JP6292429B1 - Adhesive and adhesive sheet - Google Patents
Adhesive and adhesive sheet Download PDFInfo
- Publication number
- JP6292429B1 JP6292429B1 JP2017158327A JP2017158327A JP6292429B1 JP 6292429 B1 JP6292429 B1 JP 6292429B1 JP 2017158327 A JP2017158327 A JP 2017158327A JP 2017158327 A JP2017158327 A JP 2017158327A JP 6292429 B1 JP6292429 B1 JP 6292429B1
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- pressure
- resin
- sensitive adhesive
- bismuth
- 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.)
- Active
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- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 52
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 25
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 22
- 239000004840 adhesive resin Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 abstract description 24
- 238000004040 coloring Methods 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 239000000178 monomer Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 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 12
- 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 12
- 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 12
- 239000012790 adhesive layer Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 azo compound Chemical class 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 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 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000010330 laser marking Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-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
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- RCYIWFITYHZCIW-UHFFFAOYSA-N 4-methoxybut-1-yne Chemical compound COCCC#C RCYIWFITYHZCIW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical compound O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression 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
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QWVYNEUUYROOSZ-UHFFFAOYSA-N trioxido(oxo)vanadium;yttrium(3+) Chemical compound [Y+3].[O-][V]([O-])([O-])=O QWVYNEUUYROOSZ-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
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Abstract
【課題】本発明は、印字後のコントラストが良好であり、着色を抑制した粘着層を形成できる粘着剤および粘着シートの提供を目的とする。【解決手段】粘着性樹脂（Ａ）、およびビスマス系レーザ発色剤（Ｂ）を含む、粘着剤。なお、前記ビスマス系レーザ発色剤（Ｂ）は、Ｄ５０平均粒子径が０．０５〜５μｍであることが好ましい。また、前記粘着性樹脂（Ａ）１００質量部に対して、ビスマス系レーザ発色剤（Ｂ）を０．１〜５質量部含むことが好ましい。【選択図】なしAn object of the present invention is to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that can form a pressure-sensitive adhesive layer that has good contrast after printing and suppresses coloring. An adhesive comprising an adhesive resin (A) and a bismuth-based laser color former (B). The bismuth laser color former (B) preferably has a D50 average particle diameter of 0.05 to 5 μm. Moreover, it is preferable that 0.1-5 mass parts of bismuth type | system | group laser color formers (B) are included with respect to 100 mass parts of said adhesive resins (A). [Selection figure] None
Description
本発明は、粘着剤に関する。 The present invention relates to an adhesive.
各種包装材や容器に貼付されるラベルは、製品名に加え生産ロット等が印字されていることが多く、インクジェット法やレーザマーキング法での印字が一般的であった。
しかし、インクジェット法は、感熱性インクを使用するため耐熱性が悪く、例えば冷凍食品のラベルに使用すると電子レンジでの加熱で印字部分以外も発色してしまい、印字内容が解読ができない問題があった。そのため用途が限定されないレーザマーキング法での印字が増えている。
In many cases, labels attached to various packaging materials and containers are printed with production lots and the like in addition to product names, and printing by an ink jet method or a laser marking method is common.
However, since the ink jet method uses heat-sensitive ink, its heat resistance is poor. For example, when it is used on a label for frozen foods, there is a problem that colors other than the printed part are colored by heating in a microwave oven, and the printed content cannot be decoded. It was. For this reason, printing by the laser marking method, whose application is not limited, is increasing.
例えば、特許文献１には、レーザ発色剤として酸化銅や三酸化モリブデンを含む粘着剤が開示されている。 For example, Patent Document 1 discloses an adhesive containing copper oxide or molybdenum trioxide as a laser color former.
しかし、従来の粘着剤は、酸化銅を含むためレーザ発色部（印字部）と非発色部とコントラストが低下し、印字部の視認性が低下する問題があった。また、三酸化モリブデンを含むと粘着層が黄色に着色するため、透明ラベルにこの粘着層に使用するとラベルの商品性が低下する問題、さらに例えば生鮮食品のラベルに使用すると消費者に対して、その黄色から新鮮さにマイナスのイメージを与えて当該生鮮食品の販売量が低下し易い問題があった。 However, since the conventional adhesive contains copper oxide, there is a problem that the contrast between the laser coloring portion (printing portion) and the non-coloring portion is lowered, and the visibility of the printing portion is lowered. In addition, when molybdenum trioxide is included, the adhesive layer is colored yellow, so when used for this adhesive layer for transparent labels, the problem of reducing the merchandise of the label, and for example, when used for fresh food labels, There was a problem that the sales volume of the perishable food was likely to be reduced by giving a negative image to freshness from the yellow.
本発明は、印字後のコントラストが良好であり、着色を抑制した粘着層を形成できる粘着剤および粘着シートの提供を目的とする。 An object of the present invention is to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that have good contrast after printing and can form a pressure-sensitive adhesive layer with suppressed coloring.
本発明の粘着剤は、粘着性樹脂（Ａ）、およびビスマス系レーザ発色剤（Ｂ）を含む。 The pressure-sensitive adhesive of the present invention contains a pressure-sensitive resin (A) and a bismuth-based laser color former (B).
上記の本発明によれば、印字後のコントラストが良好であり、着色を抑制する粘着層を形成できる粘着剤および粘着シートを提供できる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that have good contrast after printing and can form a pressure-sensitive adhesive layer that suppresses coloring.
本明細書でシート、フィルム、テープは、同義語である。
本明細書で被着体は、粘着シートを貼り合わせる相手方である。
本明細書で（メタ）アクリル酸は、アクリル酸およびメタクリル酸を含む。また、モノマーは、エチレン性不飽和基含有単量体を意味する。
In this specification, a sheet, a film, and a tape are synonymous.
In this specification, the adherend is a counterpart to which the adhesive sheet is bonded.
As used herein, (meth) acrylic acid includes acrylic acid and methacrylic acid. The monomer means an ethylenically unsaturated group-containing monomer.
本明細書において、特に明記しない限り、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定によって求めたポリスチレン換算値であり、後記［実施例］の項に記載の方法にて測定することができる。 In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-converted values determined by gel permeation chromatography (GPC) measurement, and are described later in [Examples]. It can be measured by the method described.
本発明の粘着剤は、粘着性樹脂（Ａ）、およびビスマス系レーザ発色剤（Ｂ）を含む。
本発明の粘着剤は、塗工により粘着層を形成し、基材、および粘着層を備えた粘着シートとして使用することが好ましい。
The pressure-sensitive adhesive of the present invention contains a pressure-sensitive resin (A) and a bismuth-based laser color former (B).
The pressure-sensitive adhesive of the present invention is preferably used as a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer by forming a pressure-sensitive adhesive layer by coating.
本発明の粘着剤は、ビスマス系レーザ発色剤（Ｂ）を使用しているため、粘着層が着色し難く透明性が高い。これによりラベル用途に使用した場合、ラベル全体が粘着層に由来する着色を有さないため、例えば透明ラベル、生鮮食品ラベルに使用した場合、被着体である商品の商品性に悪影響を与えない。さらに、レーザ照射による発色が良好であるため印字部と非印字部のコントラストが高く、印字部の視認性が高い。 Since the pressure-sensitive adhesive of the present invention uses the bismuth-based laser color former (B), the pressure-sensitive adhesive layer is hardly colored and has high transparency. As a result, when used for labeling, the entire label does not have a color derived from the adhesive layer. For example, when used for a transparent label or a fresh food label, it does not adversely affect the merchantability of the product that is the adherend. . Further, since the color developed by laser irradiation is good, the contrast between the printed portion and the non-printed portion is high, and the visibility of the printed portion is high.
（粘着性樹脂（Ａ））
粘着性樹脂（Ａ）は、粘着剤用途に使用できる樹脂であり粘着層形成後には、粘着層に適度な粘着性（タック）が得られる。また、粘着性樹脂（Ａ）は、ガラス転移温度（Ｔｇ）０℃以下が好ましく、−１０℃以下がより好ましく、−２０℃以下がさらに好ましい。Ｔｇは、粘着性樹脂（Ａ）を構成するモノマーのホモポリマーのガラス転移温度を用いて、ＦＯＸの式により求めることができる。モノマーのＴｇは、ポリマーハンドブック等既知の数値を使用できる。なお、モノマーのＴｇが不明である場合、粘着性樹脂（Ａ）のＴｇは、ＤＳＣで求めることができる。
(Adhesive resin (A))
The pressure-sensitive adhesive resin (A) is a resin that can be used for pressure-sensitive adhesives. After the pressure-sensitive adhesive layer is formed, moderate pressure-sensitive adhesiveness (tack) is obtained in the pressure-sensitive adhesive layer. The adhesive resin (A) preferably has a glass transition temperature (Tg) of 0 ° C. or lower, more preferably −10 ° C. or lower, and further preferably −20 ° C. or lower. Tg can be determined by the FOX equation using the glass transition temperature of the homopolymer of the monomer constituting the adhesive resin (A). As the monomer Tg, a known value such as a polymer handbook can be used. In addition, when Tg of a monomer is unknown, Tg of adhesive resin (A) can be calculated | required by DSC.
粘着性樹脂（Ａ）は、例えばアクリル系樹脂、ウレタン系樹脂が挙げられる。これら中でもアクリル系樹脂が好ましい。 Examples of the adhesive resin (A) include acrylic resins and urethane resins. Among these, acrylic resins are preferable.
アクリル系樹脂は、（メタ）アクリル酸エステルを主成分として重合した樹脂である。（メタ）アクリル酸エステル以外のモノマーとして反応性官能基含有モノマー、その他モノマーを使用できる。
（メタ）アクリル酸エステルは、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（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、ｉ−ペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレートが挙げられる。
反応性官能基含有モノマーの中で水酸基含有モノマーは、例えば、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等が挙げられる。
反応性官能基含有モノマーの中でカルボキシル基含有モノマーは、例えば（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸、ビニル安息香酸、クロトン酸が挙げられる。
その他モノマーは、例えば、アクリルアミド、酢酸ビニル、スチレン、プロピオン酸ビニルが挙げられる。
The acrylic resin is a resin obtained by polymerizing (meth) acrylic acid ester as a main component. As monomers other than (meth) acrylic acid esters, reactive functional group-containing monomers and other monomers can be used.
(Meth) acrylic acid ester is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl ( Examples include meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, i-pentyl (meth) acrylate, neopentyl (meth) acrylate, and n-hexyl (meth) acrylate.
Examples of the hydroxyl group-containing monomer among the reactive functional group-containing monomers include 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
Among the reactive functional group-containing monomers, examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, vinyl benzoic acid, and crotonic acid.
Examples of other monomers include acrylamide, vinyl acetate, styrene, and vinyl propionate.
これらのモノマーは、単独または２種類以上を使用できる。 These monomers can be used alone or in combination of two or more.
アクリル系樹脂の合成は、例えば、溶液重合、乳化重合、塊状重合から適宜選択できるところ、反応制御が容易な溶液重合が好ましい。
溶液重合に使用する溶剤は、例えば、エステル（例えば酢酸エチル、酢酸ブチル）、炭化水素（例えばｎ−ブタン、シクロヘキサン、トルエン、ベンゼン）、ケトン（例えばアセトン、メチルエチルケトン、メチルイソブチルケトン）などが挙げられる。
The synthesis of the acrylic resin can be appropriately selected from, for example, solution polymerization, emulsion polymerization, and bulk polymerization. Solution polymerization with easy reaction control is preferable.
Examples of the solvent used for the solution polymerization include esters (for example, ethyl acetate and butyl acetate), hydrocarbons (for example, n-butane, cyclohexane, toluene, benzene), ketones (for example, acetone, methyl ethyl ketone, and methyl isobutyl ketone). .
溶剤は、単独または２種類以上を使用できる。 The solvent can be used alone or in combination of two or more.
アクリル系樹脂の合成に使用する重合開始剤は、過酸化物、アゾ化合物が好ましい。
過酸化物は、例えば、ベンゾイルパーオキシド、ジ−ｔ−ブチルパーオキシド、ラウリルパーオキシドが挙げられる。
アゾ化合物は、例えば、アゾビスイソブチロニトリル、２，２'−アゾビス（２−メチルプロピオニトリル）、２，２'−アゾビス（２，４−ジメチルバレロニトリルなどが挙げられる。
The polymerization initiator used for the synthesis of the acrylic resin is preferably a peroxide or an azo compound.
Examples of the peroxide include benzoyl peroxide, di-t-butyl peroxide, and lauryl peroxide.
Examples of the azo compound include azobisisobutyronitrile, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like.
重合開始剤は、単独または２種類以上を使用できる。 The polymerization initiator can be used alone or in combination of two or more.
重合開始剤は、モノマー全量に対して０．０１〜０．５質量部使用することが好ましい。 The polymerization initiator is preferably used in an amount of 0.01 to 0.5 parts by mass with respect to the total amount of monomers.
アクリル系樹脂の重量平均分子量は、３０万〜１３０万が好ましく、４０万〜１００万がより好ましく、５０万〜８０万がさらに好ましい。重量平均分子量が３０万以上であれば、粘着層の凝集力がより向上し、連続塗工後に粘着シートを巻き取った塗工ロールがタケノコ状にズレ難い。また、１３０万以下であれば、粘着層の表面平滑性がより向上しラベルの商品性が向上する。重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により得られるポリスチレン換算の値である。 The weight average molecular weight of the acrylic resin is preferably 300,000 to 1,300,000, more preferably 400,000 to 1,000,000, and even more preferably 500,000 to 800,000. If the weight average molecular weight is 300,000 or more, the cohesive force of the pressure-sensitive adhesive layer is further improved, and the coating roll obtained by winding the pressure-sensitive adhesive sheet after continuous coating is difficult to shift into a bamboo shoot shape. Moreover, if it is 1.3 million or less, the surface smoothness of an adhesion layer will improve more and the commercial property of a label will improve. The weight average molecular weight is a value in terms of polystyrene obtained by GPC (gel permeation chromatography).
粘着性樹脂（Ａ）は、単独または２種類以上を使用できる。 An adhesive resin (A) can use single or 2 types or more.
本発明では、硬化剤を使用できる。硬化剤は任意成分であるが、粘着性樹脂が反応官能基を有する場合、当該反応性官能基と反応可能な硬化剤を使用することができる。
粘着性樹脂（Ａ）が水酸基を有する場合、硬化剤は、例えば、イソシアネート硬化剤が挙げられる。また粘着性樹脂（Ａ）がカルボキシル基を有する場合、硬化剤は、例えば、エポキシ硬化剤、キレート硬化剤、アジリジン硬化剤が挙げられる。
In the present invention, a curing agent can be used. The curing agent is an optional component, but when the adhesive resin has a reactive functional group, a curing agent capable of reacting with the reactive functional group can be used.
When the adhesive resin (A) has a hydroxyl group, examples of the curing agent include an isocyanate curing agent. When the adhesive resin (A) has a carboxyl group, examples of the curing agent include an epoxy curing agent, a chelate curing agent, and an aziridine curing agent.
硬化剤は、単独または２種類以上を使用できる。 The curing agent can be used alone or in combination of two or more.
硬化剤は、粘着性樹脂（Ａ）１００質量部に対して、０．１〜１０質量部を配合することが好ましい。 It is preferable that 0.1-10 mass parts is mix | blended with respect to 100 mass parts of adhesive resins (A) for a hardening | curing agent.
（ビスマス系レーザ発色剤（Ｂ））
ビスマス系レーザ発色剤（Ｂ）は、ビスマス酸化物が好ましい。ビスマス系レーザ発色剤（Ｂ）は、レーザ光を吸収し発熱することで周りの粘着性樹脂（Ａ）を炭化させる。ビスマス系レーザ発色剤（Ｂ）を使用すると、従来のレーザ発色剤では得られなかった印字後のコントラストが得られ、粘着層の着色が抑制できる。なお、前記炭化部分が、レーザ発色部（印字部）である。
(Bismuth laser color former (B))
The bismuth-based laser color former (B) is preferably a bismuth oxide. The bismuth-based laser color former (B) carbonizes the surrounding adhesive resin (A) by absorbing laser light and generating heat. When the bismuth laser color former (B) is used, contrast after printing that cannot be obtained with the conventional laser color former can be obtained, and coloring of the adhesive layer can be suppressed. The carbonized portion is a laser coloring portion (printing portion).
ビスマス酸化物は、例えば、三酸化ビスマス（Ｂｉ2Ｏ3）が挙げられる。 Examples of the bismuth oxide include bismuth trioxide (Bi 2 O 3 ).
ビスマス系レーザ発色剤（Ｂ）のＤ５０平均粒子径は、０．０５〜５μｍが好ましく、０．１〜３μｍがより好ましく、０．３〜１．５μｍがさらに好ましい。０．０５μｍ以上になるとビスマス系レーザ発色剤（Ｂ）の粒子の比表面が大きくなりレーザ光を吸収し発熱し易くなるため印字精度がより向上する。一方、５μｍ以下になると粘着層の着色をより抑制できる。なお、ビスマス系レーザ発色剤（Ｂ）は、粘着性樹脂（Ａ）と単純に配合すると凝集し易いため、分散処理を行うことが好ましい。そのためビスマス系レーザ発色剤（Ｂ）のＤ５０平均粒子径は、粘着剤に配合した後の分散粒子径である。Ｄ５０平均粒子径は、マイクロトラック粒度分布測定装置ＵＰＡ２５０(日機装社製)で測定した体積平均粒子径の積算値が５０％の粒度である。 The D50 average particle size of the bismuth-based laser color former (B) is preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm, and still more preferably 0.3 to 1.5 μm. When the thickness is 0.05 μm or more, the specific surface of the particles of the bismuth-based laser color former (B) becomes large and the laser beam is absorbed and heat is easily generated, so that the printing accuracy is further improved. On the other hand, when it becomes 5 micrometers or less, coloring of the adhesion layer can be suppressed more. The bismuth-based laser color former (B) is preferably a dispersion treatment because it easily aggregates when blended with the adhesive resin (A). Therefore, the D50 average particle size of the bismuth-based laser color former (B) is the dispersed particle size after blending with the pressure-sensitive adhesive. The D50 average particle size is a particle size in which the integrated value of the volume average particle size measured with a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso Co., Ltd.) is 50%.
ビスマス系レーザ発色剤（Ｂ）は、粘着性樹脂（Ａ）１００質量部に対して、０．１〜５量部を配合することが好ましく、０．３〜４質量部がより好ましく、０．５〜３質量部がより好ましい。０．１質量部配合すると印字後のコントラストがより向上する。また、５質量部以下配合すると粘着層の凝集力および粘着力がより向上し、コストを抑制できる。ビスマス系レーザ発色剤（Ｂ）を適量配合すると印字後のコントラストがより向上し、粘着層の着色がより抑制できる。 The bismuth-based laser color former (B) is preferably blended in an amount of 0.1 to 5 parts by weight, more preferably 0.3 to 4 parts by weight, based on 100 parts by weight of the adhesive resin (A). 5-3 mass parts is more preferable. When 0.1 part by mass is blended, the contrast after printing is further improved. Moreover, when 5 mass parts or less are mix | blended, the cohesion force and adhesive force of an adhesion layer will improve more, and cost can be suppressed. When an appropriate amount of the bismuth-based laser color former (B) is blended, the contrast after printing is further improved, and coloring of the adhesive layer can be further suppressed.
粘着剤には、本発明の課題を解決できる範囲内であれば、ビスマス系レーザ発色剤（Ｂ）以外のその他レーザ発色剤を併用できる。
その他レーザ発色剤は、例えば三酸化モリブデン、リン酸銅等が挙げられる。
In the pressure-sensitive adhesive, other laser color formers other than the bismuth-based laser color former (B) can be used in combination as long as the problems of the present invention can be solved.
Other laser color formers include, for example, molybdenum trioxide, copper phosphate, and the like.
粘着剤は、さらに無機化合物を配合できる。ビスマス系レーザ発色剤（Ｂ）と無機化合物を併用すると印字後のコントラストがより向上する場合がある。前記無機化合物は、レーザ発色剤以外の、金属酸化物、無機塩、金属、金属水酸化物等が好ましい。金属酸化物は、例えば、シリカ、酸化チタン、アルミナ、酸化鉄、酸化マグネシウム、酸化亜鉛、酸化コバルト、酸化鉛、酸化スズ、酸化アンチモン、酸化インジウム、酸化マンガン、酸化ニッケル、酸化ネオジム、酸化銅、酸化パラジウム、酸化ランタン、合成及び天然ゼオライト；マイカ、モンモリロナイト、スクメタイト、タルク、クレー等の複合金属酸化物が挙げられる。 The pressure-sensitive adhesive can further contain an inorganic compound. When the bismuth laser color former (B) and an inorganic compound are used in combination, the contrast after printing may be further improved. The inorganic compound is preferably a metal oxide, inorganic salt, metal, metal hydroxide or the like other than the laser color former. Examples of the metal oxide include silica, titanium oxide, alumina, iron oxide, magnesium oxide, zinc oxide, cobalt oxide, lead oxide, tin oxide, antimony oxide, indium oxide, manganese oxide, nickel oxide, neodymium oxide, copper oxide, Examples include palladium oxide, lanthanum oxide, synthetic and natural zeolites; and composite metal oxides such as mica, montmorillonite, scumite, talc, and clay.
無機塩は、例えば、炭酸カルシウム、炭酸銅、炭酸ニッケル、炭酸マンガン、炭酸コバルト、炭酸ランタン、硝酸マグネシウム、硝酸マンガン、硝酸鉄、硝酸カドミウム、硝酸亜鉛、硝酸コバルト、硝酸鉛、硝酸ニッケル、硝酸銅、硝酸パラジウム、硝酸ランタン、酢酸マグネシウム、酢酸マンガン、酢酸カドミウム、酢酸亜鉛、酢酸コバルト、酢酸鉛、酢酸ニッケル、酢酸銅、酢酸パラジウム等が挙げられる。
金属単体は、例えば、鉄、亜鉛、スズ、ニッケル、銅、銀、金等が挙げられる。水酸化物として、水酸化アルミニウム、水酸化マグネシウム、水酸化亜鉛、水酸化アンチモン、水酸化コバルト、水酸化ニッケル、水酸化ネオジム、水酸化鉄、水酸化ランタン等が挙げられる。
Inorganic salts include, for example, calcium carbonate, copper carbonate, nickel carbonate, manganese carbonate, cobalt carbonate, lanthanum carbonate, magnesium nitrate, manganese nitrate, iron nitrate, cadmium nitrate, zinc nitrate, cobalt nitrate, lead nitrate, nickel nitrate, copper nitrate Palladium nitrate, lanthanum nitrate, magnesium acetate, manganese acetate, cadmium acetate, zinc acetate, cobalt acetate, lead acetate, nickel acetate, copper acetate, palladium acetate and the like.
Examples of the metal simple substance include iron, zinc, tin, nickel, copper, silver, and gold. Examples of the hydroxide include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, antimony hydroxide, cobalt hydroxide, nickel hydroxide, neodymium hydroxide, iron hydroxide, and lanthanum hydroxide.
粘着剤には、さらに粘着付与樹脂を配合できる。粘着付与樹脂を含むと粘着力が向上する。
粘着付与樹脂は、ロジン系樹脂、テルペン系樹脂、芳香族系石油樹脂、脂肪族系石油樹脂等が好ましい。
ロジン系樹脂は、例えば、天然ロジン、ロジンエステル、水添ロジン、水添ロジンエステル、重合ロジン、重合ロジンエステル、不均化ロジン、不均化ロジンエステルが挙げられる。
テルペン系樹脂は、例えば、α−ピネン樹脂、β−ピネン樹脂、テルペンフェノール樹脂、水添テルペンフェノール樹脂等が挙げられる。
芳香族系石油樹脂は、例えば、スチレンオリゴマー、α−メチルスチレン／スチレン共重合体等が挙げられる。
粘着付与樹脂の軟化点は６０℃〜１７０℃が好ましい。
A tackifier resin can be further mix | blended with an adhesive. When tackifying resin is included, the adhesive strength is improved.
The tackifying resin is preferably a rosin resin, a terpene resin, an aromatic petroleum resin, an aliphatic petroleum resin, or the like.
Examples of the rosin resin include natural rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, disproportionated rosin, and disproportionated rosin ester.
Examples of the terpene resin include α-pinene resin, β-pinene resin, terpene phenol resin, hydrogenated terpene phenol resin, and the like.
Examples of aromatic petroleum resins include styrene oligomers and α-methylstyrene / styrene copolymers.
The softening point of the tackifying resin is preferably 60 ° C to 170 ° C.
粘着付与樹脂は、粘着性樹脂（Ａ）１００質量部に対して３〜３０質量部配合することが好ましい。粘着付与樹脂を適量配合すると粘着力がより向上する。 It is preferable that 3-30 mass parts of tackifying resin is mix | blended with respect to 100 mass parts of adhesive resin (A). When an appropriate amount of tackifying resin is blended, the adhesive strength is further improved.
粘着剤には、本発明の課題を解決できる範囲内であれば、その他添加剤を配合できる。
その他添加剤は、例えば、顔料、染料、充填剤、希釈剤、老化防止剤、分散安定剤、重合禁止剤、紫外線吸収剤、紫外線安定剤等が挙げられる。他の添加剤は、単独または２種類以上を使用できる。また、添加剤の添加量は、所望する物性が得られる量とすればよく、特に限定されない。
If it is in the range which can solve the subject of this invention, other additives can be mix | blended with an adhesive.
Examples of other additives include pigments, dyes, fillers, diluents, anti-aging agents, dispersion stabilizers, polymerization inhibitors, ultraviolet absorbers, and ultraviolet stabilizers. Other additives can be used alone or in combination of two or more. Moreover, the addition amount of an additive should just be taken as the quantity from which the desired physical property is obtained, and is not specifically limited.
（溶剤）
粘着剤には、溶液重合で使用する他に必要に応じて、既に説明した溶剤を含むことができる。
(solvent)
The pressure-sensitive adhesive can contain the solvent already described, if necessary, in addition to the use in solution polymerization.
本発明の粘着剤は、粘着性樹脂（Ａ）、およびビスマス系レーザ発色剤（Ｂ）を配合し分散処理を行い製造することが好ましい。これによりビスマス系レーザ発色剤（Ｂ）を粘着剤中に均一に分散し易くなく。また、粘着性樹脂（Ａ）の一部と、ビスマス系レーザ発色剤（Ｂ）とを予め分散処理した分散体を、残りの粘着性樹脂（Ａ）に混合することもできる。分散処理により必要とするレーザ発色部の大きさに合わせて、ビスマス系レーザ発色剤（Ｂ）の分散粒子径を適宜調整できる。 The pressure-sensitive adhesive of the present invention is preferably produced by blending a pressure-sensitive resin (A) and a bismuth-based laser color former (B) and subjecting it to a dispersion treatment. As a result, the bismuth-based laser color former (B) is not easily dispersed uniformly in the adhesive. Further, a dispersion obtained by previously dispersing a part of the adhesive resin (A) and the bismuth-based laser color former (B) can be mixed with the remaining adhesive resin (A). The dispersed particle diameter of the bismuth-based laser color former (B) can be appropriately adjusted according to the size of the laser color development portion required by the dispersion treatment.
分散処理は、公知の分散機を使用できる。分散機は、例えば、ボールミル、ビーズミル等が挙げられる。 A known disperser can be used for the dispersion treatment. Examples of the disperser include a ball mill and a bead mill.
本発明の粘着シートは、基材と、粘着剤を含む粘着層とを備えることが好ましい。粘着層は、粘着剤を塗工することで形成できる。粘着層の基材と接していない面は、通常、粘着シートを使用する直前まで剥離性シートを貼り付けて異物の付着を防止する。
粘着シートは、例えば、基材に粘着剤を塗工、乾燥することで粘着層を形成して作製する。また、剥離性シートに粘着剤を塗工、乾燥することで粘着層を形成し、基材を貼り合わせて作製する。また、剥離性シートに粘着剤を塗工、乾燥することで粘着層を形成し、さらに他の剥離性シートを貼り合わせて作製することもできる。基材を使用しない粘着シートをキャスト粘着シートという。
It is preferable that the adhesive sheet of this invention is equipped with a base material and the adhesion layer containing an adhesive. The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive. The surface of the pressure-sensitive adhesive layer that is not in contact with the base material is usually attached with a peelable sheet until just before the pressure-sensitive adhesive sheet is used to prevent foreign matter from adhering.
The pressure-sensitive adhesive sheet is produced, for example, by forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive to a substrate and drying it. Moreover, a pressure-sensitive adhesive layer is formed by applying and drying a pressure-sensitive adhesive on a peelable sheet, and a base material is bonded thereto. Alternatively, the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive to the peelable sheet and drying, and further bonding another peelable sheet. An adhesive sheet that does not use a substrate is called a cast adhesive sheet.
粘着剤は、塗工の際、適当な溶媒を使用して粘度を調整することができる。また粘着剤を加熱して粘度を調整することもできる。 The pressure-sensitive adhesive can be adjusted in viscosity by using an appropriate solvent during coating. The viscosity can also be adjusted by heating the pressure-sensitive adhesive.
粘着層は、粘着剤を公知の方法で塗工し、乾燥して形成する。塗工方法は、例えば、マイヤーバー、アプリケーター、刷毛、スプレー、ローラー、グラビアコーター、ダイコーター、リップコーター、コンマコーター、ナイフコーター、リバースコ−ター、スピンコーターが挙げられる。乾燥方法は、例えば、熱風乾燥、赤外線や減圧法が挙げられる。乾燥温度は、通常６０〜１６０℃程度である。 The pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive by a known method and drying it. Examples of the coating method include Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, and spin coater. Examples of the drying method include hot air drying, infrared rays, and a decompression method. The drying temperature is usually about 60 to 160 ° C.
粘着層の厚さは、５〜１５０μｍが好ましく、１０〜５０μｍがより好ましい。５〜１５０μｍに調整することで適度な粘着力が得られる。 The thickness of the adhesive layer is preferably 5 to 150 μm, and more preferably 10 to 50 μm. By adjusting to 5 to 150 μm, an appropriate adhesive strength can be obtained.
基材は、例えば、プラスチック、紙、金属箔等のシートまたは板材が挙げられる。
前記プラスチックは、例えば、ポリエチレン、ポリプロピレン、ポリエステル（例えば、ポリエチレンテレフタレート（ＰＥＴ））、ポリスチレン、ポリ塩化ビニル、ポリカーボネート、セロファン等が挙げられる。
Examples of the substrate include sheets or plate materials such as plastic, paper, and metal foil.
Examples of the plastic include polyethylene, polypropylene, polyester (for example, polyethylene terephthalate (PET)), polystyrene, polyvinyl chloride, polycarbonate, cellophane, and the like.
基材の厚さは、５〜２００μｍ程度である。 The thickness of the substrate is about 5 to 200 μm.
剥離性シートは、通常、フィルムまたは紙基材に、シリコーン化合物やフッ素化合物等から形成された公知の剥離層が形成されている。
剥離性シートの厚さは、通常１０〜２００μｍ程度である。
In the release sheet, a known release layer formed from a silicone compound, a fluorine compound, or the like is usually formed on a film or paper substrate.
The thickness of the peelable sheet is usually about 10 to 200 μm.
本発明の粘着シートは、一般用、工業用に使用されるフィルムラベル、紙ラベル等の粘着加工品用途に好適に使用できる。 The pressure-sensitive adhesive sheet of the present invention can be suitably used for pressure-sensitive adhesive products such as film labels and paper labels used for general and industrial purposes.
以下、合成例、本発明に係る実施例、および比較例について説明する。しかし、本発明は、実施例に限定されないことはいうまでもない。なお、以下の記載において、特に明記しない限り、「部」は「質量部」を意味し、「％」は「質量％」を意味するものとする。表中の配合量は、質量部である。 Hereinafter, synthesis examples, examples according to the present invention, and comparative examples will be described. However, it goes without saying that the present invention is not limited to the examples. In the following description, “part” means “part by mass” and “%” means “mass%” unless otherwise specified. The compounding quantity in a table | surface is a mass part.
[実施例１]
反応槽、攪拌器機、温度計、滴下漏斗、触媒槽、還流器冷却管を備えた重合装置に、窒素雰囲気下、アクリル酸ブチル３０部、アクリル酸２-エチルヘキシル６９部、アクリル酸２−ヒドロキシエチル０．７部、アクリル酸０．２部、２，２'−アゾビスイソブチロニトリル０．１部、酢酸エチル６０部を仕込み、反応槽を撹拌しながら加熱を行った。反応開始を確認後、還流下で７時間反応を行った。反応終了後、冷却し、酢酸エチルで希釈し不揮発分を４５％に調整して重量平均分子量が６５万のアクリル樹脂（Ａ−１）溶液を得た。得られたアクリル樹脂（Ａ−１）溶液中のアクリル樹脂（Ａ−１）１００部に対して、ロジン樹脂（パインクリスタルＫＥ−３５９、ロジンエステル、荒川化学工業社製）を２５部配合し、混合した。
次いで前記混合液中のアクリル樹脂（Ａ−１）１００部に対して、平均粒子径が１．０μｍの市販三酸化ビスマス（三酸化モリブデン含有量９９％、三酸化ネオジム１％）を１．０部添加し、ビーズミル分散機で分散処理を行った。次いで得られた混合液中のアクリル樹脂（Ａ−１）１００部に対して、タケネートＤ−１１０Ｎ（キシリレンジイソシアネートのトリメチロールプロパンアダクト体、三井化学社製）を不揮発分換算で０．８部を配合して、粘度３０００ｍＰａ・ｓ、不揮発分４０％の粘着剤を得た。粘着剤中の三酸化ビスマスのＤ５０平均粒子径を測定したところ１．４μｍであった。粘度は２５℃、Ｂ型粘度計（♯３ローター．１２ｒｐｍ）で測定した値である。
[Example 1]
In a polymerization apparatus equipped with a reaction vessel, a stirrer, a thermometer, a dropping funnel, a catalyst vessel, and a reflux condenser, in a nitrogen atmosphere, 30 parts of butyl acrylate, 69 parts of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate 0.7 parts, 0.2 part of acrylic acid, 0.1 part of 2,2′-azobisisobutyronitrile and 60 parts of ethyl acetate were charged, and the reaction vessel was heated while stirring. After confirming the start of the reaction, the reaction was carried out for 7 hours under reflux. After completion of the reaction, the reaction mixture was cooled and diluted with ethyl acetate to adjust the nonvolatile content to 45% to obtain an acrylic resin (A-1) solution having a weight average molecular weight of 650,000. For 100 parts of the acrylic resin (A-1) in the resulting acrylic resin (A-1) solution, 25 parts of rosin resin (Pine Crystal KE-359, rosin ester, manufactured by Arakawa Chemical Industries, Ltd.) Mixed.
Next, 1.0 part of commercial bismuth trioxide (99% molybdenum trioxide content, 1% neodymium trioxide) having an average particle size of 1.0 μm per 100 parts of the acrylic resin (A-1) in the mixed solution. A part was added and the dispersion process was performed with a bead mill disperser. Next, 0.8 parts of Takenate D-110N (trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd.) with respect to 100 parts of the acrylic resin (A-1) in the obtained mixed liquid was converted into non-volatile content. Was added to obtain an adhesive having a viscosity of 3000 mPa · s and a nonvolatile content of 40%. It was 1.4 micrometers when D50 average particle diameter of bismuth trioxide in an adhesive was measured. The viscosity is a value measured with a B-type viscometer (# 3 rotor, 12 rpm) at 25 ° C.
剥離性シート（厚さ３８μｍ、ポリエチレンテレフタレート製）の剥離面に得られた粘着剤を乾燥後の粘着剤層の厚みが２０μｍになるように塗工した。次いで、１００℃で２分間乾燥を行い、粘着層を形成した。この粘着層上に、基材として厚さ５０μｍのポリエチレンテレフタレートフィルム（ＰＥＴフィルム、ルミラーＴ−６０：東レ社製）を貼着して、粘着シートを得た。２３℃で７日間養生した後、下記評価を行った。 The pressure-sensitive adhesive obtained on the release surface of the peelable sheet (thickness 38 μm, made of polyethylene terephthalate) was applied so that the thickness of the pressure-sensitive adhesive layer after drying was 20 μm. Subsequently, it dried at 100 degreeC for 2 minute (s), and formed the adhesion layer. On this adhesive layer, a polyethylene terephthalate film (PET film, Lumirror T-60: manufactured by Toray Industries, Inc.) having a thickness of 50 μm was stuck as a substrate to obtain an adhesive sheet. After curing at 23 ° C. for 7 days, the following evaluation was performed.
［分子量の測定］
重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）法により測定した。測定条件は以下の通りである。なお、ＭｗおよびＭｎはいずれも、ポリスチレン換算値である。
装置：ＬＣ−ＧＰＣシステム「Ｐｒｏｍｉｎｅｎｃｅ」（島津製作所社製）、
カラム：ＧＭＨＸＬ４本（東ソー社製）、ＨＸＬ-Ｈ１本（東ソー社製）を直列に連結、
検出器：示差屈折率検出器、
移動相溶媒：テトラヒドロフラン（ＴＨＦ）、
カラム温度：４０℃、
流量：１．０ｍｌ／ｍｉｎ、
試料濃度：０．０２％、
試料注入量：１００μＬ
[Measurement of molecular weight]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method. The measurement conditions are as follows. Mw and Mn are both polystyrene equivalent values.
Apparatus: LC-GPC system “Prominence” (manufactured by Shimadzu Corporation),
Column: 4 GMHXL (Tosoh Corp.), 1 HXL-H (Tosoh Corp.) connected in series,
Detector: differential refractive index detector,
Mobile phase solvent: tetrahydrofuran (THF),
Column temperature: 40 ° C
Flow rate: 1.0 ml / min,
Sample concentration: 0.02%
Sample injection volume: 100 μL
（実施例２〜６、比較例１〜３）
実施例１の配合を表１に記載した通りに変更した以外は、実施例１と同様に行い、それぞれ実施例２〜６、比較例１〜３の粘着剤および粘着シートを得た。実施例４に使用した酸化チタン分散体（「マルチラックＳ−１６１」、トーヨーケム社製）は、アクリル樹脂１００部に対して、酸化チタンが０．５部になるようにイソシアネート硬化剤と同時に配合した。なお、三酸化ビスマスは、分散条件を適宜調整し分散粒子径が異なる三酸化ビスマスを作製して使用した。
(Examples 2-6, Comparative Examples 1-3)
Except having changed the mixing | blending of Example 1 as having described in Table 1, it carried out similarly to Example 1 and obtained the adhesive and adhesive sheet of Examples 2-6 and Comparative Examples 1-3, respectively. The titanium oxide dispersion used in Example 4 (“Multilac S-161”, manufactured by Toyochem Co., Ltd.) was blended with the isocyanate curing agent so that the titanium oxide was 0.5 parts with respect to 100 parts of the acrylic resin. did. In addition, bismuth trioxide was used by preparing bismuth trioxide having different dispersion particle sizes by appropriately adjusting dispersion conditions.
[実施例７]
撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコに窒素雰囲気下、クラレポリオールＰ−１０１０（２官能ポリエステルポリオール、クラレ社製）８１重量部、サンニックスＧＰ３０００（３官能ポリエーテルポリオール、三洋化成工業社製）１０１ｇ、デスモジュールＨ（ヘキサメチレンジイソシアネート、住化コベストロウレタン社製）１９重量部、トルエン１３４重量部、触媒としてジブチル錫ジラウレート０．０５重量部、２−エチルヘキサン酸錫０．０２重量部を仕込み、９０℃まで徐々に昇温し、９０℃で２時間反応を行った。次いで、サンプリングを行い、ＩＲで残存イソシアネート基の消滅を確認した上で冷却し反応を終了した。次いでトルエンで適宜添加して、不揮発分６０％、かつ重量平均分子量が１０万のウレタン樹脂（Ａ−２）溶液を得た。ウレタン樹脂溶液（Ａ−２）の粘度は３，３００ｍＰａ・ｓであった。
次いで、ウレタン樹脂（Ａ−２）溶液中のウレタン樹脂（Ａ−２）１００質量部に対して上記市販三酸化ビスマスを１．０部添加し、ビーズミル分散機で分散処理を行った。次いで得られた混合液中のウレタン樹脂（Ａ−２）１００部に対して、デュラネート３０１−７５Ｅ（ヘキサメチレンジイソシアネートのトリメチレンプロパンアダクト体、旭化成社製）を不揮発分換算で３．０部を配合し、粘着剤を得た。粘着剤中の三酸化ビスマスのＤ５０平均粒子径を測定したところ１．４μｍであった。さらに実施例１と同様に行い粘着シートを得た。
[Example 7]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, under a nitrogen atmosphere, 81 parts by weight of Kuraray polyol P-1010 (bifunctional polyester polyol, manufactured by Kuraray), Sanix GP3000 ( 101 g of trifunctional polyether polyol (manufactured by Sanyo Chemical Industries), 19 parts by weight of Desmodur H (hexamethylene diisocyanate, manufactured by Sumika Cobestrourethane), 134 parts by weight of toluene, 0.05 part by weight of dibutyltin dilaurate as a catalyst, 0.02 part by weight of tin 2-ethylhexanoate was charged, the temperature was gradually raised to 90 ° C., and the reaction was performed at 90 ° C. for 2 hours. Next, sampling was performed, and after the disappearance of the remaining isocyanate groups was confirmed by IR, the reaction was terminated by cooling. Subsequently, toluene was added as appropriate to obtain a urethane resin (A-2) solution having a nonvolatile content of 60% and a weight average molecular weight of 100,000. The viscosity of the urethane resin solution (A-2) was 3,300 mPa · s.
Next, 1.0 part of the above-mentioned commercial bismuth trioxide was added to 100 parts by mass of the urethane resin (A-2) in the urethane resin (A-2) solution, and dispersion treatment was performed with a bead mill disperser. Next, with respect to 100 parts of the urethane resin (A-2) in the obtained mixed liquid, 3.0 parts of Duranate 301-75E (trimethylenepropane adduct of hexamethylene diisocyanate, manufactured by Asahi Kasei Co., Ltd.) in terms of nonvolatile content was added. Blended to obtain an adhesive. It was 1.4 micrometers when D50 average particle diameter of bismuth trioxide in an adhesive was measured. Furthermore, it carried out similarly to Example 1 and obtained the adhesive sheet.
［評価項目および評価方法］
評価項目および評価方法は、以下の通りである。
[Evaluation items and methods]
Evaluation items and evaluation methods are as follows.
（視認性）
得られた粘着シートを幅１００ｍｍ・長さ１００ｍｍの大きさに準備し、測定試料とした。次いで、２３℃−５０％ＲＨの雰囲気下で、バナジウム酸イットリウム結晶を用いたＱスイッチパルス発振レーザ光増幅光波（ＹＶＯ社製 ｉ−ＭａｒｋｅｒＬＴ−０１０ 波長約１０６４ｎｍ）を、測定試料の基材側から、基材面に垂直にレーザ光が当たるよう設定し、基材面に平行にレーザ光を走査し、レーザ発色部を作製した。照射条件は、スイッチ周波数３００００Ｈｚ，出力４６％，描画速度２０００ｍｍ／Ｓで行った。照射により発現する黒色度の鮮明性を目視判定した。評価基準は以下の通りである。
Ａ：鮮明でコントラストの高い黒色度が得られた。良好。
Ｂ：必要な黒色度は有するがコントラストは、Ａよりやや低い。実用域。
Ｃ：黒色度が不足し、コントラストが低い。実用不可。
(Visibility)
The obtained adhesive sheet was prepared to have a width of 100 mm and a length of 100 mm, and used as a measurement sample. Next, under an atmosphere of 23 ° C.-50% RH, a Q-switched pulsed laser light amplification light wave using an yttrium vanadate crystal (i-MarkerLT-010, a wavelength of about 1064 nm manufactured by YVO) was applied from the substrate side of the measurement sample. The laser beam was set to be perpendicular to the substrate surface, and the laser beam was scanned in parallel to the substrate surface to produce a laser coloring portion. The irradiation conditions were a switch frequency of 30000 Hz, an output of 46%, and a drawing speed of 2000 mm / S. Visibility of blackness developed by irradiation was visually determined. The evaluation criteria are as follows.
A: A clear and high contrast blackness was obtained. Good.
B: Necessary blackness is obtained, but contrast is slightly lower than A. Practical area.
C: Blackness is insufficient and contrast is low. Not practical.
（透明性）
得られた粘着シートを幅１００ｍｍ・長さ１００ｍｍの大きさに準備し、測定試料とした。次いで、２３℃−５０％ＲＨの雰囲気下で、測定試料から剥離性シートを剥がし、露出した粘着層の透明性を目視で評価した。評価基準は以下の通りである。
○：粘着層に着色がない。良好。
△：粘着層にわずかに黄色の着色があった。実用域。
×：粘着層が黄色に着色した。実用不可。
(transparency)
The obtained adhesive sheet was prepared to have a width of 100 mm and a length of 100 mm, and used as a measurement sample. Next, the peelable sheet was peeled off from the measurement sample in an atmosphere of 23 ° C.-50% RH, and the transparency of the exposed adhesive layer was visually evaluated. The evaluation criteria are as follows.
○: The adhesive layer is not colored. Good.
(Triangle | delta): The adhesion layer had slightly yellow coloring. Practical area.
X: The adhesive layer was colored yellow. Not practical.
（印字性）
得られた粘着シートを幅１００ｍｍ・長さ１００ｍｍの大きさに準備し、測定試料とした。前記視認性試験と同様に測定試料の基材側からレーザ照射を行い発色させることでバーコードを印字した。前記印字をバーコード検証機（アイニックス社製ＲＥＡ Ｃｈｅｃｋ ＥＲ）を使用して、アルファベット評点を付与して評価した。
○：Ａ〜Ｃ。 良好。
△：Ｄ。使用可。
×：Ｆ。使用不可。
(Printability)
The obtained adhesive sheet was prepared to have a width of 100 mm and a length of 100 mm, and used as a measurement sample. Similar to the visibility test, a barcode was printed by irradiating a laser beam from the substrate side of the measurement sample to cause color development. The printing was evaluated using a bar code verifier (REA Check ER manufactured by Ainix Co., Ltd.) with an alphabet score.
○: A to C. Good.
Δ: D. Can be used.
X: F. Usage prohibited.
表１の結果より本発明の粘着剤は、印字後のコントラストが良好であり、着色を抑制した粘着層を形成できる粘着剤および粘着シートを提供できる。 From the results shown in Table 1, the pressure-sensitive adhesive of the present invention has a good contrast after printing and can provide a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that can form a pressure-sensitive adhesive layer.
Claims (5)
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