宜のものが用いられる。例えば、放射線として紫外線を使用する場合は、従来公知の光重合開始剤として、α−ケトール系化合物、アセトフェノン系化合物、ベンゾインエーテル系化合物、ベンゾフェノン系化合物、チオキサンソン系化合物などが挙げられ、その他、ベンジルジメチルケタールなどのケタール系化合物、２−ナフタレンスルホニルクロリドなどの芳香族スルホニルクロリド系化合物、１−フェノン−１，１−プロパンジオン−２−（ｏ−エトキシカルボニル）オキシムなどの光活性オキシム系化合物、カンファーキノン、ハロゲン化ケトン、アシルホスフィノキシド、アシルホスフォナートなどが挙げられる。
The radiation reaction initiator is a reaction initiator for curing the radiation curable resin by irradiation with radiation, and an appropriate one according to the type of radiation is used. For example, when ultraviolet rays are used as radiation, conventionally known photopolymerization initiators include α-ketol compounds, acetophenone compounds, benzoin ether compounds, benzophenone compounds, thioxanthone compounds, and others. Ketal compounds such as dimethyl ketal, aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride, photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime, Examples include camphor quinone, halogenated ketone, acyl phosphinoxide, and acyl phosphonate.
上記のα−ケトール系化合物には、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、α−ヒドロキシ−α，α′−ジメチルアセトフェノン、２−メチル−２−ヒドロキシプロピオフェノン、１−ヒドロキシシクロヘキシルフェニルケトンなどがある。上記のアセトフェノン系化合物には、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、２，２−ジエトキシアセトフェノン、２−メチル−１−〔４−（メチルチオ）−フェニル〕−２−モルホリノプロパン−１などがある。上記のベンゾインエーテル系化合物には、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アニソインメチルエーテルなどがある。
また、上記のベンゾフェノン系化合物としては、ベンゾフェノン、ベンゾイル安息香酸、３，３′−ジメチル−４−メトキシベンゾフェノンなどが挙げられる。さらに、上記のチオキサンソン系化合物としては、チオキサンソン、２−クロロチオキサンソン、２−メチルチオキサンソン、２，４−ジメチルチオキサンソン、イソプロピルチオキサンソン、２，４−ジクロロチオキサンソン、２，４−ジエチルチオキサンソン、２，４−ジイソプロピルチオキサンソンなどが挙げられる。
The above α-ketol compounds include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypro Examples include piophenone and 1-hydroxycyclohexyl phenyl ketone. The acetophenone compounds include methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane. -1 etc. Examples of the benzoin ether compounds include benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether.
Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, and 3,3′-dimethyl-4-methoxybenzophenone. Further, the above thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2, Examples include 4-diethylthioxanthone and 2,4-diisopropylthioxanthone.
放射線反応開始剤の使用量は、放射線硬化型樹脂および放射線反応開始剤の種類により決定されるが、通常は、放射線硬化型樹脂に対し、２〜１０重量％となる割合で使用するのがよく、とくに望ましくは、５〜８重量％となる割合で使用するのがよい。
放射線反応開始剤が、放射線硬化型樹脂に対し、２重量％未満となると、放射線照射による硬化が十分に起こらず、粘着力の低下効果が得られない。また、放射線硬化型樹脂に対し、１０重量％を超えると、粘着剤層の塗工外観が低下する傾向にある。
The amount of radiation reaction initiator used is determined by the type of radiation curable resin and radiation reaction initiator, but it is usually better to use it at a ratio of 2 to 10% by weight with respect to the radiation curable resin. Particularly preferably, it should be used in a proportion of 5 to 8% by weight.
When the radiation reaction initiator is less than 2 % by weight with respect to the radiation curable resin, curing due to radiation irradiation does not occur sufficiently, and the effect of reducing the adhesive strength cannot be obtained. Moreover, when it exceeds 10 weight% with respect to radiation curable resin, it exists in the tendency for the coating external appearance of an adhesive layer to fall.
架橋剤は、ポリエステル樹脂の分子内に含まれる官能基（とくに、水酸基）と反応して上記樹脂を架橋構造化することにより、粘着剤層のゲル分率を適正範囲に調整し、放射線照射前の粘着剤層に良好な凝集力を付与するものである。
このような架橋剤には、上記官能基と反応する多官能性化合物が用いられる。例えば、ポリイソシアネート化合物、ポリイソシアヌレート化合物、ポリメラミン化合物、ポリエポキシ化合物、ポリオキサゾリン化合物、ポリアジリジン化合物、金属キレート化合物などが挙げられる。中でも、汎用性のあるポリイソシアネート化合物が好ましい。
The cross-linking agent reacts with functional groups (particularly hydroxyl groups) contained in the polyester resin molecule to form a cross-linked structure of the resin, thereby adjusting the gel fraction of the pressure-sensitive adhesive layer to an appropriate range before radiation irradiation. A good cohesive force is imparted to the pressure-sensitive adhesive layer.
As such a crosslinking agent, a polyfunctional compound that reacts with the functional group is used. Examples include polyisocyanate compounds, polyisocyanurate compounds, polymelamine compounds, polyepoxy compounds, polyoxazoline compounds, polyaziridine compounds, metal chelate compounds. Among these, versatile polyisocyanate compounds are preferable.
ポリイソシアネート化合物としては、ブチレンジイソシアネート、ヘキサメチレンジイソシアネートなどの脂肪族ポリイソシアネート類、シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネートなどの脂環族ポリイソシアネート類、２，４−トリレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート類、トリメチロールプロパンのトリレンジイソシアネート付加物やヘキサメチレンジイソシアネート付加物などが挙げられる。これらは、２種以上を併用してもよい。
Examples of the polyisocyanate compound include aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2,4-tolylene diisocyanate, 4, Examples thereof include aromatic polyisocyanates such as 4'-diphenylmethane diisocyanate and xylylene diisocyanate, tolylene diisocyanate adduct of trimethylolpropane, hexamethylene diisocyanate adduct and the like. Two or more of these may be used in combination.
架橋剤の量は、架橋処理後の粘着剤層のゲル分率（放射線照射前のゲル分率）が２０〜８０重量％となるように、とくに望ましくは３０〜７０重量％となるように、ポリエステル樹脂および架橋剤の種類に応じて、適宜選択することができる。
上記のゲル分率が２０重量％未満となると、適度な凝集力が得られず、被着体から剥がした際に汚染や糊残りの原因となりやすい。また、８０重量％を超えると、粘着剤層の弾性率が高くなってタックがなくなり初期粘着力が低くなり、粘着剤としての機能が低下し被着体の表面保護や固定などの目的を達成しにくい。
The amount of the crosslinking agent is such that the gel fraction (gel fraction before irradiation) of the pressure-sensitive adhesive layer after the crosslinking treatment is 20 to 80% by weight, particularly preferably 30 to 70% by weight. It can select suitably according to the kind of polyester resin and a crosslinking agent.
When the gel fraction is less than 20% by weight, an appropriate cohesive force cannot be obtained, and when peeled off from the adherend, it tends to cause contamination and adhesive residue. On the other hand, if it exceeds 80% by weight, the elastic modulus of the pressure-sensitive adhesive layer is increased, tack is eliminated, the initial adhesive strength is lowered, the function as the pressure-sensitive adhesive is lowered, and the purpose of surface protection and fixing of the adherend is achieved. Hard to do.
ポリイソシアネート化合物では、ポリエステル樹脂（原料成分であるジカルボン酸とジオールとの合計量）１００重量部あたり、１．５〜２０重量部とするのが好ましく、特に好ましくは２〜１５重量部とするのがよい。
なお、ゲル分率を効率良く得るため、架橋剤と共に適宜の触媒を用いることができる。例えば、テトラ−ｎ−ブチルチタネート、テトライソプロピルチタネート、ブチルスズオキシド、ジオクチルスズジラウレートなどが用いられる。
In the polyisocyanate compound, the amount is preferably 1.5 to 20 parts by weight, particularly preferably 2 to 15 parts by weight per 100 parts by weight of the polyester resin (total amount of dicarboxylic acid and diol as raw material components). Is good.
In addition, in order to obtain a gel fraction efficiently, a suitable catalyst can be used with a crosslinking agent. For example, tetra-n-butyl titanate, tetraisopropyl titanate, butyltin oxide, dioctyltin dilaurate and the like are used.
本発明においては、このように調製される粘着剤を基材上に塗布し、通常６０〜１２０℃の温度で基材の樹類に応じた所定時間乾燥して、また、この乾燥と同時またはその後に架橋処理して、基材上に厚さが通常５〜１００μｍ、好ましくは１０〜８０μｍの範囲にある架橋処理した粘着剤層を有する放射線硬化再剥離型粘着シートを得る。
In the present invention, the pressure-sensitive adhesive thus prepared is applied onto a substrate and dried at a temperature of usually 60 to 120 ° C. for a predetermined time according to the tree of the substrate. Thereafter, a crosslinking treatment is performed to obtain a radiation-curing re-peelable pressure-sensitive adhesive sheet having a crosslinked pressure-sensitive adhesive layer having a thickness of usually 5 to 100 μm, preferably 10 to 80 μm on the substrate.
粘着剤層を設ける基材には、プラスチックフィルム（またはシート）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、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、プラスチックフィルム（またはシート）同士の積層体など〕の適宜の薄葉体を用いることができる。
このような基材の厚さは、基材の強度や柔軟性、使用目的などに応じて、適宜に選択することができる。一般には、１，０００μｍ以下（１〜１，０００μｍ）、好ましくは１〜５００μｍ、さらに好ましくは３〜３００μｍ、最も好ましくは５〜２５０μｍであるのがよい、ただし、これらに限定されるものではない。
The base material on which the pressure-sensitive adhesive layer is provided includes plastic base materials such as plastic films (or sheets), rubber base materials such as rubber sheets, foams such as foam sheets, and laminates thereof [particularly plastic base materials. And a laminate of other substrate, a laminate of plastic films (or sheets), etc.] can be used.
The thickness of such a base material can be appropriately selected according to the strength, flexibility, purpose of use, and the like of the base material. Generally, it should be 1,000 μm or less (1 to 1,000 μm), preferably 1 to 500 μm, more preferably 3 to 300 μm, and most preferably 5 to 250 μm, but is not limited thereto. .
プラスチック系基材における素材としては、例えば、ポリエチレン、ポリプロピレン、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などの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レート、ポリエチレンナフタレート、ポリブチレンテレフタレートなどのポリエステル、ポリ塩化ビニル、ポリフェニレンスルフィド、ポリアミド、全芳香族ポリアミド（アラミド）などのアミド系樹脂、ポリエーテルエーテルケトンなどが挙げられる。これらの素材は、単独でまたは２種以上を組み合わせて使用することができる。
Examples of the material in the plastic base material include, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and other olefin resins having a monomer component such as polyethylene terephthalate, polyethylene naphthalate, Examples thereof include polyesters such as polybutylene terephthalate, polyvinyl chloride, polyphenylene sulfide, polyamides, amide resins such as wholly aromatic polyamides (aramids), and polyether ether ketones. These materials can be used alone or in combination of two or more.
基材として、プラスチック系基材を使用する場合は、延伸処理などにより伸び率などの変形性を制御して用いてもよい。また、基材としては、放射線の透過を阻害しない透明なものを使用するのが望ましい。さらに、バイオマス基材であるポリ乳酸基材を用いると、バイオマス度を高めることができので、望ましい。
When using a plastic-type base material as a base material, you may control and use deformability, such as elongation rate, by extending | stretching process. Further, it is desirable to use a transparent substrate that does not inhibit the transmission of radiation. Furthermore, it is desirable to use a polylactic acid base material which is a biomass base material because the degree of biomass can be increased.
また、基材の表面は、基材上に形成される粘着剤層との密着性を高めるため、慣用の表面処理、例えば、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理などの化学的または物理的方法による酸化処理などが施されていてもよく、下塗り剤によるコーティング処理などが施されていてもよい。
In addition, the surface of the base material has a conventional surface treatment, for example, chromic acid treatment, ozone exposure, flame exposure, high-voltage impact exposure, ionizing radiation treatment, in order to improve adhesion with the adhesive layer formed on the base material. An oxidation treatment or the like by a chemical or physical method such as the above may be applied, or a coating treatment with a primer may be applied.
本発明の放射線硬化再剥離型粘着シートは、放射線照射前の粘着力が１．４Ｎ／２０mm以上（通常、１０Ｎ／２０mm以下、特に７Ｎ／２０mm以下）で、放射線（４，８００ｍＪ／ｃｍ2 の紫外線）照射後の粘着力が０．９Ｎ／２０mm以下（好ましくは０．８Ｎ／２０mm以下、より好ましくは０．６Ｎ／２０mm以下）である。
放射線照射前の粘着力が１．４Ｎ／２０mm以上であることにより、被着体の表面保護や固定などの機能を十分に発揮させることができる。また、放射線照射後の粘着力が０．９Ｎ／２０mm以下であることにより、再剥離時に容易に剥がすことができる。
The radiation-curable re-peelable pressure-sensitive adhesive sheet of the present invention has an adhesive strength before irradiation of 1.4 N / 20 mm or more (usually 10 N / 20 mm or less, particularly 7 N / 20 mm or less), and radiation (4,800 mJ / cm 2 ). The adhesive strength after irradiation with ultraviolet rays is 0.9 N / 20 mm or less (preferably 0.8 N / 20 mm or less, more preferably 0.6 N / 20 mm or less).
When the adhesive force before irradiation is 1.4 N / 20 mm or more, functions such as surface protection and fixation of the adherend can be sufficiently exhibited. Moreover, it can peel easily at the time of re-peeling because the adhesive strength after radiation irradiation is 0.9 N / 20 mm or less.
本発明の放射線硬化再剥離型粘着シートは、各種被着体の表面保護や固定（保持）などの目的で一時的に用いられ、その後被着体より再剥離する際に放射線を照射して粘着剤層を硬化させ粘着力を低下させてから、被着体より剥離する。
被着体より剥離した上記粘着シートは、粘着剤層が植物由来材料からなるため、これを廃棄処理した場合二酸化炭素を排出してもカーボンニュートラルを実現でき、地球環境に悪影響を及ぼすことはない。
The radiation-curing re-peelable pressure-sensitive adhesive sheet of the present invention is temporarily used for the purpose of surface protection and fixing (holding) of various adherends, and then irradiated with radiation when peeled again from the adherend. After the agent layer is cured to reduce the adhesive strength, it is peeled off from the adherend.
The pressure-sensitive adhesive sheet peeled off from the adherend has a pressure-sensitive adhesive layer made of a plant-derived material. Therefore, when this is discarded, carbon neutral can be realized even if carbon dioxide is discharged, and the global environment is not adversely affected. .
つぎに、本発明の実施例を記載して、より具体的に説明する。なお、以下において、部とあるのは重量部を意味する。また、以下の実施例および比較例で使用したポリエステル樹脂Ａ〜Ｅは、下記の方法で製造したものである。
Next, examples of the present invention will be described in more detail. In the following, “parts” means parts by weight. Polyester resins A to E used in the following examples and comparative examples are produced by the following method.
＜ポリエステル樹脂Ａの製造＞
三つ口セパラブルフラスコに撹拌機、温度計、真空ポンプを付し、これにダイマー酸（商品名「プリポール１００９」Ｍｗ５６７ ユニケマ社製）１１０．７ｇ、ダイマージオール（商品名「プリポール２０３３」Ｍｗ５３７ ユニケマ社製）１００ｇ、触媒としてチタンテトライソプロポキシド（キシダ化学社製）０．５３２ｇを仕込み、減圧雰囲気で撹拌しながら２００℃まで昇温し、この温度を保持した。約３時間反応を続けてポリエステル樹脂Ａを得た。重量平均分子量Ｍｗは３万であった。なお、上記のダイマー酸とダイマージオールとの使用量は、ダイマー酸に含まれるカルボキシル基１．００モルに対して、ダイマージオールに含まれる水酸基が０．９５モルとなる割合であった。
<Manufacture of polyester resin A>
A three-necked separable flask was equipped with a stirrer, thermometer, and vacuum pump, and dimer acid (trade name “Pripol 1009” Mw567 made by Unikema Co., Ltd.) 110.7 g, dimer diol (trade name “Plipol 2033” Mw537 Unikema) 100 g) and 0.532 g of titanium tetraisopropoxide (manufactured by Kishida Chemical Co., Ltd.) as a catalyst were charged and the temperature was raised to 200 ° C. while stirring in a reduced pressure atmosphere, and this temperature was maintained. The reaction was continued for about 3 hours to obtain polyester resin A. The weight average molecular weight Mw was 30,000. In addition, the usage-amount of said dimer acid and dimer diol was the ratio from which the hydroxyl group contained in dimer diol will be 0.95 mol with respect to 1.00 mol of carboxyl groups contained in dimer acid.
＜ポリエステル樹脂Ｂの製造＞
ダイマー酸の使用量を１０４．９ｇに変更し、ダイマージオールの使用量は１００ｇのままとした以外は、ポリエステル樹脂Ａの場合と同様にして、ポリエステル樹脂Ｂを得た。重量平均分子量Ｍｗは８．５万であった。なお、上記のダイマー酸とダイマージオールとの使用量は、ダイマー酸に含まれるカルボキシル基１．００モルに対して、ダイマージオールに含まれる水酸基が１．０１モルとなる割合であった。
<Manufacture of polyester resin B>
Polyester resin B was obtained in the same manner as for polyester resin A, except that the amount of dimer acid used was changed to 104.9 g and the amount of dimer diol used was still 100 g. The weight average molecular weight Mw was 85,000. In addition, the usage-amount of said dimer acid and dimer diol was the ratio from which the hydroxyl group contained in dimer diol will be 1.01 mol with respect to 1.00 mol of carboxyl groups contained in dimer acid.
＜ポリエステル樹脂Ｃの製造＞
ダイマー酸の使用量を１００．９ｇに変更し、ダイマージオールの使用量は１００ｇのままとした以外は、ポリエステル樹脂Ａの場合と同様にして、ポリエステル樹脂Ｃを得た。重量平均分子量Ｍｗは５．５万であった。なお、上記のダイマー酸とダイマージオールとの使用量は、ダイマー酸に含まれるカルボキシル基１．００モルに対して、ダイマージオールに含まれる水酸基が１．０５モルとなる割合であった。
<Manufacture of polyester resin C>
Polyester resin C was obtained in the same manner as for polyester resin A, except that the amount of dimer acid used was changed to 100.9 g and the amount of dimer diol used was still 100 g. The weight average molecular weight Mw was 55,000. In addition, the usage-amount of said dimer acid and dimer diol was the ratio from which the hydroxyl group contained in dimer diol will be 1.05 mol with respect to 1.00 mol of carboxyl groups contained in dimer acid.
＜ポリエステル樹脂Ｄの製造＞
ダイマー酸の使用量を６２．３ｇに変更し、ダイマージオールの使用量は１００ｇのままとした以外は、ポリエステル樹脂Ａの場合と同様にして、ポリエステル樹脂Ｄを得た。重量平均分子量Ｍｗは１．１万であった。なお、上記のダイマー酸とダイマージオールとの使用量は、ダイマー酸に含まれるカルボキシル基１．００モルに対して、ダイマージオールに含まれる水酸基が１．７０モルとなる割合であった。
<Manufacture of polyester resin D>
Polyester resin D was obtained in the same manner as for polyester resin A, except that the amount of dimer acid used was changed to 62.3 g and the amount of dimer diol used was still 100 g. The weight average molecular weight Mw was 11,000. In addition, the usage-amount of said dimer acid and dimer diol was the ratio from which the hydroxyl group contained in dimer diol will be 1.70 mol with respect to 1.00 mol of carboxyl groups contained in dimer acid.
＜ポリエステル樹脂Ｅの製造＞
ダイマー酸の使用量を５８．９ｇに変更し、ダイマージオールの使用量は１００ｇのままとした以外は、ポリエステル樹脂Ａの場合と同様にして、ポリエステル樹脂Ｅを得た。重量平均分子量Ｍｗは０．８万であった。なお、上記のダイマー酸とダイマージオールとの使用量は、ダイマー酸に含まれるカルボキシル基１．００モルに対して、ダイマージオールに含まれる水酸基が１．８０モルとなる割合であった。
<Manufacture of polyester resin E>
Polyester resin E was obtained in the same manner as for polyester resin A, except that the amount of dimer acid used was changed to 58.9 g and the amount of dimer diol used was still 100 g. The weight average molecular weight Mw was 88,000. In addition, the usage-amount of said dimer acid and dimer diol was the ratio from which the hydroxyl group contained in dimer diol will be 1.80 mol with respect to 1.00 mol of carboxyl groups contained in dimer acid.
実施例１
ポリエステル樹脂Ｂ１００部に、架橋剤としてヘキサメチレンジイソシアネート（商品名「ＴＰＡ−１００」、旭化成ケミカルズ社製）１０部、放射線硬化型樹脂として１分子中に反応性不飽和結合（二重結合）を６個有する重量平均分子量２，０００の紫外線硬化型ウレタンオリゴマー〔商品名「紫光 ＵＶ−１７００Ｂ」、日本合成化学工業（株）製〕４０部を配合し、さらに放射線反応開始剤（光重合開始剤）として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン〔商品名「ＩＲＧＡＣＵＲＥ１８４」、チバジャパン（株）製〕を放射線硬化型樹脂に対し５重量％配合し、粘着剤を調製した。
これを、剥離処理を施したポリエチレンテレフタレート（ＰＥＴ）シートの剥離処理面に乾燥後の厚さが５０μｍとなるように塗布し、１２０℃で３分乾燥した。乾燥後、粘着剤層の表面保護のため、上記とは別の剥離処理を施したＰＥＴシートの剥離処理面を貼り合わせ、エージングを５０℃で５日間実施して、架橋処理した厚さが５０μｍの粘着剤層を有する剥離処理粘着シートを作製した。
つぎに、この剥離処理粘着シートを用い、粘着剤層上の一方の剥離処理ＰＥＴシートを引き剥がして、その引き剥がし面に、基材である厚さが２５μｍのポリエステルフィルム（商品名「ルミラーＳ−１０」、東レ社製）をハンドローラで貼り合わせることにより、放射線硬化再剥離型粘着シートを作製した。
Example 1
100 parts of polyester resin B, 10 parts of hexamethylene diisocyanate (trade name “TPA-100”, manufactured by Asahi Kasei Chemicals) as a crosslinking agent, and 6 reactive unsaturated bonds (double bonds) in one molecule as a radiation curable resin 40 parts of UV curable urethane oligomer having a weight average molecular weight of 2,000 (trade name “purple UV-1700B”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is added, and a radiation reaction initiator (photopolymerization initiator) is further added. 1-hydroxy-cyclohexyl-phenyl-ketone [trade name “IRGACURE184”, manufactured by Ciba Japan Co., Ltd.] was blended in an amount of 5% by weight with respect to the radiation curable resin to prepare an adhesive.
This was applied to the release-treated surface of a polyethylene terephthalate (PET) sheet subjected to a release treatment so that the thickness after drying was 50 μm, and dried at 120 ° C. for 3 minutes. After drying, in order to protect the surface of the pressure-sensitive adhesive layer, the release-treated surface of a PET sheet subjected to a separate release treatment was bonded together, and aging was carried out at 50 ° C. for 5 days, and the crosslinked thickness was 50 μm. A release-treated pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer was prepared.
Next, using this release-treated pressure-sensitive adhesive sheet, one of the release-treated PET sheets on the pressure-sensitive adhesive layer was peeled off, and a polyester film (trade name “Lumirror S” having a thickness of 25 μm as a base material was formed on the peeled surface. −10 ”(manufactured by Toray Industries, Inc.) was bonded with a hand roller to prepare a radiation-curing re-peelable pressure-sensitive adhesive sheet.
実施例２
ポリエステル樹脂Ｂ１００部に代えて、ポリエステル樹脂Ｃ１００部を使用し、架橋剤（商品名「ＴＰＡ−１００」）の使用量を４部に、放射線硬化型樹脂（商品名「紫光 ＵＶ−１７００Ｂ」）の使用量を３０部に、それぞれ変更した以外は、実施例１と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 2
Instead of 100 parts of polyester resin B, 100 parts of polyester resin C are used, the amount of crosslinking agent (trade name “TPA-100”) is 4 parts, and radiation curable resin (trade name “purple light UV-1700B”) is used. A pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the amount used was changed to 30 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例３
架橋剤（商品名「ＴＰＡ−１００」）の使用量を２部に、放射線硬化型樹脂（商品名「紫光 ＵＶ−１７００Ｂ」）の使用量を４０部に、それぞれ変更した以外は、実施例２と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 3
Example 2 except that the amount of the crosslinking agent (trade name “TPA-100”) was changed to 2 parts and the amount of the radiation curable resin (trade name “purple UV-1700B”) was changed to 40 parts. In the same manner as described above, an adhesive was prepared.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例４
架橋剤（商品名「ＴＰＡ−１００」）の使用量を４部に変更した以外は、実施例３と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 4
A pressure-sensitive adhesive was prepared in the same manner as in Example 3 except that the amount of the crosslinking agent (trade name “TPA-100”) was changed to 4 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例５
架橋剤（商品名「ＴＰＡ−１００」）の使用量を８部に変更した以外は、実施例３と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 5
A pressure-sensitive adhesive was prepared in the same manner as in Example 3 except that the amount of the crosslinking agent (trade name “TPA-100”) was changed to 8 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例６
放射線反応開始剤（商品名「ＩＲＧＡＣＵＲＥ１８４」）の使用量を放射線硬化型樹脂に対し２重量％に変更した以外は、実施例４と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 6
A pressure-sensitive adhesive was prepared in the same manner as in Example 4 except that the amount of the radiation reaction initiator (trade name “IRGACURE184”) was changed to 2% by weight with respect to the radiation curable resin.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例７
放射線反応開始剤（商品名「ＩＲＧＡＣＵＲＥ１８４」）の使用量を放射線硬化型樹脂に対し１０重量％に変更した以外は、実施例４と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 7
A pressure-sensitive adhesive was prepared in the same manner as in Example 4 except that the amount of the radiation reaction initiator (trade name “IRGACURE184”) was changed to 10% by weight with respect to the radiation-curable resin.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例８
放射線硬化型樹脂（商品名「紫光 ＵＶ−１７００Ｂ」）の使用量を６０部に変更した以外は、実施例２と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 8
A pressure-sensitive adhesive was prepared in the same manner as in Example 2 except that the amount of radiation-curable resin (trade name “purple light UV-1700B”) used was changed to 60 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例９
放射線硬化型樹脂（商品名「紫光 ＵＶ−１７００Ｂ」）の使用量を７０部に変更した以外は、実施例２と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 9
A pressure-sensitive adhesive was prepared in the same manner as in Example 2 except that the amount of radiation curable resin (trade name “purple light UV-1700B”) used was changed to 70 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
実施例１０
ポリエステル樹脂Ｂ１００部に代えて、ポリエステル樹脂Ｄ１００部を使用し、架橋剤（商品名「ＴＰＡ−１００」）の使用量を１５部に変更した以外は、実施例１と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Example 10
In place of the polyester resin B100 part, the polyester resin D100 part was used, and the adhesive was changed in the same manner as in Example 1 except that the amount of the crosslinking agent (trade name “TPA-100”) was changed to 15 parts. Prepared.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例１
放射線硬化型樹脂（商品名「紫光 ＵＶ−１７００Ｂ」）の使用量を２０部に変更した以外は、実施例２と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 1
A pressure-sensitive adhesive was prepared in the same manner as in Example 2 except that the amount of radiation-curable resin (trade name “purple light UV-1700B”) used was changed to 20 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例２
放射線硬化型樹脂（商品名「紫光 ＵＶ−１７００Ｂ」）の使用量を８０部に変更した以外は、実施例２と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 2
A pressure-sensitive adhesive was prepared in the same manner as in Example 2 except that the amount of radiation-curable resin (trade name “purple light UV-1700B”) used was changed to 80 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例３
ポリエステル樹脂Ｄ１００部に代えて、ポリエステル樹脂Ａ１００部を使用した以外は、実施例１０と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 3
A pressure-sensitive adhesive was prepared in the same manner as in Example 10 except that 100 parts of polyester resin A was used instead of 100 parts of polyester resin D.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例４
ポリエステル樹脂Ｄ１００部に代えて、ポリエステル樹脂Ｅ１００部を使用した以外は、実施例１０と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 4
An adhesive was prepared in the same manner as in Example 10 except that 100 parts of the polyester resin E was used instead of 100 parts of the polyester resin D.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例５
架橋剤（商品名「ＴＰＡ−１００」）の使用量を１部に変更した以外は、実施例３と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 5
A pressure-sensitive adhesive was prepared in the same manner as in Example 3 except that the amount of the crosslinking agent (trade name “TPA-100”) was changed to 1 part.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例６
放射線反応開始剤（商品名「ＩＲＧＡＣＵＲＥ１８４」）の使用量を放射線硬化型樹脂に対し１重量％に変更した以外は、実施例４と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 6
A pressure-sensitive adhesive was prepared in the same manner as in Example 4 except that the amount of the radiation reaction initiator (trade name “IRGACURE184”) was changed to 1% by weight with respect to the radiation-curable resin.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例７
放射線反応開始剤（商品名「ＩＲＧＡＣＵＲＥ１８４」）の使用量を放射線硬化型樹脂に対し１２重量％に変更した以外は、実施例４と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 7
A pressure-sensitive adhesive was prepared in the same manner as in Example 4 except that the amount of the radiation reaction initiator (trade name “IRGACURE184”) was changed to 12% by weight with respect to the radiation curable resin.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例８
放射線硬化型樹脂として、商品名「紫光 ＵＶ−１７００Ｂ」４０部に代えて、１分子中に反応性不飽和結合（二重結合）を２個有する重量平均分子量１８，０００の紫外線硬化型ウレタンオリゴマー〔商品名「紫光 ＵＶ−３０００Ｂ」、日本合成化学工業（株）製〕４０部を使用した以外は、実施例４と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 8
As a radiation curable resin, a UV-curable urethane oligomer having a weight average molecular weight of 18,000 having two reactive unsaturated bonds (double bonds) in one molecule, instead of 40 parts of the trade name “Shikou UV-1700B” [Product name “Shikou UV-3000B”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] A pressure-sensitive adhesive was prepared in the same manner as in Example 4 except that 40 parts were used.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例９
放射線硬化型樹脂（商品名「紫光 ＵＶ−３０００Ｂ」）の使用量を６０部に変更した以外は、比較例８と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 9
A pressure-sensitive adhesive was prepared in the same manner as in Comparative Example 8, except that the amount of radiation-curable resin (trade name “purple light UV-3000B”) was changed to 60 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
比較例１０
放射線硬化型樹脂（商品名「紫光 ＵＶ−３０００Ｂ」）の使用量を７０部に変更した以外は、比較例８と同様にして、粘着剤を調製した。
また、この粘着剤を用いて、実施例１と同様にして、剥離処理粘着シートを作製した。さらに、この剥離処理粘着シートを用いて、実施例１と同様にして、放射線硬化再剥離型粘着シートを作製した。
Comparative Example 10
A pressure-sensitive adhesive was prepared in the same manner as in Comparative Example 8, except that the amount of the radiation curable resin (trade name “purple light UV-3000B”) was changed to 70 parts.
In addition, a release-treated pressure-sensitive adhesive sheet was produced using this pressure-sensitive adhesive in the same manner as in Example 1. Further, using this release-treated pressure-sensitive adhesive sheet, a radiation-curing re-peelable pressure-sensitive adhesive sheet was produced in the same manner as in Example 1.
以上の実施例１〜１０および比較例１〜１０に関し、各剥離処理粘着シートを用いて、下記の方法により、粘着剤層の放射線照射前のゲル分率を測定し、また各放射線硬化再剥離型粘着シートを用いて、下記の方法により、放射線照射前および照射後の粘着力を測定した。これらの結果は、表１〜表６に示れるとおりであった。
なお、各表には、使用した粘着剤の組成（ポリエステル樹脂の種類および原料成分の水酸基／カルボキシル基比、ポリエステル樹脂、放射線硬化型樹脂、放射線反応開始剤および架橋剤の使用部数）を併記した。
About the above Examples 1-10 and Comparative Examples 1-10, the gel fraction before the radiation irradiation of an adhesive layer is measured by the following method using each peeling process adhesive sheet, and each radiation hardening re-peeling Using the mold pressure-sensitive adhesive sheet, the adhesive strength before and after irradiation was measured by the following method. These results were as shown in Tables 1-6.
In each table, the composition of the pressure-sensitive adhesive used (type of polyester resin and hydroxyl group / carboxyl group ratio of raw material components, polyester resin, radiation curable resin, radiation reaction initiator and number of used crosslinking agents) is also shown. .
＜粘着剤層の放射線照射前のゲル分率＞
剥離処理粘着シート（粘着剤層の厚さ５０μｍ）を５cm×５cm角に切り出し、両面側の剥離処理を施したＰＥＴシートを引き剥がして、サンプルとした。
このサンプルを、重さがわかっているポリテトラフルオロエチレン（ＰＴＦＥ）シートで包み重量を秤量し、トルエン中に２３℃で７日間放置して、サンプル中のゾル分を抽出した。その後、１３０℃で２時間乾燥し、乾燥後の重量を秤量した。粘着剤層の放射線照射前のゲル分率は、下記の式にて算出した。
ゲル分率（重量％）＝〔（乾燥後の重量−ＰＴＦＥシート重量）／（乾燥前の重量−ＰＴＦＥシート重量）〕×１００
<Gel fraction of the adhesive layer before irradiation>
A release-treated pressure-sensitive adhesive sheet (adhesive layer thickness 50 μm) was cut into a 5 cm × 5 cm square, and the PET sheet subjected to the separation treatment on both sides was peeled off to obtain a sample.
This sample was wrapped with a polytetrafluoroethylene (PTFE) sheet of known weight, and the weight was weighed and left in toluene at 23 ° C. for 7 days to extract the sol content in the sample. Then, it dried at 130 degreeC for 2 hours, and measured the weight after drying. The gel fraction before irradiation of the pressure-sensitive adhesive layer was calculated by the following formula.
Gel fraction (% by weight) = [(weight after drying−PTFE sheet weight) / (weight before drying−PTFE sheet weight)] × 100
＜放射線照射前および照射後の粘着力＞
放射線硬化再剥離型粘着シート（幅２０mmにカット）の粘着剤層に貼り合わされている剥離処理を施したＰＥＴシートを引き剥がして、その粘着剤層面を被着体としてのＳＵＳ３０４板に２kgローラー１往復にて貼着させて、測定片とした。
この測定片について、２３℃で３０分放置後、引張圧縮試験機（ミネベア社製「ＴＧ−１ｋＮ」）にて、１８０°ピール接着力（粘着力）（Ｎ／２０mm）（剥離速度：１５０mm／分、温度：２３±２℃、湿度：６５±５％ＲＨ）を測定した。この測定値を、放射線照射前の粘着力（初期粘着力）とした。
また、上記同様の測定片について、２３℃で３０分放置後に、４，８００ｍＪ／ｃｍ2 の紫外線を照射して、粘着剤層を硬化させ、その後に、上記と同様にして、１８０°ピール接着力（粘着力）を測定した。この測定値を、放射線照射後の粘着力とした。
<Adhesive strength before and after irradiation>
The PET sheet that has been subjected to the release treatment attached to the pressure-sensitive adhesive layer of the radiation-curing re-peelable pressure-sensitive adhesive sheet (cut to a width of 20 mm) is peeled off, and the surface of the pressure-sensitive adhesive layer is placed on the SUS304 plate as the adherend. A measuring piece was attached by reciprocation.
About this measurement piece, after leaving at 23 degreeC for 30 minutes, with a tension compression tester ("TG-1kN" by Minebea) 180 degree peel adhesive force (adhesive force) (N / 20mm) (peeling speed: 150mm / Minute, temperature: 23 ± 2 ° C., humidity: 65 ± 5% RH). This measured value was defined as the adhesive strength before irradiation (initial adhesive strength).
Further, the same measurement piece as described above was allowed to stand at 23 ° C. for 30 minutes, and then irradiated with ultraviolet rays of 4,800 mJ / cm 2 to cure the pressure-sensitive adhesive layer. The force (adhesive strength) was measured. This measured value was taken as the adhesive strength after irradiation.
以上の結果から明らかなように、実施例１〜１０の各放射線硬化再剥離型粘着シートは被着体に対する初期粘着力（放射線照射前の粘着力）が１．４Ｎ／２０mm以上と大きく、放射線照射後には０．９Ｎ／２０mm以下の小さい粘着力を示し、被着体より容易に再剥離が可能であることがわかる。これに対して、比較例１〜１０の各放射線硬化再剥離型粘着シートは上記いずれかの特性に劣っている。
また、実施例１〜１０の各放射線硬化再剥離型粘着シートは、上記優れた特性に加えて粘着剤層が植物由来であるため焼却処理しても二酸化炭酸の増加の抑制を期待でき、地球環境にやさしいバイオマス放射線硬化再剥離型粘着シートとしての特徴を有している。
As is clear from the above results, each of the radiation-curing re-peelable pressure-sensitive adhesive sheets of Examples 1 to 10 has a large initial adhesive strength (adhesive strength before irradiation) with respect to the adherend of 1.4 N / 20 mm or more. After irradiation, it shows a low adhesive strength of 0.9 N / 20 mm or less, and it can be seen that re-peeling is easier than the adherend. On the other hand, each radiation hardening re-peelable pressure-sensitive adhesive sheet of Comparative Examples 1 to 10 is inferior in any of the above characteristics.
In addition to the above excellent properties, each radiation-curing re-peelable pressure-sensitive adhesive sheet of Examples 1 to 10 can be expected to suppress an increase in carbon dioxide even when incinerated because the pressure-sensitive adhesive layer is derived from a plant. It has the characteristics of an environmentally friendly biomass radiation-curing re-peelable adhesive sheet.
Claims (2)
On the base material, dimer acid , which is a plant-derived dicarboxylic acid , and dimer diol, which is a plant-derived diol , have a hydroxyl group contained in the diol in an amount of 1.01-1. A functional group having a weight average molecular weight of 11,000 to 85,000 obtained by condensation polymerization at a ratio of 70 mol, and an amount of 30 to 70 parts by weight per 100 parts by weight of the polyester resin. A radiation-curable resin having a weight average molecular weight of 8,000 or less per one and a radiation reaction initiator in an amount of 2 to 10% by weight with respect to the radiation-curable resin, and a crosslinking treatment with a crosslinking agent Having a pressure-sensitive adhesive layer having a gel fraction of 20 to 80% by weight, an adhesive strength before irradiation of 1.4 N / 20 mm or more, and radiation (ultraviolet rays of 4,800 mJ / cm 2 ) A radiation-curing re-peelable pressure-sensitive adhesive sheet having an adhesive strength after irradiation of 0.9 N / 20 mm or less.
The radiation-curable re-peelable pressure-sensitive adhesive sheet according to claim 1, wherein the crosslinking agent is a polyisocyanate compound.
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