JPH0386703A - Color-developing composition - Google Patents
Color-developing compositionInfo
- Publication number
- JPH0386703A JPH0386703A JP22408789A JP22408789A JPH0386703A JP H0386703 A JPH0386703 A JP H0386703A JP 22408789 A JP22408789 A JP 22408789A JP 22408789 A JP22408789 A JP 22408789A JP H0386703 A JPH0386703 A JP H0386703A
- Authority
- JP
- Japan
- Prior art keywords
- color
- acrylic polymer
- anhydride
- acid anhydride
- parts
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- -1 cyclic acid anhydride Chemical class 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 25
- 150000002118 epoxides Chemical class 0.000 claims abstract description 20
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012970 tertiary amine catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 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 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000001227 electron beam curing Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002601 oligoester Polymers 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-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
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- DKTOWFDVEJQWPF-UHFFFAOYSA-N 1-ethylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC DKTOWFDVEJQWPF-UHFFFAOYSA-N 0.000 description 1
- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical compound ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- VZMLJEYQUZKERO-UHFFFAOYSA-N 2-hydroxy-1-(2-methylphenyl)-2-phenylethanone Chemical compound CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 VZMLJEYQUZKERO-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- BMVWCPGVLSILMU-UHFFFAOYSA-N 5,6-dihydrodibenzo[2,1-b:2',1'-f][7]annulen-11-one Chemical compound C1CC2=CC=CC=C2C(=O)C2=CC=CC=C21 BMVWCPGVLSILMU-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- QNRSQFWYPSFVPW-UHFFFAOYSA-N 5-(4-cyanobutyldiazenyl)pentanenitrile Chemical compound N#CCCCCN=NCCCCC#N QNRSQFWYPSFVPW-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- BEUGBYXJXMVRFO-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1 BEUGBYXJXMVRFO-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- RNOOHTVUSNIPCJ-UHFFFAOYSA-N butan-2-yl prop-2-enoate Chemical compound CCC(C)OC(=O)C=C RNOOHTVUSNIPCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015115 caffè latte Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 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
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 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
- 239000002932 luster Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- JUVGLPRIQOJMIR-UHFFFAOYSA-N oxiran-2-ylmethyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OCC1CO1 JUVGLPRIQOJMIR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、ポリマー自体が発色し１着色の為の成分の添
加なしに美しい色調を発現することのできる発色性組成
物に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention provides a color-forming composition in which the polymer itself develops color and can express a beautiful color tone without adding any coloring components. Regarding.
（従来の技術）
近年１合威高分子は急速な発展を遂げ、極めて広い範囲
にわたって様々な形態で用いられるようになった。しか
し、はとんどの合成高分子はそれ自体色がなく、顔料・
染料等を配合したり１表面を塗装したりして着色する必
要がある。これらの着色手段では着色剤の色調の範囲内
の色しか表現し得す、嗜好が多様化している現在、全く
新しい色彩を提供する余地がほとんどない状態にある。(Prior Art) In recent years, 1-Hewei polymers have undergone rapid development and have come to be used in various forms over a wide range of areas. However, most synthetic polymers themselves have no color, and pigments and
It is necessary to add color by adding dyes or painting one surface. These coloring means can only express colors within the range of tones of the colorant, and as tastes are diversifying, there is little room to provide completely new colors.
（発明が解決しようとする課題） 従来の着色手段を高分子材料の特性面からみると。(Problem to be solved by the invention) Looking at conventional coloring methods from the perspective of the characteristics of polymer materials.
これら着色の為に用いられる色素は物理・作字的性質を
低下させる要因となり９品質的にはマイナス要素として
とらえられる場合が多い。The pigments used for coloring are a factor that deteriorates the physical and handwriting properties, and are often seen as a negative element in terms of quality.
また、ポリマー自体に色を与える場合、ポリマ−中に色
素と同じ化学構造を持った側鎖を付加すると云った方法
では２色素をブレンドする以上にポリマーの特性を損な
うことが予想され、コスト的にもきわめて非現実的なも
のになってしまうことは明白である。In addition, when adding color to the polymer itself, adding a side chain with the same chemical structure as the dye into the polymer is expected to impair the properties of the polymer more than blending two dyes, which is costly. It is clear that this would be extremely unrealistic.
本発明は、従来の色素による着色における上記のような
問題点、即ち高分子材料の持つ優れた特性を多かれ少な
かれ損なうという欠点を、ポリマー自体が発色し着色剤
を排除することで解消し、かつ、新しい色の世界を拓こ
うとするものである。The present invention solves the above-mentioned problems with conventional coloring using dyes, namely, the disadvantage that the excellent properties of polymeric materials are more or less impaired, by allowing the polymer itself to develop color and eliminating the coloring agent. , which seeks to open up a new world of colors.
本発明者らは検討の結果、ポリマー中に可視光の波長領
域と同レベルの大きさの逅クロ相分離構造を発生させて
、光の干渉によって発色させることにより９色素の類を
用いずに色を与えることがが可能であることを見出し２
本発明に至ったものである。As a result of studies, the inventors of the present invention found that by creating a phase-separated structure in the polymer that has the same size as the wavelength range of visible light and producing color through interference of light, it was possible to eliminate the use of 9 types of dyes. Headline 2 that it is possible to give color
This led to the present invention.
単分散系のラテックスが同様の原理で発色する事はよく
知られているが、一般に固定化が因難である。It is well known that monodisperse latex develops color based on the same principle, but fixation is generally the problem.
ポリスチレンラテ・ノクスを用いた人ニオバールのよう
に固定化された例もあるが、複雑な手順が必要であり、
かつ、この場合いわばポリマー顔料とも言える役割であ
り１着色剤の範晴を出るものではなく。There are examples of immobilization, such as human niobar, using polystyrene latte nox, but this requires a complicated procedure;
Moreover, in this case, it plays a role that can be called a polymer pigment, and is not beyond the scope of a coloring agent.
必要に応じてフィルム・成形品・繊維・塗膜等の形で固
定できる本発明はこれと一線を画するものである。The present invention, which can be fixed in the form of a film, molded product, fiber, paint film, etc., is distinct from this.
このように本発明は上記の種々の欠点を解消し。The present invention thus overcomes the various drawbacks mentioned above.
合成樹脂製品に新しい色彩の世界を提供するものである
。It provides a new world of colors for synthetic resin products.
本発明は、水酸基を有するアクリルポリマー（Ａ）に環
状酸無水物（Ｂ）およびエポキシド（Ｃ）′とを三級ア
旦ン触媒（Ｄ）の存在下に反応させて得られる発色性組
成物である。The present invention provides a color-forming composition obtained by reacting an acrylic polymer (A) having a hydroxyl group with a cyclic acid anhydride (B) and an epoxide (C)' in the presence of a tertiary ammonium catalyst (D). It is.
本発明の発色組成物の発色原理は必ずしも明確ではない
が、主鎖であるアクリルポリマーとグラフト鎖であるポ
リエステルとの間の相溶性の問題に起因するミクロ相分
離構造の生成によるものであろうと考えられる。すなわ
ち、いくつかのポリエステル鎖が会合して球状のコアが
形成され、主鎖であるアクリルポリマー鎖が周囲に配さ
れた。スタビライザーで安定化されたラテックスに類似
の構造をなしているものと思われる。この場合、コアの
粒径が揃い。The coloring principle of the coloring composition of the present invention is not necessarily clear, but it is probably due to the formation of a microphase-separated structure due to the compatibility problem between the acrylic polymer as the main chain and the polyester as the graft chain. Conceivable. That is, several polyester chains joined together to form a spherical core, and acrylic polymer chains as the main chain were arranged around it. It appears to have a structure similar to latex stabilized with a stabilizer. In this case, the core particle sizes are uniform.
適当な間隔で規則的な配列をすることが発色の要件とな
ると思われるれが、杢組戒物がその要件を満たすのに適
しているものと予想される。It seems that a regular arrangement at appropriate intervals is a requirement for color development, and Mokugumi Kaimono is expected to be suitable to meet this requirement.
本発明において、水酸基を有するアクリルポリマー（Ａ
）としては、水酸基を有するアクリルモノマーと、アク
リル酸、メタクリル酸、アルキルアクリレート、アルキ
ルメタクリレート、スチレン、酢酸ビニル、プロピオン
酸ビニル、ビニルエーテル、アクリロニトリル、等との
共重合体である。In the present invention, an acrylic polymer having hydroxyl groups (A
) is a copolymer of an acrylic monomer having a hydroxyl group and acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, styrene, vinyl acetate, vinyl propionate, vinyl ether, acrylonitrile, etc.
水酸基を有するモノマーとしては、２−ヒドロキシエチ
ル（メタ）アクリレート、２−ヒドロキシプロピル（メ
タ）アクリレート、３−ヒドロキシプロピル（メタ）ア
クリレート、２−ヒドロキシブチル（メタ）アクリレー
ト、４−ヒドロキシブチル（メタ）アクリレートなどの
ヒドロキシアルキル（メタ）アクリレートやＮ−メチロ
ールアクリルアミド。Examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. hydroxyalkyl (meth)acrylates such as acrylates and N-methylol acrylamide;
アリルアルコールなどがあるが、これらの中でも。Among these, there are allyl alcohols.
２−ヒドロキシエチルアクリレート、２−ヒドロキシエ
チルメタクリレートを用いるのが好ましく、更に好まし
くはこれらのモノマーをアクリルポリマー中３〜１０モ
ル％になるように用いるのがよい。It is preferable to use 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, and it is more preferable to use these monomers in an amount of 3 to 10 mol % in the acrylic polymer.
アルキル（メタ）アクリレートとしては、メチル（メタ
）アクリレート、エチル（メタ）アクリレート、ブチル
（メタ）アクリレート、２−エチルヘキシル（メタ）ア
クリレート、オクチル（メタ）アクリレートなどがある
。また、上記のモノマーの他に。Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate. In addition to the monomers listed above.
ジメチルア藁ノエチル（メタ）アクリレートなどの三級
アミノ基含有のアクリルモノマーや、ビニルフェノール
の様なモノマーを用いることもできる。Acrylic monomers containing a tertiary amino group, such as dimethylacrylate (meth)acrylate, and monomers such as vinylphenol can also be used.
反応は通常のラジカル重合であり、反応方法に何等制限
を加えるものではないが、直接法の反応に移れる点や反
応のコントロールが容易な点から溶液反応が好ましい。The reaction is a normal radical polymerization, and there are no restrictions on the reaction method; however, a solution reaction is preferable because it can be transferred to a direct reaction method and the reaction can be easily controlled.
溶液にする場合に用いる溶媒としては、メチルエチルケ
トン、トルエン、セロソルブ、酢酸エチル。Solvents used when making a solution include methyl ethyl ketone, toluene, cellosolve, and ethyl acetate.
等溶解性のあるものであれば何でもよく、単独でも複数
の溶媒を混合して用いてもよい。Any solvent may be used as long as it has equal solubility, and it may be used alone or in combination of a plurality of solvents.
本発明において環状酸無水物（Ｂ）としては多価カルボ
ン酸の分子内無水物であり、飽和または不飽和の脂肪族
多価カルボン酸無水物、脂環式多価カルボン酸無水物、
芳香族多価カルボン酸無水物など。In the present invention, the cyclic acid anhydride (B) is an intramolecular anhydride of polycarboxylic acid, such as saturated or unsaturated aliphatic polycarboxylic acid anhydride, alicyclic polycarboxylic acid anhydride,
Aromatic polycarboxylic acid anhydrides, etc.
あるいはこれらの一部が飽和または不飽和の炭化水素基
、芳香環基、ハロゲン原子、複素環基なとで置換された
ものがあり、これらの具体例としては、無水こはく酸、
無水フタル酸、無水マレイン酸、無水イタコン酸、無水
グルタル酸、無水ドデセニルこはく酸、無水クロレンデ
ック酸、無水ピロメリット酸。Alternatively, some of these may be substituted with saturated or unsaturated hydrocarbon groups, aromatic ring groups, halogen atoms, heterocyclic groups, etc. Specific examples of these include succinic anhydride,
Phthalic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, dodecenylsuccinic anhydride, chlorendic anhydride, pyromellitic anhydride.
無水トリメリット酸、シクロペンクンテトラカルボン酸
二無水物、ヘキサヒドロ無水フタル酸、メチルへキサヒ
ドロ無水フタル酸、テトラメチレン無水マレイン酸、テ
トラヒドロ無水フタル酸、メチルテトラヒドロ無水フタ
ル酸、エンドメチレンテトラヒドロ無水フタル酸、メチ
ルエンドメチレンテトラヒドロ無水フタル酸、５− （
２，５−ジオキソテトラヒドロキシフリル）−３−メチ
ル−３−シクロヘキセン−１，２−ジカルボン酸無水物
、無水メチルナジック酸、無水ベンゾフェノンテトラカ
ルボン酸、エチレングリコールビス（アンヒドロトリメ
リテート）グリセロールトリス（アンヒドロトリメリテ
ート）などがある。これらの中でも、架橋構造を作らな
いジカルボン酸の無水物を用いることが好ましい。Trimellitic anhydride, cyclopenkune tetracarboxylic dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride , methylendomethylenetetrahydrophthalic anhydride, 5-(
2,5-dioxotetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, methylnadic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate) glycerol Examples include Tris (anhydrotrimellitate). Among these, it is preferable to use a dicarboxylic acid anhydride that does not form a crosslinked structure.
本発明において、エポキシド（Ｃ）としては、エピクロ
ルヒドリン、フェニルグリシジルエーテル。In the present invention, the epoxide (C) includes epichlorohydrin and phenylglycidyl ether.
グリシジル（メタ）アクリレート、グリシジルシンナメ
ート、アリルグリシジルエーテル、ビニルシクロヘキセ
ンモノエポキサイド、１，３−ブタジェンエノエボキサ
イドなどがあり、これらは飽和もしくは不飽和の炭化水
素基、芳香環基、ハロゲン原子。These include glycidyl (meth)acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, and 1,3-butadiene enoepoxide, which contain saturated or unsaturated hydrocarbon groups, aromatic ring groups, and halogen atoms. .
複素環基なとで置換されていてもよい。It may be substituted with a heterocyclic group.
また、水酸基を有するアクリルポリマー（Ａ）に環状酸
無水物（Ｂ）とエポキシド（Ｃ）を反応させる際の触媒
である三級アミン（Ｄ）としては、トリエチルアξン、
トリブチルアミン、Ｎ、Ｎ−ジエチルアニリン、Ｎ、Ｎ
−ジメチルベンジルアミン、Ｎ。In addition, as the tertiary amine (D) which is a catalyst for reacting the acrylic polymer (A) having a hydroxyl group with the cyclic acid anhydride (B) and the epoxide (C), triethylamine,
Tributylamine, N,N-diethylaniline, N,N
-dimethylbenzylamine, N.
Ｎ−ジメチルアニリンなどの三級アミンなどが使用でき
る。更に、エポキシド（Ｃ）としてエチレン性不飽和基
を有するものを用いた場合１反応中手飽和基を安定に保
つために、ハイドロキノン、ハイドロキノンモノメチル
エーテル、ｔｅｒｔ−ブチルカテコール、ｐ−ベンゾキ
ノンなどのラジカル重合禁止剤を添加した状態で行なう
ことができる。Tertiary amines such as N-dimethylaniline can be used. Furthermore, when an epoxide (C) having an ethylenically unsaturated group is used, radical polymerization of hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, p-benzoquinone, etc. is performed to keep the saturated group stable during the first reaction. This can be done with the addition of an inhibitor.
反応は、まず、水酸基を含むアクリルポリマー（Ａ）の
水酸基と、環状酸無水物（Ｂ）の酸無水物基とが優先的
に反応し１次いで、この反応により生じたカルボキシル
基とエポキシド（Ｃ）のエポキシ基が反応し二級の水酸
基を生じる。さらに、生じた水酸基と環状酸無水物（Ｂ
）の酸無水物基が反応するというように、順次同様の反
応を進行させることができ、水酸基を含むアクリルポリ
マー（Ａ）の量に対して反応させられる環状酸無水物（
Ｂ）およびエポキシド（Ｃ）の量を調整することにより
、水酸基を有するアクリルポリマー（Ａ）に、所望の長
さの側鎖を導入することができる。In the reaction, first, the hydroxyl groups of the acrylic polymer (A) containing hydroxyl groups and the acid anhydride groups of the cyclic acid anhydride (B) react preferentially, and then the carboxyl groups produced by this reaction react with the epoxide (C ) reacts to produce a secondary hydroxyl group. Furthermore, the generated hydroxyl group and cyclic acid anhydride (B
Similar reactions can proceed in sequence, such that the acid anhydride groups of ) react, and the cyclic acid anhydride (
By adjusting the amounts of B) and epoxide (C), a side chain of a desired length can be introduced into the acrylic polymer (A) having a hydroxyl group.
環状酸無水物（Ｂ）がジカルボン酸無水物である場合に
は、水酸基を有するアクリルポリマー（Ａ）の水酸基１
モルに対して環状酸無水物（Ｂ）１〜２０モル、および
エポキシド（Ｃ）１〜２０モルの割合で、また、環状酸
無水物（Ｂ）に対してエポキシド（Ｃ）をほぼ等モルの
割合で反応させることが好ましい。環状酸無水物（Ｂ）
がトリカルボン酸無水物である場合には、水酸基を有す
るアクリルポリマー（Ａ）の水酸基１モルに対して環状
酸無水物（Ｂ）１〜１０モルおよびエポキシド（Ｃ）１
〜２０モルの割合で、また、環状酸無水物（Ｂ）１モル
に対してエポキシド（Ｃ）をほぼ１〜２モルの割合で反
応させることが好ましい。When the cyclic acid anhydride (B) is a dicarboxylic acid anhydride, the hydroxyl group 1 of the acrylic polymer (A) having a hydroxyl group
The ratio of 1 to 20 moles of cyclic acid anhydride (B) and 1 to 20 moles of epoxide (C) per mole, and approximately equal moles of epoxide (C) to cyclic acid anhydride (B). It is preferable to react in proportion. Cyclic acid anhydride (B)
is a tricarboxylic anhydride, 1 to 10 mol of cyclic acid anhydride (B) and 1 mol of epoxide (C) per 1 mol of hydroxyl groups of the acrylic polymer (A) having hydroxyl groups.
It is preferable to react the epoxide (C) at a ratio of ~20 moles, and approximately 1 to 2 moles of the epoxide (C) per mole of the cyclic acid anhydride (B).
水酸基を含むアクリルポリマー（Ａ）の水酸基１モルに
対して反応させられる環状酸無水物（Ｂ）の量が１モル
未満の場合には、得られる樹脂のミクロ相分離形成が不
十分で発色しなくなることがあり。If the amount of the cyclic acid anhydride (B) reacted with respect to 1 mole of hydroxyl groups in the acrylic polymer (A) containing hydroxyl groups is less than 1 mole, the formation of microphase separation in the resulting resin will be insufficient and color will develop. It may disappear.
逆に、環状酸無水物（Ｂ）の量が１０モルを超える場合
には、未反応の環状酸無水物（Ｂ）やエポキシド（Ｃ）
の残存、および水酸基を有するアクリルポリマー（Ａ）
に結合していない、環状酸無水物（Ｂ）とエポキシド（
Ｃ）との反応生成物の生成が多くなり、樹脂に濁りを生
じる傾向がある。Conversely, when the amount of cyclic acid anhydride (B) exceeds 10 moles, unreacted cyclic acid anhydride (B) and epoxide (C)
, and an acrylic polymer (A) having a hydroxyl group
Cyclic acid anhydride (B) and epoxide (
The reaction product with C) tends to increase and the resin tends to become cloudy.
得られる樹脂は環状酸無水物（Ｂ）とエポキシド（Ｃ）
とからなるポリエステル鎖を側鎖とするグラフトポリマ
ーとグラフトしていない独立のポリエステルオリゴマー
との混合物であるが、幹となるアクリルポリマーの骨格
を変化させることによって最終的な樹脂の物性を変化さ
せることができる。The resulting resin is a cyclic acid anhydride (B) and an epoxide (C).
It is a mixture of a grafted polymer with side chains of polyester chains consisting of I can do it.
さらに１本発明において、エポキシド（Ｃ）としてエチ
レン性不飽和基を有するものをを用いた場合側鎖のポリ
エステル部分に不飽和基を持ち、電子線硬化もしくは適
切なラジカル発生剤との併用で紫外線硬化・熱硬化等の
硬化法により、簡単に固化させることかできる。Furthermore, in the present invention, when an epoxide (C) having an ethylenically unsaturated group is used, it has an unsaturated group in the side chain polyester portion, and can be cured by electron beam curing or UV rays in combination with an appropriate radical generator. It can be easily solidified by hardening methods such as hardening and thermosetting.
紫外線硬化の場合のラジカル発生剤としては、ベンゾイ
ン、ベンゾインメチルエーテル、ベンゾインエチルエー
テル、０−ベンゾイル安息香酸メチル−ｐ−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、α
−メチルベンゾインなどのベンゾイン類、ジメチルベン
ジルケタール、トリクロルアセトフェノン、２．２−ジ
ェトキシアセトフェノンなどのアセトフェノン類、２−
ヒドロキシ−２−メチルプロピオフェノン、２−ヒドロ
キシ−４′イソプロピル−２−メチルプロピオフェノン
などのプロピオフェノン類、α−アジロキシムエステル
。In the case of ultraviolet curing, radical generators include benzoin, benzoin methyl ether, benzoin ethyl ether, methyl 0-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, α
- Benzoins such as methylbenzoin, acetophenones such as dimethylbenzyl ketal, trichloroacetophenone, 2.2-jethoxyacetophenone, 2-
Propiophenones such as hydroxy-2-methylpropiophenone and 2-hydroxy-4'isopropyl-2-methylpropiophenone, and α-aziroxime ester.
ベンゾフェノン、メチルベンゾフェノン、ｐ−クロルベ
ンゾフェノン、ｐ−ジメチルアミノベンゾフェノンなど
のベンゾフェノン類、２−クロルチオキサントン、２−
エチルチオキサントン、２−イソプロピルチオキサント
ンなどのチオキサントン類、ベンジル、ジベンゾスベロ
ンなどの他、加藤清視編：「Ｕ■・ＥＢ硬化ハンドブッ
ク−原料線−Ｊ（１９８５年１２月、高分子刊行会列）
第６７〜７３頁あるいは山下普三、金子東助編「架橋剤
ハンドブック」 （昭和５６年１０月、大戒社刊）第５
８２〜５９３頁に記載されているものがある。他の紫外
線硬化樹脂と同様、ラジカル発生の促進剤を併用するこ
とも効果的であり、このような促進剤としては、４゜４
′−ビス（ジエチルアご）〉ベンゾフェノン、Ｎ−ジメ
チルアミノ安息香酸エチル、ジメチルエタノ−ルアξン
、グリシンなどの他、加藤清視編：前掲書、第６７〜７
３頁に記載されたものを用いることができる。Benzophenones such as benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, 2-chlorothioxanthone, 2-
In addition to thioxanthone such as ethylthioxanthone and 2-isopropylthioxanthone, benzyl, dibenzosuberone, etc., edited by Kiyoshi Kato, "U■・EB Curing Handbook - Raw Material Wire - J (December 1985, Kobunshi Publishing Association Series)
Pages 67-73 or “Crosslinking Agent Handbook” edited by Fuzo Yamashita and Tosuke Kaneko (October 1980, published by Daikaisha) No. 5
Some are described on pages 82-593. As with other ultraviolet curing resins, it is also effective to use a radical generation accelerator.
'-Bis(diethyl ago)> Benzophenone, ethyl N-dimethylaminobenzoate, dimethylethanolane, glycine, etc., edited by Kiyoshi Kato, supra, No. 67-7
Those described on page 3 can be used.
また、熱硬化の場合のラジカル発生剤としては。Also, as a radical generator for thermosetting.
ベンゾイルパーオキサイド、アセチルパーオキサイド、
メチルエチルケトンパーオキサイド、ラウロイルパーオ
キサイド、ジクミルバーオキサイド、ジーｔｅｒｔ−ブ
チルパーオキサイド、ｔｅｒｔ−ブチルヒドロパーオキ
サイド、クメンヒドロパーオキサイドなどの有機過酸化
物、アゾビスイソブチロニトリル、アゾビスバレロニト
リルなどのアブ系ラジカル発生剤などが用いられる。こ
こで、ラジカル発生速度の小さい有機過酸化物を用いる
場合には、トリブチルア旦ン、トリエチルアξン、ジメ
チル−ｐ−トルイジン、ジメチルアニリン、トリエタノ
ールアミン、ジェタノールアニリンなどの三級アミン、
あるいはナフテン酸コバルト、オクトエ酸コバルト。benzoyl peroxide, acetyl peroxide,
Organic peroxides such as methyl ethyl ketone peroxide, lauroyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobisvaleronitrile, etc. Ab-based radical generators and the like are used. Here, when using an organic peroxide with a low radical generation rate, tertiary amines such as tributylamine, triethylamine, dimethyl-p-toluidine, dimethylaniline, triethanolamine, and jetanolaniline,
Or cobalt naphthenate, cobalt octoate.
ナフテン酸マンガンなどの金属石けんを促進剤として用
いることができる。Metal soaps such as manganese naphthenate can be used as accelerators.
以上に述べたラジカル発生剤は２本発明の発色性組成物
中の、不飽和二重結合を有する化合物の全量１００重量
部に対して１通常０．０５〜２０部、好ましくは０．５
〜ｌＯ部の割合で用いられる。The above-mentioned radical generators are usually 0.05 to 20 parts, preferably 0.5 parts per 100 parts by weight of the total amount of compounds having unsaturated double bonds in the color-forming composition of the present invention.
~10 parts.
硬化後の構造をさらに強固なものとするために。To further strengthen the structure after curing.
本発明の発色性組成物においては、ラジカル発生剤およ
び促進剤の他に、さらに（メタ）アクリロイル基などの
エチレン性不飽和基を有するモノマーやオリゴマーを添
加することができる。このようなモノマーやオリゴマー
としては、スチレン、アルキル（メタ）アクリレート、
（メタ）アクリル酸、多価アルコールポリ （メタ）
アクリレート、エポキシポリ （メタ）アクリレート、
オリゴエステルポリ （メタ）アクリレートポリウレタ
ンポリ （メタ）アクリレート、ジアリルフタレート、
ジアリルイソフタレートなどがある。また、硬化後の構
造の強化に加え１発色の度合を調整する目的で、水酸基
、−級アミノ基、二級アξノ基または三級アミノ基を有
する低分子化合物、環状酸無水物、およびエポキシドを
反応させて得られるオリゴエステルを用いることができ
る。In the color-forming composition of the present invention, in addition to the radical generator and accelerator, a monomer or oligomer having an ethylenically unsaturated group such as a (meth)acryloyl group can be added. Such monomers and oligomers include styrene, alkyl (meth)acrylates,
(meth)acrylic acid, polyhydric alcohol poly(meth)
Acrylate, epoxy poly(meth)acrylate,
Oligoester poly(meth)acrylate polyurethane poly(meth)acrylate, diallyl phthalate,
Examples include diallyl isophthalate. In addition, in order to strengthen the structure after curing and adjust the degree of color development, low molecular compounds, cyclic acid anhydrides, and Oligoesters obtained by reacting epoxides can be used.
本発明の発色性組成物には、その性能を阻害しない範囲
で、必要に応じて顔料、染料、マイカ等の無機充填剤、
銀粉、銅粉、ニッケル粉などの金属粉。The color-forming composition of the present invention may optionally contain pigments, dyes, inorganic fillers such as mica, etc., as long as they do not impede its performance.
Metal powders such as silver powder, copper powder, and nickel powder.
カーボンブラック、グラファイト、シランカップリング
剤、あるいは、トリレンジイソシアネート、イソフォロ
ンジイソシアネート、などのイソシアネート化合物など
を加えることができる。Carbon black, graphite, a silane coupling agent, or isocyanate compounds such as tolylene diisocyanate and isophorone diisocyanate can be added.
勿論９色素等を添加せずに発色させるという本発明の目
的からみれば、第二成分を用いることは好ましいことで
はないが、効果的な量で用いれば２色調の幅を広げたり
機能を向上させたりすることは可能である。Of course, from the point of view of the purpose of the present invention, which is to develop color without adding dyes, it is not preferable to use the second component, but if used in an effective amount, the range of two tones can be expanded and the functionality improved. It is possible to do so.
本発明の発色性Ｍｉ戒物は、溶液の状態で塗料や接着剤
として用いた後、紫外線、電子線、熱などによって硬化
させても良く、溶媒を除去して、フィルム。The color-forming Mi compound of the present invention may be used as a paint or adhesive in the form of a solution, and then cured by ultraviolet rays, electron beams, heat, etc., and the solvent may be removed to form a film.
繊維、成形品等にした後に硬化させたり、硬化させた後
に加工を施しても良い。It may be cured after being made into fibers, molded articles, etc., or may be processed after being cured.
（実施例）
以下、実施例により本発明を説明する。例中９部とは重
量部を９％とは重量％を、それぞれ表わす。(Example) The present invention will be explained below with reference to Examples. In the examples, 9 parts means parts by weight, and 9% means % by weight.
実施例１
ブチルアクリレ−） ８８．２
部酢酸ビニル ５，６部
２−ヒドロキシエチルアクリレ−） ６．２部
アゾビスイソブチロニトリル ０．３部酢
酸エチル ２３０．０部８０
℃に加熱した上記組成の混合物１６７部に。Example 1 Butyl acrylate) 88.2
5.6 parts vinyl acetate 6.2 parts azobisisobutyronitrile 0.3 parts ethyl acetate 230.0 parts 80 parts
167 parts of a mixture of the above composition heated to .
上記Ｍｉ戒の混合物１６７部を滴下し１滴下終了後。After dropping 167 parts of the above Mi precept mixture, one drop was completed.
１２時間加熱還流させ、冷却し水酸基を含むアクリルポ
リマーの溶液（固形分３０％）を得た。The mixture was heated under reflux for 12 hours and cooled to obtain a solution (solid content: 30%) of an acrylic polymer containing hydroxyl groups.
得られた水酸基を含むアクリルポリマーの溶液１００部
、無水フタル酸２２．２部、フェニルグリシジルエーテ
ル２３．６部を加え２８０℃で１２時間反応させた後、
酢酸エチル１０７部を加え、樹脂溶液（固形分３０％）
を得た。After adding 100 parts of the obtained acrylic polymer solution containing hydroxyl groups, 22.2 parts of phthalic anhydride, and 23.6 parts of phenyl glycidyl ether and reacting at 280°C for 12 hours,
Add 107 parts of ethyl acetate to create a resin solution (solid content 30%).
I got it.
得られた樹脂の溶液は虹彩色を呈しているが、全体が白
濁しており、オパールに酷似していた。The resulting resin solution had an iridescent color, but was cloudy throughout, resembling opal.
実施例２
ブチルアクリレート ９１，４部
酢酸ビニル ３．４部２
−ヒドロキシエチルメタクリレート５．２部アゾビスイ
ソブチロニトリル ０．３部酢酸エチル
２３０．０部上記組成の混合
物を実施例１と同様にして反応させ、水酸基を含むアク
リルポリマーの溶液（固形分３０％）を得た。Example 2 Butyl acrylate 91.4 parts Vinyl acetate 3.4 parts 2
-Hydroxyethyl methacrylate 5.2 parts Azobisisobutyronitrile 0.3 parts Ethyl acetate
230.0 parts A mixture having the above composition was reacted in the same manner as in Example 1 to obtain a solution (solid content: 30%) of an acrylic polymer containing hydroxyl groups.
得られた水酸基を含むアクリルポリマーの溶液１００部
、ヘキサヒドロ無水フタル酸１８．４部、グリシジルメ
タクリレート１６．９部、およびハイドロキノン０．２
部を混合し、実施例１と同様にして反応させた後、酢酸
エチル８２．４部を加え、側鎖にエチレン性不飽和基を
有する樹脂の溶液（固形分３０％）を得た。100 parts of the obtained acrylic polymer solution containing hydroxyl groups, 18.4 parts of hexahydrophthalic anhydride, 16.9 parts of glycidyl methacrylate, and 0.2 parts of hydroquinone.
After reacting in the same manner as in Example 1, 82.4 parts of ethyl acetate was added to obtain a solution (solid content: 30%) of a resin having an ethylenically unsaturated group in its side chain.
得られた側鎖にエチレン性不飽和基を有する樹脂の溶液
をガラス板上に流展し、溶剤を揮発させて乾燥膜にした
ところ、実施例１と同様な色調を呈した。When the obtained solution of the resin having an ethylenically unsaturated group in the side chain was spread on a glass plate and the solvent was evaporated to form a dry film, the same color tone as in Example 1 was obtained.
更に、この乾燥膜をエレクトロカーテン型の電子線照射
機（エナジーサイエンス社製Ｂ−１５０−１５−１０Ｌ
型）を用いて１０メガランドの電子線を照射したところ
硬い皮膜となったが２色相に変化は認められなかった。Furthermore, this dried film was subjected to an electrocurtain type electron beam irradiation machine (B-150-15-10L manufactured by Energy Science Co., Ltd.).
When irradiated with an electron beam of 10 Megaland using a mold), a hard film was formed, but no change was observed in the two hues.
この皮膜の吸収スペクトルは５００ ｎｍ付近にブロー
ドなピークを示した。The absorption spectrum of this film showed a broad peak around 500 nm.
実施例３
ブチルアクリレート ９５．０部
２−ヒドロキシプロピルメタクリレート ５．０部ア
ゾビスイソブチロニトリル ０．３部酢酸
エチル ２３０．０部上記組
戒の混合物を実施例１と同様にして反応させ、水酸基を
含むアクリルポリマーの溶液（固形分３０％〉を得た。Example 3 Butyl acrylate 95.0 parts 2-hydroxypropyl methacrylate 5.0 parts Azobisisobutyronitrile 0.3 parts Ethyl acetate 230.0 parts A mixture of the above components was reacted in the same manner as in Example 1, A solution (solid content: 30%) of an acrylic polymer containing hydroxyl groups was obtained.
得られた水酸基を含むアクリルポリマーの溶液１００部
、無水こはく酸１１．６部、フェニルグリシジルエーテ
ル１７．４部を混合し、実施例１と同様にして反応させ
た後、酢酸エチル６８部を加え、樹脂溶液（固形分３０
％）を得た。100 parts of the obtained acrylic polymer solution containing hydroxyl groups, 11.6 parts of succinic anhydride, and 17.4 parts of phenyl glycidyl ether were mixed and reacted in the same manner as in Example 1, and then 68 parts of ethyl acetate was added. , resin solution (solid content 30
%) was obtained.
得られた樹脂溶液は、黄緑色系のパール光沢を有した半
透明を呈していた。The resulting resin solution was translucent with a yellow-green pearlescent luster.
［発明の効果〕
本発明の発色性組成物は、上記実施例に示すとおり１通
常のラジカル重合とグラフト反応の組合せのみで、それ
以外の複雑な操作は必要としない。[Effects of the Invention] The color-forming composition of the present invention requires only a combination of ordinary radical polymerization and grafting reaction, as shown in the above examples, and does not require any other complicated operations.
従ってきわめて容易に発色性のポリマーが得られ。Therefore, a color-forming polymer can be obtained very easily.
新しい色彩の可能性を提供するものである。It offers new color possibilities.
Claims (1)
水物（Ｂ）およびエポキシド（Ｃ）を三級アミン触媒（
Ｄ）の存在下に反応させて得られる発色性組成物。 ２、水酸基を含むアクリルポリマー（Ａ）が２−ヒドロ
キシエチルアクリレートまたは、２−ヒドロキシエチル
メタクリレートをモノマーとして使用してなる請求項１
記載の発色性組成物。 ３、水酸基を含むアクリルポリマー（Ａ）が２−ヒドロ
キシエチルアクリレートまたは、２−ヒドロキシエチル
メタクリレートをモノマーとして使用し、その量がアク
リルポリマー中３〜１０モル％である請求項１記載の発
色性組成物。 ４、水酸基を含むアクリルポリマー（Ａ）中の水酸基１
モルに対し、環状酸無水物（Ｂ）およびエポキシド（Ｃ
）をそれぞれ１〜２０モル用いてなる請求項１ないし３
いずれか記載の発色性組成物。[Claims] 1. A cyclic acid anhydride (B) and an epoxide (C) are added to an acrylic polymer (A) having a hydroxyl group using a tertiary amine catalyst (
A color-forming composition obtained by reacting in the presence of D). 2. Claim 1 in which the acrylic polymer (A) containing hydroxyl groups uses 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate as a monomer.
The color-forming composition described. 3. The color-forming composition according to claim 1, wherein the hydroxyl group-containing acrylic polymer (A) uses 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate as a monomer, and the amount thereof is 3 to 10 mol% in the acrylic polymer. thing. 4. Hydroxyl group 1 in acrylic polymer (A) containing hydroxyl group
Cyclic acid anhydride (B) and epoxide (C
), each using 1 to 20 moles of
Color-forming composition according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1224087A JP2544814B2 (en) | 1989-08-30 | 1989-08-30 | Chromogenic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1224087A JP2544814B2 (en) | 1989-08-30 | 1989-08-30 | Chromogenic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0386703A true JPH0386703A (en) | 1991-04-11 |
| JP2544814B2 JP2544814B2 (en) | 1996-10-16 |
Family
ID=16808351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1224087A Expired - Lifetime JP2544814B2 (en) | 1989-08-30 | 1989-08-30 | Chromogenic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2544814B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778292A3 (en) * | 1995-12-04 | 1998-11-04 | Bayer Corporation | Method for the production of anhydride modified polyvinyl acetals useful for photosensitive compositions |
| WO2023018212A1 (en) * | 2021-08-11 | 2023-02-16 | 주식회사 삼양사 | Composition for adhesion of dissimilar materials, and preparation method therefor |
-
1989
- 1989-08-30 JP JP1224087A patent/JP2544814B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778292A3 (en) * | 1995-12-04 | 1998-11-04 | Bayer Corporation | Method for the production of anhydride modified polyvinyl acetals useful for photosensitive compositions |
| WO2023018212A1 (en) * | 2021-08-11 | 2023-02-16 | 주식회사 삼양사 | Composition for adhesion of dissimilar materials, and preparation method therefor |
| KR20230024455A (en) * | 2021-08-11 | 2023-02-21 | 주식회사 삼양사 | Composition for bonding heretogeneous materials and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2544814B2 (en) | 1996-10-16 |
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