JP6787493B2 - Compositions and printing inks - Google Patents
Compositions and printing inks Download PDFInfo
- Publication number
- JP6787493B2 JP6787493B2 JP2019530997A JP2019530997A JP6787493B2 JP 6787493 B2 JP6787493 B2 JP 6787493B2 JP 2019530997 A JP2019530997 A JP 2019530997A JP 2019530997 A JP2019530997 A JP 2019530997A JP 6787493 B2 JP6787493 B2 JP 6787493B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- mass
- printing ink
- resin
- 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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- 238000007639 printing Methods 0.000 title claims description 60
- 239000000203 mixture Substances 0.000 title claims description 31
- 239000000976 ink Substances 0.000 title description 44
- -1 acrylate compound Chemical class 0.000 claims description 81
- 239000004925 Acrylic resin Substances 0.000 claims description 49
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 150000004696 coordination complex Chemical class 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000005056 polyisocyanate Substances 0.000 claims description 13
- 229920001228 polyisocyanate Polymers 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 44
- 239000000049 pigment Substances 0.000 description 27
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000002596 lactones Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007645 offset printing Methods 0.000 description 6
- 229920000193 polymethacrylate Polymers 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- 239000004641 Diallyl-phthalate Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 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 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- BKNMHPNFWBRRFC-UHFFFAOYSA-N (2-hydroxy-1-phenylethyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)C1=CC=CC=C1 BKNMHPNFWBRRFC-UHFFFAOYSA-N 0.000 description 1
- NSIHCJDYMGWYKW-UHFFFAOYSA-N (2-hydroxy-2-phenylethyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)C1=CC=CC=C1 NSIHCJDYMGWYKW-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- QZSWQQATTVDWCI-UHFFFAOYSA-N (4-acetyl-3-hydroxyphenyl) prop-2-enoate Chemical compound CC(=O)C1=CC=C(OC(=O)C=C)C=C1O QZSWQQATTVDWCI-UHFFFAOYSA-N 0.000 description 1
- NIUHGYUFFPSEOW-UHFFFAOYSA-N (4-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=C(OC(=O)C=C)C=C1 NIUHGYUFFPSEOW-UHFFFAOYSA-N 0.000 description 1
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical class O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical class C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- UGAGPNKCDRTDHP-UHFFFAOYSA-N 16-hydroxyhexadecanoic acid Chemical compound OCCCCCCCCCCCCCCCC(O)=O UGAGPNKCDRTDHP-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 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
- YSUGIEHWIVGUDE-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethyl prop-2-enoate Chemical compound OC1=CC=C(CCOC(=O)C=C)C=C1 YSUGIEHWIVGUDE-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- JGHSBPIZNUXPLA-UHFFFAOYSA-N 2-Hydroxyhexadecanoic acid Natural products CCCCCCCCCCCCCCC(O)C(O)=O JGHSBPIZNUXPLA-UHFFFAOYSA-N 0.000 description 1
- ZIAGYKQVFTXUQH-UHFFFAOYSA-N 2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)CC1=CC=C(C)C=C1 ZIAGYKQVFTXUQH-UHFFFAOYSA-N 0.000 description 1
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-UHFFFAOYSA-N 0.000 description 1
- OMOYYCNTSLVTOE-SYXWNFKLSA-N 2-[[(e)-3-(carboxymethylimino)prop-1-enyl]amino]acetic acid Chemical compound OC(=O)CN\C=C\C=NCC(O)=O OMOYYCNTSLVTOE-SYXWNFKLSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- AFENDNXGAFYKQO-UHFFFAOYSA-N 2-hydroxybutyric acid Chemical compound CCC(O)C(O)=O AFENDNXGAFYKQO-UHFFFAOYSA-N 0.000 description 1
- YDZIJQXINJLRLL-UHFFFAOYSA-N 2-hydroxydodecanoic acid Chemical compound CCCCCCCCCCC(O)C(O)=O YDZIJQXINJLRLL-UHFFFAOYSA-N 0.000 description 1
- KUZABABLVHWUGR-UHFFFAOYSA-N 2-hydroxyheptadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)C(O)=O KUZABABLVHWUGR-UHFFFAOYSA-N 0.000 description 1
- RGMMREBHCYXQMA-UHFFFAOYSA-N 2-hydroxyheptanoic acid Chemical compound CCCCCC(O)C(O)=O RGMMREBHCYXQMA-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- BTJFTHOOADNOOS-UHFFFAOYSA-N 2-hydroxynonanoic acid Chemical compound CCCCCCCC(O)C(O)=O BTJFTHOOADNOOS-UHFFFAOYSA-N 0.000 description 1
- ZRIAELJUCLIMFF-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O.CCCCCCCCCCCCCCCCC(O)C(O)=O ZRIAELJUCLIMFF-UHFFFAOYSA-N 0.000 description 1
- JKRDADVRIYVCCY-UHFFFAOYSA-N 2-hydroxyoctanoic acid Chemical compound CCCCCCC(O)C(O)=O JKRDADVRIYVCCY-UHFFFAOYSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- WACQLQIAUWURGA-UHFFFAOYSA-N 3-hydroxy-2,2-bis(hydroxymethyl)propanoic acid Chemical compound OCC(CO)(CO)C(O)=O WACQLQIAUWURGA-UHFFFAOYSA-N 0.000 description 1
- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- AAPAKNYBKJJABI-UHFFFAOYSA-N 4-hydroxy-3-(hydroxymethyl)butanoic acid Chemical compound OCC(CO)CC(O)=O AAPAKNYBKJJABI-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- APONQNCLCAEVQE-UHFFFAOYSA-L [Ti+4].C(C)(=O)CC(=O)[O-].C(C)(=O)CC(=O)[O-].[Ti+4] Chemical compound [Ti+4].C(C)(=O)CC(=O)[O-].C(C)(=O)CC(=O)[O-].[Ti+4] APONQNCLCAEVQE-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 1
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- ZRHOFLXFAAEXEE-UHFFFAOYSA-J butanoate;titanium(4+) Chemical compound [Ti+4].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O ZRHOFLXFAAEXEE-UHFFFAOYSA-J 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
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WPCPXPTZTOMGRF-UHFFFAOYSA-K di(butanoyloxy)alumanyl butanoate Chemical compound [Al+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O WPCPXPTZTOMGRF-UHFFFAOYSA-K 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- LMHJFKYQYDSOQO-UHFFFAOYSA-N hydroxydecanoic acid Natural products CCCCCC(O)CCCC(O)=O LMHJFKYQYDSOQO-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- QGMRQYFBGABWDR-UHFFFAOYSA-N sodium;5-ethyl-5-pentan-2-yl-1,3-diazinane-2,4,6-trione Chemical compound [Na+].CCCC(C)C1(CC)C(=O)NC(=O)NC1=O QGMRQYFBGABWDR-UHFFFAOYSA-N 0.000 description 1
- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は印刷インキ用途に好適に用いることができる組成物及びこれを用いた印刷インキ、前記印刷インキを印刷してなる印刷物に関する。 The present invention relates to a composition that can be suitably used for printing ink applications, a printing ink using the same, and a printed matter obtained by printing the printing ink.
活性エネルギー線硬化型印刷インキは、紫外線等のエネルギー線照射により瞬時に硬化し得るため作業性に優れること、基本的に無溶剤で用いられるために環境負荷が比較的低いこと等の利点から、紙面印刷の他、プラスチック包装材等様々な用途に用いられている。しかしながらその一方で、前述の即硬化性に起因して印刷面のレベリング性が低く光沢が出にくい、油性インキと比較して印刷面への密着性が低いなど、活性エネルギー線硬化型印刷インキ独特の課題もあり、これら課題の効果的な解決策が求められている。 The active energy ray-curable printing ink has advantages such as excellent workability because it can be instantly cured by irradiation with energy rays such as ultraviolet rays, and because it is basically used without a solvent and has a relatively low environmental load. In addition to paper printing, it is used for various purposes such as plastic packaging materials. However, on the other hand, it is unique to active energy ray-curable printing inks, such as low leveling property of the printed surface and low gloss due to the above-mentioned immediate curability, and low adhesion to the printed surface compared to oil-based inks. There are also issues, and effective solutions to these issues are required.
活性エネルギー線硬化型印刷インキのバインダー樹脂としては、ジペンタエリスリトールポリアクリレート等の反応性希釈剤との相溶性に優れるジアリルフタレート樹脂や、基材密着性に優れるロジン変性（メタ）アクリレート樹脂等が知られているが、何れの技術においても印刷面光沢に関する課題は残ったままであった。 Examples of the binder resin for the active energy ray-curable printing ink include diallyl phthalate resin having excellent compatibility with a reactive diluent such as dipentaerythritol polyacrylate, and rosin-modified (meth) acrylate resin having excellent substrate adhesion. As is known, the problem of print surface gloss remains in any of the techniques.
従って、本発明が解決しようとする課題は印刷面光沢に優れる印刷インキを提供することにある。 Therefore, the problem to be solved by the present invention is to provide a printing ink having excellent print surface gloss.
発明者らは上記課題を解決すべく鋭意研究を重ねた結果、酸基含有ウレタン（メタ）アクリレート樹脂と金属錯体とを含有する組成物を印刷インキに配合することにより、印刷インキの流動性が向上し、結果、高光沢の印刷面が得られることを見出し、本発明を完成するに至った。 As a result of intensive research to solve the above problems, the inventors have added a composition containing an acid group-containing urethane (meth) acrylate resin and a metal complex to the printing ink to improve the fluidity of the printing ink. We have found that a high-gloss printed surface can be obtained as a result of the improvement, and have completed the present invention.
即ち、本発明は、酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）と、金属錯体（Ｂ）とを含有する組成物に関する。 That is, the present invention relates to a composition containing an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B).
本発明は、更に、前記組成物を用いてなる印刷インキに関する。 The present invention further relates to a printing ink made by using the above composition.
本発明は、更に、前記印刷インキを印刷してなる印刷物に関する。 The present invention further relates to a printed matter obtained by printing the printing ink.
本発明によれば、印刷面光沢に優れる印刷インキ及びこれを用いた印刷物、前記印刷インキ原料として有用な組成物を提供できる。 According to the present invention, it is possible to provide a printing ink having excellent print surface gloss, a printed matter using the same, and a composition useful as a raw material for the printing ink.
本発明の組成物は、酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）と金属錯体（Ｂ）とを含有する。前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）は、分子構造中にウレタン結合部位を有し、かつ、カルボキシ基等の酸基を有するものであればよく、その他の具体構造は特に限定されない。また、本発明において（メタ）アクリレート樹脂とは、分子中にアクリロイル基、メタクリロイル基、或いはその両方を有する樹脂のことをいう。また、（メタ）アクリロイル基とは、アクリロイル基、メタクリロイル基の一方或いは両方のことをいい、（メタ）アクリレートとは、アクリレート及びメタクリレートの総称である。 The composition of the present invention contains an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B). The acid group-containing urethane (meth) acrylate resin (A) may have a urethane bond site in the molecular structure and has an acid group such as a carboxy group, and other specific structures are not particularly limited. .. Further, in the present invention, the (meth) acrylate resin refers to a resin having an acryloyl group, a methacryloyl group, or both in the molecule. Further, the (meth) acryloyl group refers to one or both of an acryloyl group and a methacryloyl group, and (meth) acrylate is a general term for acrylate and methacrylate.
前記ウレタン（メタ）アクリレート樹脂（Ａ）の一例としては、例えば、ポリイソシアネート化合物（ａ１）、ヒドロキシ（メタ）アクリレート化合物（ａ２）及び酸基含有ヒドロキシ化合物（ａ３）を必須の反応原料とするもの等が挙げられる。 As an example of the urethane (meth) acrylate resin (A), for example, a polyisocyanate compound (a1), a hydroxy (meth) acrylate compound (a2) and an acid group-containing hydroxy compound (a3) as essential reaction raw materials. And so on.
前記ポリイソシアネート化合物（ａ１）は、例えば、ブタンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート化合物；ノルボルナンジイソシアネート、イソホロンジイソシアネート、水添キシリレンジイソシアネート、水添ジフェニルメタンジイソシアネート等の脂環式ジイソシアネート化合物；トリレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ジフェニルメタンジイソシアネート、１，５−ナフタレンジイソシアネート等の芳香族ジイソシアネート化合物；下記構造式（１）で表される繰り返し構造を有するポリイソシアネート化合物；これらのイソシアヌレート変性体、ビウレット変性体、アロファネート変性体等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。 The polyisocyanate compound (a1) is an aliphatic diisocyanate compound such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; norbornan diisocyanate, isophorone. Alicyclic diisocyanate compounds such as diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalenedi isocyanate; Polyisocyanate compounds having a repeating structure represented by the following structural formula (1); these isocyanurate modified products, biuret modified products, allophanate modified products and the like can be mentioned. Each of these may be used alone, or two or more types may be used in combination.
前記ポリイソシアネート化合物（ａ１）の中でも、流動性及び印刷面の光沢に優れる他、耐ミスチング性や乳化適正等の一般的な印刷適性にも優れる印刷インキが得られることから、前記構造式（１）で表される分子構造を有するポリイソシアネート化合物や、各種ジイソシアネート化合物のイソシアヌレート変性体など平均官能基数が３以上であるポリイソシアネート化合物を必須で用いることが好ましい。特に、前記ポリイソシアネート化合物（ａ１）に占める前記平均官能基数が３以上であるポリイソシアネート化合物の割合が７０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。また、ポリイソシアネート化合物がイソシアヌレート変性体である場合、原料ジイソシアネート化合物は脂肪族又は脂環式ジイソシアネート化合物であることが好ましく、脂肪族ジイソシアネート化合物が特に好ましい。 Among the polyisocyanate compounds (a1), a printing ink having excellent fluidity and gloss on the printed surface as well as general printability such as misting resistance and emulsification suitability can be obtained. Therefore, the structural formula (1) ), And a polyisocyanate compound having an average number of functional groups of 3 or more, such as an isocyanurate-modified product of various diisocyanate compounds, is preferably used indispensably. In particular, the proportion of the polyisocyanate compound having an average number of functional groups of 3 or more in the polyisocyanate compound (a1) is preferably 70% by mass or more, and more preferably 90% by mass or more. When the polyisocyanate compound is an isocyanurate modified product, the raw material diisocyanate compound is preferably an aliphatic or alicyclic diisocyanate compound, and an aliphatic diisocyanate compound is particularly preferable.
前記ヒドロキシ（メタ）アクリレート化合物（ａ２）は、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチルアクリレート等の脂肪族ヒドロキシモノ（メタ）アクリレート化合物；グリセリンジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の脂肪族ヒドロキシポリ（メタ）アクリレート化合物；アクリル酸４−ヒドロキシフェニル、アクリル酸β−ヒドロキシフェネチル、アクリル酸４−ヒドロキシフェネチル、アクリル酸１−フェニル−２−ヒドロキシエチル、アクリル酸３−ヒドロキシ−４−アセチルフェニル、２−ヒドロキシ−３−フェノキシプロピルアクリレート等の芳香族ヒドロキシモノ（メタ）アクリレート化合物；前記各種のヒドロキシ（メタ）アクリレート化合物と、エチレンオキシド、プロピレンオキシド、テトラヒドロフラン、エチルグリシジルエーテル、プロピルグリシジルエーテル、ブチルグリシジルエーテル、フェニルグリシジルエーテル、アリルグリシジルエーテル等種々の環状エーテル化合物との開環重合によって得られるポリオキシアルキレン変性モノヒドロキシ（メタ）アクリレート化合物；前記モノヒドロキシ（メタ）アクリレート化合物と、ε−カプロラクトン等のラクトン化合物との重縮合によって得られるラクトン変性ヒドロキシ（メタ）アクリレート化合物等が挙げられる。これらはそれぞれ単独で使用しても良いし、２種類以上を併用しても良い。 The hydroxy (meth) acrylate compound (a2) is, for example, an aliphatic hydroxymono (meth) acrylate compound such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl acrylate; glycerindi (meth) acrylate, Aliphatic hydroxypoly (meth) acrylate compounds such as trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate. , 4-Hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate and other aromatic hydroxymono (meth) acrylate compounds. By ring-open polymerization of the various hydroxy (meth) acrylate compounds and various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Examples thereof include a polyoxyalkylene-modified monohydroxy (meth) acrylate compound obtained; a lactone-modified hydroxy (meth) acrylate compound obtained by polycondensation of the monohydroxy (meth) acrylate compound with a lactone compound such as ε-caprolactone. .. Each of these may be used alone, or two or more types may be used in combination.
前記ヒドロキシ（メタ）アクリレート化合物（ａ２）の中でも、流動性及び印刷面の光沢に優れる他、耐ミスチング性や乳化適正等の一般的な印刷適性にも優れる印刷インキが得られることから、前記脂肪族ヒドロキシモノ（メタ）アクリレート化合物、前記脂肪族ヒドロキシポリ（メタ）アクリレート化合物、及びこれらのポリオキシアルキレン変性体或いはラクトン変性が好ましく、ラクトン変性脂肪族ヒドロキシ（メタ）アクリレート化合物がより好ましく、ラクトン変性脂肪族ヒドロキシモノ（メタ）アクリレート化合物が特に好ましい。更に、前記ヒドロキシ（メタ）アクリレート化合物（ａ２）に占める前記ラクトン変性脂肪族ヒドロキシモノ（メタ）アクリレート化合物の割合が７０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。 Among the hydroxy (meth) acrylate compounds (a2), a printing ink having excellent fluidity and gloss on the printed surface as well as general printing suitability such as misting resistance and emulsification suitability can be obtained. Group hydroxymono (meth) acrylate compounds, said aliphatic hydroxypoly (meth) acrylate compounds, and polyoxyalkylene modified products or lactone modifications thereof are preferable, and lactone-modified aliphatic hydroxy (meth) acrylate compounds are more preferable, and lactone-modified. Aliphatic hydroxymono (meth) acrylate compounds are particularly preferred. Further, the ratio of the lactone-modified aliphatic hydroxymono (meth) acrylate compound to the hydroxy (meth) acrylate compound (a2) is preferably 70% by mass or more, and more preferably 90% by mass or more.
前記酸基含有ヒドロキシ化合物（ａ３）は、分子構造中にカルボキシ基等の酸基とヒドロキシ基とを有するものであれば、カルボキシ基及びヒドロキシ基の数やその他の具体構造は特に限定されない。また、酸基含有ヒドロキシ化合物（ａ３）それぞれ単独で使用しても良いし、２種類以上を併用しても良い。中でも、流動性及び印刷面の光沢に一層優れる印刷インキが得られることから脂肪族化合物であることが好ましく、炭素原子数２〜２０の脂肪族炭化水素上にカルボキシ基を１〜３個、ヒドロキシ基を１〜３個有する化合物がより好ましい。このような化合物の具体例としては、例えば、グリコール酸、乳酸、ヒドロキシブタン酸、ヒドロキシペンタン酸、ヒドロキシヘキサン酸、ヒドロキシヘプタン酸、ヒドロキシオクタン酸、ヒドロキシノナン酸、ヒドロキシデカン酸、ヒドロキシドデカン酸、ヒドロキシテトラデカン酸、ヒドロキシヘキサデカン酸、ヒドロキシヘプタデカン酸、ヒドロキシオクタデカン酸（ヒドロキシステアリン酸）、リシノール酸等のモノヒドロキシ化合物；グリセリン酸、２−（ヒドロキシメチル）−３−ヒドロキシプロピオン酸、２−（ジヒドロキシメチル）プロピオン酸、ジメチロールプロピオン酸、３，３−ジメチロールプロピオン酸等のジヒドロキシ化合物；３−ヒドロキシ−２，２−ビス（ヒドロキシメチル）プロピオン酸等のトリヒドロキシ化合物等が挙げられる。 The number of carboxy groups and hydroxy groups and other specific structures are not particularly limited as long as the acid group-containing hydroxy compound (a3) has an acid group such as a carboxy group and a hydroxy group in its molecular structure. Further, each of the acid group-containing hydroxy compounds (a3) may be used alone, or two or more kinds may be used in combination. Among them, an aliphatic compound is preferable because a printing ink having further excellent fluidity and gloss on the printed surface can be obtained, and 1 to 3 carboxy groups and hydroxy on an aliphatic hydrocarbon having 2 to 20 carbon atoms. A compound having 1 to 3 groups is more preferable. Specific examples of such compounds include glycolic acid, lactic acid, hydroxybutanoic acid, hydroxypentanoic acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxydodecanoic acid, and hydroxy. Monohydroxy compounds such as tetradecanoic acid, hydroxyhexadecanoic acid, hydroxyheptadecanoic acid, hydroxyoctadecanic acid (hydroxystearic acid), ricinolic acid; glyceric acid, 2- (hydroxymethyl) -3-hydroxypropionic acid, 2- (dihydroxymethyl) ) Dihydroxy compounds such as propionic acid, dimethylol propionic acid, 3,3-dimethylol propionic acid; trihydroxy compounds such as 3-hydroxy-2,2-bis (hydroxymethyl) propionic acid and the like.
前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）は、前記ポリイソシアネート化合物（ａ１）、前記ヒドロキシ（メタ）アクリレート化合物（ａ２）及び前記酸基含有ヒドロキシ化合物（ａ３）の他、他の反応原料を併用したものであってもよい。他の反応原料としては、例えば、前記ヒドロキシ（メタ）アクリレート化合物（ａ２）や前記酸基含有ヒドロキシ化合物（ａ３）以外のポリオール化合物等が挙げられる。前記ポリオール化合物は、例えば、エチレングリコール、プロプレングリコール、ブタンジオール、ヘキサンジオール、グリセリン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等の脂肪族ポリオール化合物；ビフェノール、ビスフェノール等の芳香族ポリオール化合物；前記各種のポリオール化合物の分子構造中に（ポリ）オキシエチレン鎖、（ポリ）オキシプロピレン鎖、（ポリ）オキシテトラメチレン鎖等の（ポリ）オキシアルキレン鎖を導入した（ポリ）オキシアルキレン変性体；前記各種のポリオール化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性体等が挙げられる。 The acid group-containing urethane (meth) acrylate resin (A) includes the polyisocyanate compound (a1), the hydroxy (meth) acrylate compound (a2), the acid group-containing hydroxy compound (a3), and other reaction raw materials. May be used in combination. Examples of other reaction raw materials include polyol compounds other than the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3). The polyol compound is, for example, an aliphatic polyol compound such as ethylene glycol, proprene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol; aromatics such as biphenol and bisphenol. Polyol compound; (poly) oxyalkylene chain in which (poly) oxyalkylene chain such as (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain is introduced into the molecular structure of the various polyol compounds. Modified products: Examples thereof include lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds.
前記他の反応原料を用いる場合には、本発明が奏する効果が十分に発揮されることから、前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）の反応原料に占める前記ポリイソシアネート化合物（ａ１）、前記ヒドロキシ（メタ）アクリレート化合物（ａ２）及び前記酸基含有ヒドロキシ化合物（ａ３）の合計質量の割合が７０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。 When the other reaction raw material is used, the effect of the present invention is sufficiently exhibited. Therefore, the polyisocyanate compound (a1) in the reaction raw material of the acid group-containing urethane (meth) acrylate resin (A). The total mass ratio of the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3) is preferably 70% by mass or more, and more preferably 90% by mass or more.
酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）を製造する方法は特に限定されず、通常は、一般的なウレタン（メタ）アクリレート樹脂同様の方法にて製造することができる。各成分の反応割合や反応順等は所望の樹脂設計や樹脂性能に応じて適宜調整されるものであり、特に限定されるものではない。反応条件の一例としては、反応原料中のイソシアネート基１モルに対し、反応原料中の水酸基が０．９〜１．１モルの範囲となる割合で各反応原料を用い、２０〜１２０℃に加熱する方法が挙げられる。当該反応では所望に応じてオクチル酸亜鉛等の公知慣用のウレタン化触媒や、各種の酸化防止剤、重合禁止剤等を用いても良い。 The method for producing the acid group-containing urethane (meth) acrylate resin (A) is not particularly limited, and usually, it can be produced by the same method as a general urethane (meth) acrylate resin. The reaction ratio, reaction order, etc. of each component are appropriately adjusted according to the desired resin design and resin performance, and are not particularly limited. As an example of the reaction conditions, each reaction raw material is used at a ratio of the hydroxyl group in the reaction raw material in the range of 0.9 to 1.1 mol with respect to 1 mol of the isocyanate group in the reaction raw material, and heated to 20 to 120 ° C. There is a way to do it. In the reaction, a known and commonly used urethanization catalyst such as zinc octylate, various antioxidants, a polymerization inhibitor and the like may be used, if desired.
前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）の酸価は、流動性及び印刷面の光沢に一層優れる印刷インキが得られることから１〜５０ｍｇＫＯＨ/ｇの範囲であることが好ましく、３〜４０ｍｇＫＯＨ/ｇの範囲であることがより好ましく、３〜３５ｍｇＫＯＨ/ｇの範囲であることが特に好ましい。本発明において樹脂の酸価はＪＩＳ Ｋ ００７０（１９９２）の中和滴定法にて測定される値である。 The acid value of the acid group-containing urethane (meth) acrylate resin (A) is preferably in the range of 1 to 50 mgKOH / g because a printing ink having further excellent fluidity and gloss on the printed surface can be obtained. It is more preferably in the range of 40 mgKOH / g, and particularly preferably in the range of 3 to 35 mgKOH / g. In the present invention, the acid value of the resin is a value measured by the neutralization titration method of JIS K 0070 (1992).
前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）の質量平均分子量（Ｍｗ）は、印刷インキ用途に用いた際の流動性及び印刷面の光沢に一層優れる印刷インキが得られることから１，０００〜２５，０００の範囲であることが好ましく、１，０００〜１０，０００の範囲であることがより好ましい。 The mass average molecular weight (Mw) of the acid group-containing urethane (meth) acrylate resin (A) is 1,000 because a printing ink having further excellent fluidity and gloss on the printed surface can be obtained when used for printing ink applications. It is preferably in the range of ~ 25,000, and more preferably in the range of 1,000 to 10,000.
本願発明において樹脂の分子量は下記条件のゲルパーミアーションクロマトグラフィー（ＧＰＣ）により測定される値である。 In the present invention, the molecular weight of the resin is a value measured by gel permeation chromatography (GPC) under the following conditions.
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）Measuring device; HLC-8220GPC manufactured by Tosoh Corporation
Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)
前記金属錯体（Ｂ）は、例えば、アルミニウムトリエチレートアルミニウムトリプロピレート、アルミニウムジプロピレートモノブチレート、アルミニウムトリブチレート等のアルミニウムトリアルキレート；アルミニウムアセチルアセテートジプロピレート、アルミニウムアセチルアセテートジブチレート、アルミニウムトリアセチルアセテート、アルミニウムエチルアセトアセテートジプロピレート、アルミニウムトリスエチルアセトアセテート、アルミニウムオクタデシルアセトアセテートジプロピレート等のアルミニウムアルキルアセトアセテート；チタンテトラプロピレート、チタンテトラブチレート等のチタンテトラアルキレート；チタンビス（アセチルアセテート）ジプロピレート等のチタンアルキルアセトアセテート；ジルコニウムテトラブチレート等のジルコニウムテトラアルキレート等が挙げられる。これらの具体的な市販製品としては、例えば、川研ファインケミカル株式会社製のアルミニウム有機化合物シリーズ（「ＡＭＤ」、「ＡＳＢＤ」、「ＡＩＰＤ」、「ＰＡＤＭ」、「アルミニウムエトキサイド」、「ＡＬＣＨ」、「ＡＬＣＨ−ＴＲ」、「アルミキレートＭ」、「アルミキレートＤ」、「アルミキレートＡ、Ａ（Ｗ）」）、味の素ファインテクノ株式会社製「プレンアクト」シリーズ（「ＡＬ−Ｍ」、「ＴＴＳ」）、松本ファインケミカル株式会社製「オルガチックス」シリーズ（「ＡＬ−３００１」、「ＡＬ−３１００」、「ＡＬ−３２００」、「ＡＬ−３２１５」、「ＴＡ−８」、「ＴＡ−２１」、「ＴＡ−２３」、「ＴＡ−３０」、「ＴＣ−１００」、「ＴＣ−４０１」、「ＴＣ−７１０」、「ＴＣ−７５０」、「ＺＡ−４５」、「ＺＡ−６５」、「ＡＣ−１５０」、「ＺＣ−５４０」）等が挙げられる。前記金属錯体（Ｂ）は一種類を単独で用いてもよいし、二種類以上を併用してもよい。 The metal complex (B) is, for example, an aluminum triethyl chelate such as aluminum triethylate, aluminum dipropylate monobutyrate, aluminum tributyrate; aluminum acetyl acetate dipropylate, aluminum acetyl acetate dibutyrate, etc. Aluminum alkylacetate such as aluminum triacetyl acetate, aluminum ethyl acetoacetate dipropylate, aluminum trisethyl acetate, aluminum octadecyl acetoacetate dipropylate; titanium tetraalchelate such as titanium tetrapropylate and titanium tetrabutyrate; titanium bis (Acetyl acetate) Titanium alkyl acetate acetate such as dipropylate; zirconium tetraalchelate such as zirconite tetrabutyrate and the like. Specific examples of these commercially available products include aluminum organic compound series (“AMD”, “ASBD”, “AIPD”, “PADM”, “aluminum ethoxide”, “ALCH”, manufactured by Kawaken Fine Chemicals Co., Ltd. "ALCH-TR", "Aluminum chelate M", "Aluminum chelate D", "Aluminum chelate A, A (W)"), Ajinomoto Fine Techno Co., Ltd. "Plenact" series ("AL-M", "TTS" ), Matsumoto Fine Chemical Co., Ltd. "Organics" series ("AL-3001", "AL-3100", "AL-3200", "AL-3215", "TA-8", "TA-21", " TA-23 "," TA-30 "," TC-100 "," TC-401 "," TC-710 "," TC-750 "," ZA-45 "," ZA-65 "," AC- 150 ”,“ ZC-540 ”) and the like. One type of the metal complex (B) may be used alone, or two or more types may be used in combination.
前記金属錯体（Ｂ）の配合量は所望のインキ性能等に応じて適宜調整可能であるが、特に、流動性が高く印刷面の光沢に優れ、かつ、耐ミスチングや乳化適正等のその他の性能も十分に高い印刷インキとなることから、前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）１００質量部に対し０．５〜２０質量部の範囲であることが好ましく、１〜１５質量部の範囲であることが特に好ましい。 The blending amount of the metal complex (B) can be appropriately adjusted according to the desired ink performance and the like, but in particular, it has high fluidity and excellent gloss on the printed surface, and has other performances such as misting resistance and proper emulsification. Is preferably in the range of 0.5 to 20 parts by mass, and 1 to 15 parts by mass with respect to 100 parts by mass of the acid group-containing urethane (meth) acrylate resin (A), because the printing ink is sufficiently high. The range is particularly preferred.
本発明の組成物は、前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）及び金属錯体（Ｂ）の他、その他の樹脂成分（Ｃ）等、他の成分を含有していてもよい。前記その他の樹脂成分（Ｃ）の一例としては、各種の（メタ）アクリレートモノマー（Ｃ１）、前記（Ａ）成分以外のウレタン（メタ）アクリレート樹脂（Ｃ２）、エポキシ（メタ）アクリレート樹脂（Ｃ３）、ポリエステル（メタ）アクリレート樹脂（Ｃ４）、ケトン樹脂（Ｃ５）、ジアリルフタレート（ＤＡＰ）樹脂（Ｃ６）等が挙げられる。本発明の効果、即ち、酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）と金属錯体（Ｂ）とを含有する組成物を印刷インキ用途に用いることにより、流動性が高く印刷面の光沢に優れる印刷インキになるという効果は、その他の樹脂成分（Ｃ）がどのような樹脂であっても十分に発揮される。したがって、前記その他の樹脂成分（Ｃ）は印刷インキ用に利用可能な各種の樹脂材料を任意に用いることができ、特に限定されるものではないが、具体例の一部を以下に列記する。 The composition of the present invention may contain other components such as the acid group-containing urethane (meth) acrylate resin (A) and the metal complex (B), as well as other resin components (C). Examples of the other resin component (C) include various (meth) acrylate monomers (C1), urethane (meth) acrylate resin (C2) other than the component (A), and epoxy (meth) acrylate resin (C3). , Polyester (meth) acrylate resin (C4), ketone resin (C5), diallyl phthalate (DAP) resin (C6) and the like. By using the effect of the present invention, that is, the composition containing the acid group-containing urethane (meth) acrylate resin (A) and the metal complex (B) for printing ink applications, the fluidity is high and the gloss of the printed surface is excellent. The effect of becoming a printing ink is fully exhibited regardless of the resin having the other resin component (C). Therefore, various resin materials that can be used for printing ink can be arbitrarily used as the other resin component (C), and although not particularly limited, some specific examples are listed below.
前記（メタ）アクリレートモノマー（Ｃ１）は、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート等の脂肪族モノ（メタ）アクリレート化合物；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチルモノ（メタ）アクリレート等の脂環型モノ（メタ）アクリレート化合物；グリシジル（メタ）アクリレート、テトラヒドロフルフリルアクリレート等の複素環型モノ（メタ）アクリレート化合物；ベンジル（メタ）アクリレート、フェノキシ（メタ）アクリレート等の芳香族モノ（メタ）アクリレート化合物；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、等の水酸基含有モノ（メタ）アクリレート化合物；前記各種のモノ（メタ）アクリレート化合物の分子構造中にポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入したポリオキシアルキレン変性モノ（メタ）アクリレート化合物；前記各種のモノ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性モノ（メタ）アクリレート化合物； The (meth) acrylate monomer (C1) is an aliphatic mono (meth) acrylate compound such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; cyclohexyl (meth). ) Alicyclic mono (meth) acrylate compounds such as acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; Aromatic mono (meth) acrylate compounds such as (meth) acrylate and phenoxy (meth) acrylate; hydroxyl group-containing mono (meth) acrylate compounds such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; A polyoxyalkylene-modified mono (meth) acrylate compound in which a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain is introduced into the molecular structure of the (meth) acrylate compound; A lactone-modified mono (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the meta) acrylate compound;
エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等の脂肪族ジ（メタ）アクリレート化合物；ノルボルナンジ（メタ）アクリレート、ノルボルナンジメタノールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート等の脂環型ジ（メタ）アクリレート化合物；ビフェノールジ（メタ）アクリレート、ビスフェノールジ（メタ）アクリレート等の芳香族ジ（メタ）アクリレート化合物；前記各種のジ（メタ）アクリレート化合物の分子構造中にポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入したポリオキシアルキレン変性ジ（メタ）アクリレート化合物；前記各種のジ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性ジ（メタ）アクリレート化合物； An aliphatic di (meth) acrylate compound such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. Alicyclic di (meth) acrylate compounds such as norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate; biphenol Aromatic di (meth) acrylate compounds such as di (meth) acrylate and bisphenol di (meth) acrylate; polyoxyethylene chain, polyoxypropylene chain, polyoxytetra in the molecular structure of the various di (meth) acrylate compounds. Polyoxyalkylene-modified di (meth) acrylate compound introduced with a polyoxyalkylene chain such as a methylene chain; lactone-modified di (meth) having a (poly) lactone structure introduced into the molecular structure of the various di (meth) acrylate compounds. Acrylate compound;
トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等の脂肪族トリ（メタ）アクリレート化合物；ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート等の水酸基含有トリ（メタ）アクリレート化合物；前記各種のトリ（メタ）アクリレート化合物の分子構造中にポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入したポリオキシアルキレン変性トリ（メタ）アクリレート化合物；前記各種のトリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性トリ（メタ）アクリレート化合物； Alidiform tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) A hydroxyl group-containing tri (meth) acrylate compound such as acrylate; a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain was introduced into the molecular structure of the various tri (meth) acrylate compounds. Polyoxyalkylene-modified tri (meth) acrylate compound; A lactone-modified tri (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various tri (meth) acrylate compounds;
ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の４官能以上の脂肪族ポリ（メタ）アクリレート化合物；ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の４官能以上の水酸基含有ポリ（メタ）アクリレート化合物；前記各種のポリ（メタ）アクリレート化合物の分子構造中にポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入した４官能以上のポリオキシアルキレン変性ポリ（メタ）アクリレート化合物；前記各種のポリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入した４官能以上のラクトン変性ポリ（メタ）アクリレート化合物等が挙げられる。 Tetrafunctional or higher functional poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropantetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; dipentaerythritol tetra (meth) acrylate, di. Pentaerythritol Pental (meth) acrylate or other tetrafunctional or higher hydroxyl group-containing poly (meth) acrylate compound; polyoxyethylene chain, polyoxypropylene chain, polyoxytetramethylene in the molecular structure of the various poly (meth) acrylate compounds. 4-functional or higher polyoxyalkylene-modified poly (meth) acrylate compound having a polyoxyalkylene chain such as a chain introduced; tetrafunctional or higher having a (poly) lactone structure introduced into the molecular structure of the various poly (meth) acrylate compounds. Examples thereof include lactone-modified poly (meth) acrylate compounds.
前記ウレタン（メタ）アクリレート樹脂（Ｃ２）は、例えば、各種のポリイソシアネート化合物、水酸基含有（メタ）アクリレート化合物、及び必要に応じて各種のポリオール化合物を反応させて得られるものが挙げられる。これら各反応原料の具体例は、酸基含有前記ウレタン（メタ）アクリレート樹脂（Ａ）の説明にて例示したもの等が挙げられる。 Examples of the urethane (meth) acrylate resin (C2) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as needed. Specific examples of each of these reaction raw materials include those exemplified in the description of the urethane (meth) acrylate resin (A) containing an acid group.
前記エポキシ（メタ）アクリレート化合物（Ｃ３）は、ビスフェノール型エポキシ樹脂や、トリメチロールプロパントリグリシジルエーテル等のエポキシ基含有化合物の（メタ）アクリル酸エステルが挙げられる。エポキシ（メタ）アクリレート化合物（Ｃ３）は分子構造中にポリオキシアルキレン鎖を有するものであってもよい。 Examples of the epoxy (meth) acrylate compound (C3) include a bisphenol type epoxy resin and a (meth) acrylic acid ester of an epoxy group-containing compound such as trimethylolpropane triglycidyl ether. The epoxy (meth) acrylate compound (C3) may have a polyoxyalkylene chain in its molecular structure.
前記ポリエステル（メタ）アクリレート樹脂（Ｃ４）は、分子構造中にポリエステル構造部位を有する（メタ）アクリレート樹脂であればよく、反応原料の一部に油脂や脂肪酸を含むアルキド型や、反応原料の一部にポリイソシアネートを含むウレタン変性型であってもよい。 The polyester (meth) acrylate resin (C4) may be any (meth) acrylate resin having a polyester structural portion in the molecular structure, and may be an alkyd type containing fats and oils or fatty acids as part of the reaction raw material, or one of the reaction raw materials. It may be a urethane modified type containing polyisocyanate in the portion.
本発明の組成物において、前記その他の樹脂成分（Ｃ）の配合量は所望のインキ性能等に応じて適宜調整可能であるが、本発明の効果が一層効果的に奏されることから、前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）、前記金属錯体（Ｂ）及びその他の樹脂成分（Ｃ）の合計に対する前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）と前記金属錯体（Ｂ）との合計質量が０．５〜２０質量％の範囲であることが好ましく、１〜１０質量％の範囲であることがより好ましい。 In the composition of the present invention, the blending amount of the other resin component (C) can be appropriately adjusted according to the desired ink performance and the like, but the effects of the present invention are more effectively exhibited. The acid group-containing urethane (meth) acrylate resin (A) and the metal complex (B) with respect to the total of the acid group-containing urethane (meth) acrylate resin (A), the metal complex (B) and other resin components (C). The total mass of the above is preferably in the range of 0.5 to 20% by mass, and more preferably in the range of 1 to 10% by mass.
本発明の組成物は主に活性エネルギー線硬化型印刷インキ用に好適に用いることができ、照射する活性エネルギー線に応じた光重合開始剤を含有することが好ましい。光重合開始剤としては、例えば、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン等のアルキルフェノン系光重合開始剤；２，４，６−トリメチルベンゾイル−ジフェニル−ホスフィンオキサイド等のアシルホスフィンオキサイド系光重合開始剤；ベンゾフェノン化合物等の分子内水素引き抜き型光重合開始剤等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。また、光重合開始剤の選択は照射する活性エネルギー線の種類等により適切なものを選択して用いればよい。 The composition of the present invention can be suitably used mainly for active energy ray-curable printing inks, and preferably contains a photopolymerization initiator according to the active energy rays to be irradiated. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-. Alkylphenone-based photopolymerization initiators such as [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Acylphosphine oxide-based photopolymerization initiator; Examples thereof include an intramolecular hydrogen abstraction type photopolymerization initiator such as a benzophenone compound. Each of these may be used alone, or two or more types may be used in combination. Further, the photopolymerization initiator may be selected and used depending on the type of active energy ray to be irradiated.
前記光重合開始剤の市販品は、例えば、ＢＡＳＦ社製の「ＩＲＧＡＣＵＲＥ」シリーズ（「ＩＲＧＡＣＵＲＥ１２７」、「ＩＲＧＡＣＵＲＥ１８４」、「ＩＲＧＡＣＵＲＥ２５０」、「ＩＲＧＡＣＵＲＥ２７０」、「ＩＲＧＡＣＵＲＥ２９０」、「ＩＲＧＡＣＵＲＥ３６９Ｅ」、「ＩＲＧＡＣＵＲＥ３７９ＥＧ」、「ＩＲＧＡＣＵＲＥ５００」、「ＩＲＧＡＣＵＲＥ６５１」、「ＩＲＧＡＣＵＲＥ７５４」、「ＩＲＧＡＣＵＲＥ８１９」、「ＩＲＧＡＣＵＲＥ９０７」、「ＩＲＧＡＣＵＲＥ１１７３」、「ＩＲＧＡＣＵＲＥ２９５９」、「ＩＲＧＡＣＵＲＥ ＭＢＦ」、「ＩＲＧＡＣＵＲＥ ＴＰＯ」、「ＩＲＧＡＣＵＲＥ ＯＸＥ ０１」、「ＩＲＧＡＣＵＲＥ ＯＸＥ ０２」）、ＩＧＭ ＲＥＳＩＮＳ社製の「ＯＭＮＩＲＡＤ」シリーズ（「ＯＭＮＩＲＡＤ１８４」、「ＯＭＮＩＲＡＤ２５０」、「ＯＭＮＩＲＡＤ３６９」、「ＯＭＮＩＲＡＤ３６９Ｅ」、「ＯＭＮＩＲＡＤ６５１」、「ＯＭＮＩＲＡＤ９０７ＦＦ」、「ＯＭＮＩＲＡＤ１１７３」）、大同化成工業株式会社製「ＤＡＩＤＯ ＵＶ−ＣＵＲＥ」シリーズ、「ＢＥＮＺＯＰＨＥＮＯＮＥ」、「ＰＨＯＴＯＣＵＲＥ ５０」、「ＰＨＯＴＯＣＵＲＥ ５５０」、「ＥＡＢ−ＳＳ」等が挙げられる。これら光重合開始剤は組成物の合計１００質量部中０．０５〜２０質量部程度の範囲で用いることが好ましい。 Commercially available products of the photopolymerization initiator are, for example, "IRGACURE" series ("IRGACURE127", "IRGACURE184", "IRGACURE250", "IRGACURE270", "IRGACURE290", "IRGACURE369E", "IRGACURE379EG", "IRGACURE379EG" manufactured by BASF. IRGACURE500, "IRGACURE651", "IRGACURE754", "IRGACURE819", "IRGACURE907", "IRGACURE1173", "IRGACURE2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE", "IRGACURE", "IRGACURE" "OMNIRAD" series ("OMNIRAD184", "OMNIRAD250", "OMNIRAD369", "OMNIRAD369E", "OMNIRAD651", "OMNIRAD907FF", "OMNIRAD1173") manufactured by IGM RESINS, "DAIDOUV" manufactured by Daido Kasei Kogyo Co., Ltd. Series, "BENZOPHENONE", "PHOTOCURE 50", "PHOTOCURE 550", "EAB-SS" and the like. These photopolymerization initiators are preferably used in the range of about 0.05 to 20 parts by mass out of a total of 100 parts by mass of the composition.
本発明の組成物は、前記重合開始剤と併せて光増感剤を含有しても良い。前記光増感剤は、例えば、脂肪族アミン等のアミン化合物、ｏ−トリルチオ尿素等の尿素類、ナトリウムジエチルジチオホスフェート、ｓ−ベンジルイソチウロニウム−ｐ−トルエンスルホネート等の硫黄化合物などが挙げられる。これら光増感剤は組成物の合計１００質量部中０．１〜１０質量部程度の範囲で用いることが好ましい。 The composition of the present invention may contain a photosensitizer in addition to the polymerization initiator. Examples of the photosensitizer include amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfonate. .. These photosensitizers are preferably used in the range of about 0.1 to 10 parts by mass out of a total of 100 parts by mass of the composition.
本発明の組成物は、更に、顔料、染料、体質顔料、有機又は無機フィラー、有機溶剤、帯電防止剤、消泡剤、粘度調整剤、重合禁止剤、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、レベリング剤、顔料分散剤、ワックス等、通常の印刷インキが含有する各種の添加剤を含有しても良い。 The composition of the present invention further comprises pigments, dyes, extender pigments, organic or inorganic fillers, organic solvents, antistatic agents, defoamers, viscosity modifiers, polymerization inhibitors, light-resistant stabilizers, weather-resistant stabilizers, and heat-resistant stabilizers. It may contain various additives contained in ordinary printing inks such as agents, ultraviolet absorbers, antioxidants, leveling agents, pigment dispersants, and waxes.
前記顔料は、公知公用の着色用有機顔料を挙げることができ、例えば「有機顔料ハンドブック（著者：橋本勲、発行所：カラーオフィス、２００６年初版）」に掲載される印刷インキ用有機顔料等が挙げられ、溶性アゾ顔料、不溶性アゾ顔料、縮合アゾ顔料、金属フタロシアニン顔料、無金属フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ペリノン顔料、イソインドリノン顔料、イソインドリン顔料、ジオキサジン顔料、チオインジゴ顔料、アンスラキノン系顔料、キノフタロン顔料、金属錯体顔料、ジケトピロロピロール顔料、カーボンブラック顔料、その他多環式顔料等が使用可能である。これら顔料の添加量は顔料の種類等により最適値が異なるが、組成物の合計１００質量部に対し５〜３０質量部となる範囲であることが好ましい。 Examples of the pigment include publicly known and publicly available organic pigments for coloring, such as organic pigments for printing inks published in "Organic Pigments Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)". Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, thioindigo pigments, anthracinone System pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, other polycyclic pigments and the like can be used. The optimum value of the amount of these pigments added varies depending on the type of pigment and the like, but it is preferably in the range of 5 to 30 parts by mass with respect to 100 parts by mass in total of the composition.
前記体質顔料は、例えば、酸化チタン、クラファイト、亜鉛、炭酸石灰粉、沈降性炭酸カルシウム、石膏、クレイ、シリカ粉、珪藻土、タルク、カオリン、アルミナホワイト、硫酸バリウム、ステアリン酸アルミニウム、炭酸マグネシウム、バライト粉、ガラスビーズ等が上げられる。これら体質顔料の添加量は顔料の種類等により最適値が異なるが、組成物の合計１００質量部に対し０．１〜２０質量部となる範囲であることが好ましい。 The extender pigments include, for example, titanium oxide, clafite, zinc, lime carbonate powder, precipitated calcium carbonate, gypsum, clay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, and the like. Barite powder, glass beads, etc. can be raised. The optimum value of the amount of these extender pigments added varies depending on the type of pigment and the like, but it is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the composition.
本発明の組成物及び印刷インキにおいて各成分の配合割合等は特に限定されず、目的の印刷用途や性能等に応じて適宜配合物や配合割合を調整することができる。各成分は全て一括で配合してもよいし、一部を先に配合してプレミックスを作った後にその他の成分と配合するなどの分割配合でもよい。混合方法は特に限定されず、ミキサー等で撹拌混合する方法、三本ロールミルを用いる方法、ビーズミル等の分散機を用いる方法等が挙げられる。 In the composition and printing ink of the present invention, the blending ratio of each component is not particularly limited, and the blending ratio and blending ratio can be appropriately adjusted according to the target printing application and performance. Each component may be blended all at once, or a part may be blended first to make a premix and then blended with other ingredients. The mixing method is not particularly limited, and examples thereof include a method of stirring and mixing with a mixer or the like, a method of using a three-roll mill, a method of using a disperser such as a bead mill, and the like.
本発明の印刷インキは、活性エネルギー線を照射することにより硬化させることができる。前記活性エネルギー線は、例えば、紫外線、電子線、α線、β線、γ線のような電離放射線が挙げられる。光源としては、例えば、殺菌灯、紫外線用蛍光灯、ＵＶ−ＬＥＤ、カーボンアーク、キセノンランプ、複写用高圧水銀灯、中圧又は高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、自然光等を光源とする紫外線、走査型やカーテン型の電子線加速器による電子線等が挙げられる。 The printing ink of the present invention can be cured by irradiating it with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Light sources include, for example, germicidal lamps, fluorescent lamps for ultraviolet rays, UV-LEDs, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, and the like. Examples thereof include ultraviolet rays, electron beams generated by scanning type or curtain type electron beam accelerators.
本発明の印刷インキは、紙や各種のプラスチックフィルム等、様々な基材に対し印刷することができる。具体的には、カタログ、ポスター、チラシ、ＣＤジャケット、ダイレクトメール、パンフレット、化粧品や飲料、医薬品、おもちゃ、機器等のパッケージ等に用いる紙基材；ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム等、食品や飲料、化粧品等の包装資材用のプラスチックフィルム基材；アルミニウムホイル、合成紙、その他従来から印刷基材として使用されている各種基材を印刷対象物とすることができる。 The printing ink of the present invention can be printed on various substrates such as paper and various plastic films. Specifically, paper base materials used for packaging of catalogs, posters, leaflets, CD jackets, direct mails, brochures, cosmetics and beverages, pharmaceuticals, toys, equipment, etc .; polypropylene films, polyethylene terephthalate films, foods and beverages, etc. Plastic film base material for packaging materials such as cosmetics; aluminum foil, synthetic paper, and various other base materials conventionally used as printing base materials can be used as printing objects.
本発明の印刷インキの印刷方式は特に限定されず、例えば、平版オフセット印刷、凸版印刷、グラビア印刷、グラビアオフセット印刷、フレキソ印刷、スクリーン印刷等により印刷することができる。これらの中でも特に、版面に水を連続的に供給する平版オフセット印刷において好適に利用することができる。水を連続供給するオフセット印刷機は多数の印刷機メーカーによって製造販売されており、一例としてハイデルベルグ社、小森コーポレーション社、リョービＭＨＩグラフィックテクノロジー社、マンローランド社、ＫＢＡ社等を挙げることができ、またシート形態の印刷用紙を用いる枚葉オフセット印刷機、リール形態の印刷用紙を用いるオフセット輪転印刷機、いずれの用紙供給方式においても本発明を好適に利用することが可能である。更に具体的には、ハイデルベルグ社製スピードマスターシリーズ、小森コーポレーション社製リスロンシリーズ、リョービＭＨＩグラフィックテクノロジー社製ダイヤモンドシリーズ等のオフセット印刷機を挙げることができる。 The printing method of the printing ink of the present invention is not particularly limited, and for example, printing can be performed by flat plate offset printing, letterpress printing, gravure printing, gravure offset printing, flexo printing, screen printing, or the like. Among these, it can be suitably used in lithographic offset printing in which water is continuously supplied to the plate surface. Offset printing machines that continuously supply water are manufactured and sold by a large number of printing machine manufacturers. Examples include Heidelberg, Komori Corporation, Ryobi MHI Graphic Technology, Munroland, KBA, etc. The present invention can be suitably used in any paper supply method, such as a sheet-fed offset printing machine that uses sheet-type printing paper and an offset rotary printing machine that uses reel-type printing paper. More specifically, offset printing machines such as the Speedmaster series manufactured by Heidelberg, the Lithrone series manufactured by Komori Corporation, and the diamond series manufactured by Ryobi MHI Graphic Technology can be mentioned.
以下、実施例により本発明をより詳細に説明する。なお、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples.
赤外吸収スペクトルの測定
［機種］ 日本分光株式会社製 ＦＴ／ＩＲ−４１００
［測定条件］イソシアネート基を示す２２５０ｃｍ-1の赤外吸収スペクトルを確認することで反応完結を確認した。Measurement of infrared absorption spectrum [Model] FT / IR-4100 manufactured by JASCO Corporation
[Measurement conditions] The reaction completion was confirmed by confirming the infrared absorption spectrum of 2250 cm -1 showing the isocyanate group.
質量平均分子量（Ｍｗ）の測定
下記条件のゲルパーミアーションクロマトグラフィー（ＧＰＣ）により測定した。
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）Measurement of mass average molecular weight (Mw) Measurement was performed by gel permeation chromatography (GPC) under the following conditions.
Measuring device; HLC-8220GPC manufactured by Tosoh Corporation
Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)
酸価の測定条件
ＪＩＳ Ｋ ００７０（１９９２）の中和滴定法にて測定した。Acid Value Measurement Conditions Measured by the neutralization titration method of JIS K 0070 (1992).
製造例１ ウレタン（メタ）アクリレート樹脂（Ａ−１）の製造
攪拌機、ガス導入管、コンデンサー及び温度計を備えたフラスコに、ラクトン変性ヒドロキシエチルアクリレート（株式会社ダイセル製「プラクセルＦＡ２Ｄ」）１８７．１質量部、１２−ヒドロキシステアリン酸１６．１質量部、Ｎ−ニトロソ−Ｎ−フェニルヒドロキシルアミンアルミニウム０．１７質量部を加え、６５℃まで加熱した。イソシアヌレート変性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株式会社製「スミジュールＮ３３００」）１０８．６質量部を１時間かけて滴下した。滴下終了後、９５℃まで加熱して２時間反応させた。イソシアネート基を示す２２５０ｃｍ−１の赤外吸収スペクトルが消失したのを確認し、目的のウレタン（メタ）アクリレート樹脂（Ａ−１）を得た。ウレタン（メタ）アクリレート樹脂（Ａ−１）の質量平均分子量（Ｍｗ）は４，４７７、酸価は１１．２ｍｇＫＯＨ/ｇであった。Production Example 1 Production of Urethane (Meta) Acrylate Resin (A-1) In a flask equipped with a stirrer, a gas introduction tube, a condenser and a thermometer, a lactone-modified hydroxyethyl acrylate (“Placel FA2D” manufactured by Daicel Co., Ltd.) 187.1 By weight, 16.1 parts by mass of 12-hydroxystearic acid and 0.17 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added, and the mixture was heated to 65 ° C. 108.6 parts by mass of isocyanurate-modified hexamethylene diisocyanate (“Sumijour N3300” manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After completion of the dropping, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm -1 showing an isocyanate group had disappeared, and the target urethane (meth) acrylate resin (A-1) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-1) was 4,477, and the acid value was 11.2 mgKOH / g.
製造例２ ウレタン（メタ）アクリレート樹脂（Ａ−２）の製造
攪拌機、ガス導入管、コンデンサー及び温度計を備えたフラスコに、ラクトン変性ヒドロキシエチルアクリレート（株式会社ダイセル製「プラクセルＦＡ２Ｄ」）１４３．３質量部、１２−ヒドロキシステアリン酸６．０質量部、Ｎ−ニトロソ−Ｎ−フェニルヒドロキシルアミンアルミニウム０．１２質量部を加え、６５℃まで加熱した。イソシアヌレート変性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株式会社製「スミジュールＮ３３００」）７９．８質量部を１時間かけて滴下した。滴下終了後、９５℃まで加熱して２時間反応させた。イソシアネート基を示す２２５０ｃｍ−１の赤外吸収スペクトルが消失したのを確認し、目的のウレタン（メタ）アクリレート樹脂（Ａ−２）を得た。ウレタン（メタ）アクリレート樹脂（Ａ−２）の質量平均分子量（Ｍｗ）は４，２７５、酸価は６．０ｍｇＫＯＨ/ｇであった。Production Example 2 Production of Urethane (Meta) Acrylate Resin (A-2) In a flask equipped with a stirrer, a gas introduction tube, a condenser and a thermometer, a lactone-modified hydroxyethyl acrylate (“Placel FA2D” manufactured by Daicel Co., Ltd.) 143.3 A parts by mass, 6.0 parts by mass of 12-hydroxystearic acid and 0.12 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added, and the mixture was heated to 65 ° C. 79.8 parts by mass of isocyanurate-modified hexamethylene diisocyanate (“Sumijour N3300” manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After completion of the dropping, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm -1 showing an isocyanate group had disappeared, and the target urethane (meth) acrylate resin (A-2) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-2) was 4,275, and the acid value was 6.0 mgKOH / g.
製造例３ ウレタン（メタ）アクリレート樹脂（Ａ−３）の製造
攪拌機、ガス導入管、コンデンサー及び温度計を備えたフラスコに、ラクトン変性ヒドロキシエチルアクリレート（株式会社ダイセル製「プラクセルＦＡ２Ｄ」）１１６．４質量部、１２−ヒドロキシステアリン酸３１．３質量部、Ｎ−ニトロソ−Ｎ−フェニルヒドロキシルアミンアルミニウム０．１２質量部を加え、６５℃まで加熱した。イソシアヌレート変性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株式会社製「スミジュールＮ３３００」）７９．１質量部を１時間かけて滴下した。滴下終了後、９５℃まで加熱して２時間反応させた。イソシアネート基を示す２２５０ｃｍ−１の赤外吸収スペクトルが消失したのを確認し、目的のウレタン（メタ）アクリレート樹脂（Ａ−３）を得た。ウレタン（メタ）アクリレート樹脂（Ａ−３）の質量平均分子量（Ｍｗ）は４，６６３、酸価は２７．３ｍｇＫＯＨ/ｇであった。Production Example 3 Production of Urethane (Meta) Acrylate Resin (A-3) In a flask equipped with a stirrer, a gas introduction tube, a condenser and a thermometer, a lactone-modified hydroxyethyl acrylate (“Placel FA2D” manufactured by Daicel Co., Ltd.) 116.4 By weight, 31.3 parts by mass of 12-hydroxystearic acid and 0.12 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added, and the mixture was heated to 65 ° C. 79.1 parts by mass of isocyanurate-modified hexamethylene diisocyanate (“Sumijour N3300” manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After completion of the dropping, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm -1 showing an isocyanate group had disappeared, and the target urethane (meth) acrylate resin (A-3) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-3) was 4,663, and the acid value was 27.3 mgKOH / g.
製造例４ ウレタン（メタ）アクリレート樹脂（Ａ−４）の製造
攪拌機、ガス導入管、コンデンサー及び温度計を備えたフラスコに、ラクトン変性ヒドロキシエチルアクリレート（株式会社ダイセル製「プラクセルＦＡ２Ｄ」）２０１．４質量部、グリコール酸３．８質量部、Ｎ−ニトロソ−Ｎ−フェニルヒドロキシルアミンアルミニウム０．１７質量部を加え、６５℃まで加熱した。イソシアヌレート変性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株式会社製「スミジュールＮ３３００」）１１６．７質量部を１時間かけて滴下した。滴下終了後、９５℃まで加熱して２時間反応させた。イソシアネート基を示す２２５０ｃｍ−１の赤外吸収スペクトルが消失したのを確認し、目的のウレタン（メタ）アクリレート樹脂（Ａ−４）を得た。ウレタン（メタ）アクリレート樹脂（Ａ−４）の質量平均分子量（Ｍｗ）は４，１３５、酸価は８．９ｍｇＫＯＨ/ｇであった。Production Example 4 Production of Urethane (Meta) Acrylate Resin (A-4) Lactone-modified hydroxyethyl acrylate (“Placel FA2D” manufactured by Daicel Co., Ltd.) 201.4 in a flask equipped with a stirrer, gas introduction tube, condenser and thermometer. A parts by mass, 3.8 parts by mass of glycolic acid, and 0.17 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added and heated to 65 ° C. 116.7 parts by mass of isocyanurate-modified hexamethylene diisocyanate (“Sumijour N3300” manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After completion of the dropping, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm -1 showing an isocyanate group had disappeared, and the target urethane (meth) acrylate resin (A-4) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-4) was 4,135, and the acid value was 8.9 mgKOH / g.
製造例５ ウレタン（メタ）アクリレート樹脂（Ａ−５）の製造
攪拌機、ガス導入管、コンデンサー及び温度計を備えたフラスコに、ラクトン変性ヒドロキシエチルアクリレート（株式会社ダイセル製「プラクセルＦＡ２Ｄ」）１６７．９質量部、ジメチロールプロピオン酸３．４質量部、Ｎ−ニトロソ−Ｎ−フェニルヒドロキシルアミンアルミニウム０．１７質量部を加え、６５℃まで加熱した。イソシアヌレート変性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株式会社製「スミジュールＮ３３００」）１１６．９質量部を１時間かけて滴下した。滴下終了後、９５℃まで加熱して２時間反応させた。イソシアネート基を示す２２５０ｃｍ−１の赤外吸収スペクトルが消失したのを確認し、目的のウレタン（メタ）アクリレート樹脂（Ａ−５）を得た。ウレタン（メタ）アクリレート樹脂（Ａ−５）の質量平均分子量（Ｍｗ）は４，３８９、酸価は５．５ｍｇＫＯＨ/ｇであった。Production Example 5 Production of Urethane (Meta) Acrylate Resin (A-5) In a flask equipped with a stirrer, gas introduction tube, condenser and thermometer, lactone-modified hydroxyethyl acrylate (“Plaxel FA2D” manufactured by Daicel Co., Ltd.) 167.9 A parts by mass, 3.4 parts by mass of dimethylol propionic acid, and 0.17 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added and heated to 65 ° C. 116.9 parts by mass of isocyanurate-modified hexamethylene diisocyanate (“Sumijour N3300” manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After completion of the dropping, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm- 1 showing an isocyanate group had disappeared, and the target urethane (meth) acrylate resin (A-5) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-5) was 4,389, and the acid value was 5.5 mgKOH / g.
実施例１〜７ 組成物（１）〜（８）の製造
下記表１に示す割合で各成分を配合し、１時間撹拌して組成物（１）〜（８）を得た。金属錯体の詳細は以下の通り。
・（メタ）アクリレートモノマー：ダイセル・オルネクス株式会社製「ＯＴＡ ４８０」、プロピレンオキサイド変性グリセリントリアクリレート、１分子あたりのプロピレンオキサイド平均付加数３
・金属錯体（Ｂ−１）：川研ファインケミカル株式会社製「ＡＬＣＨ−ＴＲ」、アルミニウムトリス（エチルアセトアセテート）
・金属錯体（Ｂ−２）：味の素ファインテクノ株式会社製「プレンアクト ＡＬ−Ｍ」、アルミニウムアルキルアセトアセテートジイソプロピレートExamples 1 to 7 Production of Compositions (1) to (8) Compositions (1) to (8) were obtained by blending each component in the ratio shown in Table 1 below and stirring for 1 hour. Details of the metal complex are as follows.
(Meta) acrylate monomer: "OTA 480" manufactured by Daicel Ornex Co., Ltd., propylene oxide-modified glycerin triacrylate, average addition number of propylene oxide per molecule 3
-Metal complex (B-1): "ALCH-TR" manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum tris (ethylacetacetate)
-Metal complex (B-2): "Plenact AL-M" manufactured by Ajinomoto Fine-Techno Co., Ltd., aluminum alkyl acetoacetate diisopropylate
実施例９〜２１及び比較例１ 印刷インキの製造
下記表３〜５に示す割合で各成分を配合し、ミキサー（単軸ディゾルバー）で撹拌した後、３本ロールミルを用いて練肉して印刷インキを得た。実施例１４については、組成物（１）以外の成分を配合してミキサー（単軸ディゾルバー）で撹拌し、３本ロールミルを用いて練肉した後、組成物（１）を添加して混合し、印刷インキを得た。
得られた印刷インキについて下記の要領で種々の評価を行った。結果を表３〜５に示す。Examples 9 to 21 and Comparative Example 1 Production of printing inks Each component is mixed in the proportions shown in Tables 3 to 5 below, stirred with a mixer (single-axis dissolver), and then kneaded and printed using a three-roll mill. Obtained ink. In Example 14, components other than the composition (1) were mixed, stirred with a mixer (uniaxial dissolver), kneaded using a three-roll mill, and then the composition (1) was added and mixed. , Obtained printing ink.
The obtained printing ink was evaluated in various ways as follows. The results are shown in Tables 3-5.
製造例６ ウレタン（メタ）アクリレート樹脂の製造
撹拌機、ガス導入管、コンデンサー、及び温度計を備えた四つ口フラスコにポリメリックジフェニルメタンジイソシアネート（日本ポリウレタン工業株式会社製「ミリオネートＭＲ−４００」）６０．３質量部、ターシャリブチルヒドロキシトルエン０．１質量部、メトキシハイドロキノン０．０２質量部、オクチル酸亜鉛０．０２質量部を加え、７５℃まで加熱した。フラスコ内を撹拌しながら２−ヒドロキシエチルアクリレート３５．７質量部を１時間かけて滴下した。滴下終了後、７５℃で更に３時間反応させた。グリセリン４．０質量部を添加し、７５℃で反応を続け、イソシアネート基を示す２２５０ｃｍ−１の赤外吸収スペクトルが消失したのを確認し、ウレタン（メタ）アクリレート樹脂を得た。Production Example 6 Production of urethane (meth) acrylate resin Polymeric diphenylmethane diisocyanate (“Millionate MR-400” manufactured by Nippon Polyurethane Industry Co., Ltd.) in a four-necked flask equipped with a stirrer, gas introduction tube, condenser, and thermometer 60. 3 parts by mass, 0.1 part by mass of tertiary butyl hydroxytoluene, 0.02 part by mass of methoxyhydroquinone, and 0.02 part by mass of zinc octylate were added and heated to 75 ° C. While stirring the inside of the flask, 35.7 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 1 hour. After completion of the dropping, the reaction was carried out at 75 ° C. for another 3 hours. 4.0 parts by mass of glycerin was added, and the reaction was continued at 75 ° C., and it was confirmed that the infrared absorption spectrum of 2250 cm -1 showing an isocyanate group disappeared, and a urethane (meth) acrylate resin was obtained.
流動性の評価
２５℃に空調した室内において、地平面と７０゜の角度をなすガラス板の上端に印刷インキ１．０ｍｌを置き、１日後に流動した距離を測定した。数値が大きいほど流動性が良好であることを示す。Evaluation of fluidity In a room air-conditioned at 25 ° C, 1.0 ml of printing ink was placed on the upper end of a glass plate at an angle of 70 ° with the ground plane, and the distance of fluidity was measured one day later. The larger the value, the better the fluidity.
展色物の作製方法
簡易展色機（豊栄精工社製「ＲＩテスター」）を用い、印刷インキ０．１０ｍｌをＲＩテスターのゴムロール及び金属ロール上に均一に引き伸ばした。アート紙（王子製紙社製「ＯＫ金藤片面」）の表面に、２００ｃｍ２の面積にわたって黄濃度１．４（Ｘ−Ｒｉｔｅ社製「ＳｐｅｃｔｒｏＥｙｅ濃度計」で計測）で均一に塗布されるように展色し、展色物を作製した。なおＲＩテスターとは、紙やフィルムにインキを展色する試験機であり、インキの転移量や印圧を調整することが可能である。Method for Producing Color-Expanded Material Using a simple color-developing machine (“RI tester” manufactured by Hoei Seiko Co., Ltd.), 0.10 ml of printing ink was uniformly spread on a rubber roll and a metal roll of the RI tester. Spread so that it is evenly applied to the surface of art paper ("OK Kanto one side" manufactured by Oji Paper Co., Ltd.) with a yellow density of 1.4 (measured with "SpectroEye densitometer" manufactured by X-Rite) over an area of 200 cm 2. Colored and made a colored product. The RI tester is a testing machine that spreads ink on paper or film, and can adjust the amount of ink transfer and printing pressure.
紫外線（ＵＶ）ランプ光源による硬化方法
先で得た展色物に紫外線（ＵＶ）を照射し、印刷インキを硬化させた。具体的には、水冷メタルハライドランプ（出力１２０Ｗ／ｃｍ１灯）およびベルトコンベアを搭載した紫外線（ＵＶ）照射装置（アイグラフィックス社製、コールドミラー付属）を使用し、展色物をコンベア上に載せ、ランプ直下（照射距離１１ｃｍ）を分速４０メートルの速度で通過させることにより、印刷インキを硬化させた。Curing method using an ultraviolet (UV) lamp light source The printed ink was cured by irradiating the developed color obtained above with ultraviolet (UV). Specifically, a water-cooled metal halide lamp (output 120 W / cm 1 lamp) and an ultraviolet (UV) irradiation device equipped with a belt conveyor (manufactured by Eye Graphics, attached to a cold mirror) are used to place the colored object on the conveyor. The printing ink was cured by passing directly under the lamp (irradiation distance 11 cm) at a speed of 40 meters per minute.
印刷面の光沢
硬化後の展色物における印刷面の光沢値を６０°光沢計（ＢＹＫ Ｇａｒｄｅｒ ＧｍｂＨ製）で測定し、次の３段階で評価した。数値が高い程、光沢が良い事を示す。
（評価基準）
Ａ：光沢５５以上
Ｂ：光沢４５以上 ５５未満
Ｃ：光沢４５未満Gloss of printed surface The gloss value of the printed surface of the developed color after curing was measured with a 60 ° gloss meter (manufactured by BYK Gardener GmbH) and evaluated in the following three stages. The higher the value, the better the gloss.
(Evaluation criteria)
A: Gloss 55 or more B: Gloss 45 or more and less than 55 C: Gloss less than 45
Claims (6)
前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）、前記金属錯体（Ｂ）及び前記その他の樹脂成分（Ｃ）の合計に対する前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）と前記金属錯体（Ｂ）との合計質量が０．５〜２０質量％の範囲であり、
前記酸基含有ウレタン（メタ）アクリレート樹脂（Ａ）１００質量部に対する前記金属錯体（Ｂ）の配合量が０．５〜２０質量部の範囲である印刷インキ。 A printing ink using a composition containing an acid group-containing urethane (meth) acrylate resin (A), a metal complex (B), and another resin component (C).
The acid group-containing urethane (meth) acrylate resin (A) and the metal complex (A) with respect to the total of the acid group-containing urethane (meth) acrylate resin (A), the metal complex (B) and the other resin component (C). B) ranges der total mass of 0.5 to 20 mass% with is,
A printing ink in which the blending amount of the metal complex (B) with respect to 100 parts by mass of the acid group-containing urethane (meth) acrylate resin (A) is in the range of 0.5 to 20 parts by mass .
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| TWI796344B (en) | 2023-03-21 |
| JPWO2019017270A1 (en) | 2020-05-28 |
| CN110945044A (en) | 2020-03-31 |
| WO2019017270A1 (en) | 2019-01-24 |
| CN110945044B (en) | 2023-04-04 |
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