WO2022163449A1 - Colored resin composition, colored film, and decorative substrate - Google Patents
Colored resin composition, colored film, and decorative substrate Download PDFInfo
- Publication number
- WO2022163449A1 WO2022163449A1 PCT/JP2022/001701 JP2022001701W WO2022163449A1 WO 2022163449 A1 WO2022163449 A1 WO 2022163449A1 JP 2022001701 W JP2022001701 W JP 2022001701W WO 2022163449 A1 WO2022163449 A1 WO 2022163449A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- mass
- colored
- colored resin
- group
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 95
- 239000000758 substrate Substances 0.000 title claims description 23
- 239000003086 colorant Substances 0.000 claims abstract description 89
- 239000011347 resin Substances 0.000 claims abstract description 83
- 229920005989 resin Polymers 0.000 claims abstract description 83
- 239000002253 acid Chemical group 0.000 claims abstract description 73
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 67
- 239000002270 dispersing agent Substances 0.000 claims abstract description 59
- 239000012948 isocyanate Substances 0.000 claims abstract description 31
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims description 45
- 239000002981 blocking agent Substances 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- 125000001302 tertiary amino group Chemical group 0.000 claims description 5
- 150000003217 pyrazoles Chemical class 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 21
- 239000006185 dispersion Substances 0.000 description 114
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 73
- 239000011324 bead Substances 0.000 description 47
- 239000000463 material Substances 0.000 description 43
- 238000004040 coloring Methods 0.000 description 38
- 239000004094 surface-active agent Substances 0.000 description 35
- 238000004519 manufacturing process Methods 0.000 description 31
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 239000000049 pigment Substances 0.000 description 20
- 229920001296 polysiloxane Polymers 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- -1 polyazo Polymers 0.000 description 12
- 239000004925 Acrylic resin Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000976 ink Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000012860 organic pigment Substances 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000001054 red pigment Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000001023 inorganic pigment Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000007607 die coating method Methods 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001055 blue pigment Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000007646 gravure printing Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000001052 yellow pigment Substances 0.000 description 3
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
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- 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
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- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
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- OWSKJORLRSWYGK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) propanoate Chemical compound CCC(=O)OCCC(C)(C)OC OWSKJORLRSWYGK-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- XUKSWKGOQKREON-UHFFFAOYSA-N 1,4-diacetoxybutane Chemical compound CC(=O)OCCCCOC(C)=O XUKSWKGOQKREON-UHFFFAOYSA-N 0.000 description 1
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- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
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- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
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- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 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
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical compound CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- YSGBMDFJWFIEDF-UHFFFAOYSA-N methyl 2-hydroxy-3-methylbutanoate Chemical compound COC(=O)C(O)C(C)C YSGBMDFJWFIEDF-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical group 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005192 partition 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
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether 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
- 239000002243 precursor Substances 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 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
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical group C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- YKSGNOMLAIJTLT-UHFFFAOYSA-N violanthrone Chemical compound C12=C3C4=CC=C2C2=CC=CC=C2C(=O)C1=CC=C3C1=CC=C2C(=O)C3=CC=CC=C3C3=CC=C4C1=C32 YKSGNOMLAIJTLT-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 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
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/22—Dyes with unsubstituted amino groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/22—Monoazo compounds containing other metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B7/00—Indigoid dyes
-
- 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
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
Definitions
- the present invention relates to colored resin compositions, colored films, and decorative substrates.
- Touch panels in various information terminals such as smartphones and in-vehicle displays have a light-shielding film formed in the non-display area of the cover lens, which is located on the outermost layer when viewed from the user side, and the light-shielding film hides electrodes such as the lead-out wiring of the touch sensor. have a role to play.
- In-vehicle displays and smartwatches require reliability such that operability and design do not change even under ultraviolet irradiation of sunlight or in high temperature and high humidity environments. It is required that it does not decrease.
- Patent Document 1 discusses an inkjet printing ink containing a carboxyl group-containing binder polymer having a weight average molecular weight of 20,000 to 300,000 and a curing agent containing a blocked isocyanate and an epoxy resin.
- Patent Document 2 as an ink that can be printed on a non-heat-resistant, non-absorbent medium and that can be cured at a low temperature, an acrylic resin containing a glycol ether-based solvent and an acetate solvent and having a hydroxyl group and a low-temperature Ink jet printing inks containing dissociated blocked isocyanates have been investigated.
- the ink described in Patent Document 1 can maintain high adhesion even after various reliability tests by using both a blocked isocyanate and an epoxy resin. Therefore, when used for long-term printing, the film thickness and printing accuracy change, resulting in insufficient viscosity stability.
- the ink described in Patent Document 2 can be cured at a low temperature and has excellent viscosity stability. It lacked features.
- the object of the present invention is to provide a colored resin composition that can be cured at a low temperature, has excellent viscosity stability at room temperature, and maintains high adhesion even after a light resistance test and a high temperature and high humidity test.
- a colored resin composition contains a hydroxyl- or acid-containing resin, a coloring agent, a dispersant, and a blocked isocyanate, and an acrylic dispersant having a basic group as a dispersant.
- the inventors have found that the above problems can be solved by applying the method, and completed the present invention.
- the object of the present invention is mainly achieved by the following configurations.
- the colored resin composition of the present invention can be cured at a low temperature and has excellent viscosity stability at room temperature, so that a colored film that maintains high adhesion even after a light resistance test and a high temperature and high humidity test can be obtained.
- the colored resin composition of the present invention contains (A) a hydroxyl group- or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate.
- A The hydroxyl group- or acid group-containing resin acts as a binder in the composition.
- B The coloring agent has the effect of shielding visible light.
- C The dispersing agent has the function of dispersing the coloring material uniformly and preventing reaggregation.
- the blocked isocyanate has the action of reacting with hydroxyl groups or acid groups contained in the resin only during heating and baking.
- the present invention is characterized in that the (C) dispersant is an acrylic dispersant having a basic group.
- Acrylic dispersants are excellent in reliability such as light resistance and high temperature and high humidity resistance. Furthermore, since the dispersant has a basic group, the dispersant adsorbs to the surface of the coloring agent, finely disperses the coloring agent when dispersing the coloring agent, stabilizes the dispersion state due to steric hindrance between the dispersing agents, and increases over time. It has the effect of suppressing stickiness and reaggregation.
- (D) blocked isocyanate does not have reactivity due to the function of the blocking agent at room temperature, and has reactivity only when heated, so that the viscosity stability of the colored resin composition can be maintained well, and the blocking agent is used.
- the blocking agent can dissociate at low temperatures and react with hydroxyl groups or acid groups.
- a hydroxyl- or acid-group-containing resin is a resin having a hydroxyl group or an acid group.
- hydroxyl group- or acid group-containing resins include acrylic resins, cardo resins, siloxane resins, polyimide resins, polyimide precursors, polyurethane resins, polyester resins, and vinyl chloride resins. You may contain 2 or more types of these. Among these, acrylic resins, polyurethane resins and polyester resins are preferred, and acrylic resins are particularly preferred, from the viewpoint of storage stability of the colored resin composition and adhesion and reliability of the colored film.
- the hydroxyl or acid group-containing resin has a hydroxyl value or acid value of 10 mgKOH/g or more, and the viscosity stability of the colored resin composition, the curing speed, the adhesion of the colored film, and the reliability of the colored film is preferable from the viewpoint of
- the hydroxyl value is preferably 20-300 mgKOH/g, more preferably 90-250 mgKOH/g.
- the acid value is preferably 20-300 mgKOH/g, more preferably 60-150 mgKOH/g.
- the sum of acid value and hydroxyl value is preferably 80-300 mgKOH/g, more preferably 100-300 mgKOH/g.
- the total acid value and hydroxyl value is less than 80 mgKOH/g, the number of functional groups that react with (D) the blocked isocyanate is reduced, resulting in a decrease in curing speed, adhesion of the colored film, and deterioration in adhesion after various reliability tests. is concerned.
- the total of the acid value and the hydroxyl value is less than 80 mgKOH/g, a decrease in viscosity stability and an increase in the diffuse reflectance of the resulting colored film are observed.
- the decrease in viscosity stability and the increase in the diffuse reflectance of the colored film are caused by deterioration in compatibility between (A) the hydroxyl- or acid-containing resin and (D) the blocked isocyanate. It is thought to be caused to inhibit dispersion.
- the diffuse reflectance is preferably low from the viewpoint of design.
- the hydroxyl value refers to the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of (A) the hydroxyl- or acid-containing resin is acetylated (unit :mg KOH/g).
- the acid value refers to the number of mg of potassium hydroxide required to neutralize 1 g of (A) a hydroxyl group- or acid group-containing resin according to JIS K0070 (1992) (unit: mgKOH/g).
- the weight average molecular weight (Mw) of the hydroxyl group- or acid group-containing resin is preferably 500 or more and 150,000 or less. From the viewpoint of the reliability of the colored film, the weight average molecular weight is preferably 5,000 or more and 150,000 or less, more preferably 10,000 or more and 150,000 or less.
- the weight average molecular weight (Mw) refers to a value analyzed by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve.
- Examples of the hydroxyl group or acid group possessed by the hydroxyl group- or acid group-containing resin include a hydroxyl group, a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, and a phosphoric acid group. You may contain 2 or more types of these. Among these, a hydroxy group or a carboxyl group is particularly preferable from the viewpoint of adhesion after a reliability test of the coating film and low-temperature curability.
- the content of the hydroxyl group- or acid group-containing resin is the total solid content of 100 mass from the viewpoint of the storage stability of the pigment dispersion, the curability of the colored resin composition, and the adhesion of the resulting colored film to the substrate. %, preferably 10 to 99% by mass, more preferably 25 to 85% by mass.
- the solid content is a component other than the solvent among the components contained in the composition.
- the solid content includes (A) hydroxyl group- or acid group-containing resin, (B) colorant, (C) dispersant, (D) blocked isocyanate, and other additives.
- the curability of the colored resin composition and the adhesion of the colored film to the substrate are also affected by the content of (D) blocked isocyanate, which will be described later.
- Colorants include, for example, organic pigments, inorganic pigments, and dyes.
- Organic pigments or inorganic pigments are preferred in order to improve the heat resistance, reliability and light resistance of the colored film.
- organic pigments include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine; Anthraquinone pigments such as pyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; quinophthalone-based pigments; threne-based pigments; and metal complex-based pigments.
- diketopyrrolopyrrole pigments such as azo, disazo and polyazo
- phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine
- Anthraquinone pigments such as pyrimidine, flavanthron
- inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum. Red, molybdate orange, chrome vermillion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, Viridian, titanium cobalt green, cobalt green, cobalt chrome green, victoria green, ultramarine blue, dark blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, and the like.
- Dyes include, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine dyes, and polymethine dyes.
- black coloring materials include black organic pigments, mixed color organic pigments, and inorganic pigments.
- black organic pigments include carbon black, perylene black, aniline black, and benzofuranone pigments.
- mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan.
- black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; oxides, composite oxides, sulfides, and nitrides of the above metals. , oxynitrides, and the like.
- white coloring materials include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, and silicon dioxide.
- Two or more of these coloring materials may be contained.
- the (B) colorant in the colored resin composition of the present invention is preferably finely dispersed and the dispersion is stabilized. If the coloring material is not sufficiently dispersed, the resulting colored film contains coarse particles of the coloring material, resulting in unevenness in the film. It is considered to be a factor to
- the average particle size of the coloring material in the colored resin composition is preferably 30 to 200 nm, more preferably 30 to 120 nm.
- an acrylic dispersant having a basic group is used as the dispersant, and the colorant is dispersed stably and uniformly in a fine state without reaggregating the colorant in the resin.
- a method of finely dispersing a coloring agent by a salt milling method or the like, or a method of finely dispersing the coloring agent by a bead mill, which will be described later, can be used to produce a colored resin composition.
- the content of the (B) colorant in the colored resin composition of the present invention is preferably 1 to 60% by mass with respect to 100% by mass of the total solid content.
- the content of the coloring agent (B) is preferably 1 part by mass or more, the resulting colored film can be improved in its ability to block visible light.
- the coloring material is a component that does not shrink during curing, the more the coloring material, the less the film stress and the better the adhesion. From this point of view, the content of the coloring material is more preferably 13% by mass or more.
- the content of the coloring agent (B) is preferably 60% by mass or less, more preferably 48% by mass or less.
- the dispersant in the colored resin composition of the present invention is an acrylic dispersant having a basic group.
- a dispersant is a substance having both a colorant affinity group having chemical bonding or adsorption action to the colorant surface and a polymer chain or group having solvent affinity.
- An acrylic dispersant refers to a dispersant having a main chain obtained by copolymerizing a monomer containing a (meth)acrylic group.
- the main chain may be a block copolymer or a random copolymer, or may have a side chain such as a graft copolymer.
- the dispersant improves the wettability of the colorant to the dispersion medium in the dispersion treatment described later, promotes disaggregation of the colorant, and stabilizes the particle size and viscosity of the colorant by steric hindrance and/or electrostatic repulsion effects. Furthermore, it has the effect of suppressing the occurrence of color separation during storage or coating of the colored resin composition.
- the (C) dispersant in the colored resin composition of the present invention an acrylic resin with excellent reliability such as light resistance and high temperature and high humidity resistance is selected. Furthermore, since the dispersant (C) has a basic group, the dispersant adsorbs to the surface of the colorant, finely disperses the colorant when the colorant is dispersed, and stabilizes the dispersed state due to steric hindrance between the dispersants. , has the effect of suppressing thickening and reaggregation over time.
- Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, amide groups, imino groups, imidazoline groups, pyrrole groups, imidazole groups, benzimidazole groups, pyrazole groups, A pyridine group, a pyrimidine group, a pyrazine group, a pyrrolidine group, a piperidine group, a piperazine group, an indole group, an indoline group, a purine group, a quinoline group, an isoquinoline group, a quinuclidine group, a triazine group, and the like.
- the dispersant can have one or more of these basic groups.
- a dispersant containing at least one of a tertiary amino group and a quaternary ammonium base is preferable because it has good adsorptive power to a coloring material and high dispersibility. Dispersants with both ammonium bases are particularly preferred. If the adsorption power to the coloring material is good, the amount of dispersant released into the colored film by desorption from the coloring material will decrease during the high-temperature, high-humidity test and light resistance test. It is considered that the adhesion of the colored film after the wet test is improved.
- the amine value of the dispersant (C) is preferably 1 mgKOH/g or more and 200 mgKOH/g or less, more preferably 20 mgKOH/g or more and 150 mgKOH/g or less.
- the weight average molecular weight (Mw) is preferably 500 or more and 150,000 or less, more preferably 5000 or more and 150,000 or less.
- the amine value in the present invention represents the number of mg of KOH equivalent to the acid required to neutralize 1 g of the dispersant.
- acrylic dispersants having a basic group examples include DISPERBYK (registered trademark)-112, 116, 151, 155, 156, 187, 190, 191, 194N, 199, 2000, 2001, 2006, 2008, 2009, 2010, 2012, 2013, 2015, 2020, 2022, 2025, 2050, 2055, 2070, DISPERBYK (registered trademark) LPN6919, LPN21116, LPN22102 (all manufactured by BYK-Chemie).
- DISPERBYK registered trademark
- LPN6919, LPN21116, LPN22102 all manufactured by BYK-Chemie.
- acrylic dispersants containing at least one of a tertiary amino group and a quaternary ammonium base include, for example, DISPERBYK (registered trademark)-187, 190, 191, 194N, 199, 2000, 2001, 2006 , 2009, 2010, 2012, 2013, 2015, 2022, 2025, 2050, 2055, DISPERBYK® LPN6919, LPN21116, and acrylic dispersants having both a tertiary amine and a quaternary ammonium salt, For example, DISPERBYK® LPN21116 may be mentioned.
- the content of (C) the dispersant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the coloring material (B).
- the content of the dispersant is preferably 100 parts by mass or less, more preferably 60 parts by mass or less with respect to 100 parts by mass of the coloring agent, from the viewpoint of improving the adhesion and reliability of the colored film.
- Blocked isocyanate is a compound having two or more isocyanate groups blocked by a blocking agent. Since the blocking agent is dissociated by heating to regenerate the isocyanate group, the blocked isocyanate has a long pot life and the ink containing it has excellent viscosity stability.
- a blocked isocyanate is used as a curing agent in the colored resin composition of the present invention. The blocked isocyanate dissociates (deprotects) the blocking agent by heating at a relatively low temperature to regenerate the isocyanate group. The regenerated isocyanate group thermally reacts with the hydroxyl group or acid group of the hydroxyl group- or acid group-containing resin (A) to cure the ink.
- the type of isocyanate is not particularly limited, but includes aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, dimers or trimers obtained by modifying diisocyanates, and compounds containing terminal isocyanate groups. These may be used alone or in combination.
- aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate and dianisidine diisocyanate.
- Aliphatic diisocyanates include, for example, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter referred to as HMDI), 2,2,4-trimethyl-1,6-hexamethylene and diisocyanate.
- HMDI 1,6-hexamethylene diisocyanate
- diisocyanate examples include lysine diisocyanate, isophorone diisocyanate (hereinafter IPDI), 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate and the like. Dimers or trimers by modification of these diisocyanates are also included.
- Modification methods include biuret formation, isocyanurate formation, and the like.
- a terminal isocyanate group-containing compound obtained by reacting the aforementioned diisocyanate compound or polyisocyanate compound with an active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, polyester polyol, polyether polyol, polyamide, etc. is mentioned.
- Blocking agents include, for example, known blocking agents such as phenol, methyl ethyl ketoxime, and sodium bisulfite.
- a resin such as a polycarbonate or a PET film
- Examples of such blocking agents that can be dissociated at lower temperatures include active methylene compounds and pyrazole compounds.
- Active methylene compounds include Meldrum's acid, dialkyl malonate, alkyl acetoacetate, 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate.
- Pyrazole compounds include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethyl pyrazole, 3-methyl-5-phenylpyrazole and the like. Among them, diethyl malonate, 3,5-dimethylpyrazole and the like are preferable.
- “Blocked isocyanate” is available as a commercial product.
- Coronate (registered trademark) AP Stable M Coronate (registered trademark) 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate (registered trademark) 17B- 60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, Asahi Kasei Chemicals ), Desmodur BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Su
- the contents of (A) a hydroxyl group- or acid group-containing resin and (D) a blocked isocyanate are preferably selected so that their respective functional groups are consumed after curing.
- the content of (D) blocked isocyanate is preferably 1 to 300 parts by mass, more preferably 5 to 150 parts by mass, more preferably 10 to 100 parts by mass, with the mass of (A) hydroxyl group- or acid group-containing resin being 100 parts by mass. Part is more preferred.
- the content of the blocked isocyanate is within these ranges, the effect of efficiently curing the hydroxyl group- or acid group-containing resin can be obtained.
- the colored resin composition of the present invention preferably further contains (E) an organic solvent because it can improve the applicability.
- the organic solvent has the effect of uniformly dissolving or dispersing (A) the hydroxyl group- or acid group-containing resin, (B) the coloring agent, (C) the dispersant, and (D) the blocked isocyanate.
- As the organic solvent a compound having a boiling point of 110 to 250° C. under atmospheric pressure is preferable.
- the colored resin composition of the present invention is assumed to be applied by a printing method such as spin coater, slit coater, screen printing, inkjet, gravure printing or bar coater, if the boiling point is less than 110 ° C., the drying of the organic solvent The speed is high, and problems with coating uniformity are likely to occur. On the other hand, if the boiling point exceeds 250° C., the organic solvent may remain in the resulting colored film and the chemical resistance of the colored film may deteriorate.
- a printing method such as spin coater, slit coater, screen printing, inkjet, gravure printing or bar coater
- Organic solvents include, for example, ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.
- ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl.
- Acetates include, for example, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether.
- esters include lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate and 3-methoxypropionic acid; ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate , ethyl
- ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like.
- aromatic hydrocarbons include toluene and xylene.
- Amides include, for example, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and the like.
- alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol and the like. be done. You may contain 2 or more types of these.
- the content of acetates in the organic solvent is preferably 50 to 100% by mass, more preferably 70 to 100% by mass.
- the organic solvent (E) preferably contains 3 to 90% by mass, more preferably 10 to 75% by mass, of an organic solvent having a boiling point of 150 to 250°C.
- the content of the (E) organic solvent is preferably 50% by mass or more of the entire composition from the viewpoint of uniformity of the coating film thickness in the coating step, and more preferably 70% by mass or more. preferable.
- the content of the (E) organic solvent is preferably 95% by mass or less, more preferably 90% by mass or less, of the entire composition from the viewpoint of suppressing pigment sedimentation.
- the colored resin composition of the present invention may contain a leveling agent.
- a leveling agent By containing a leveling agent, the coatability and the surface smoothness of the colored film can be improved.
- leveling agents include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; Amphoteric surfactants such as methylhydroxyethylimidazolium betaine; Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate; Silicone surfactants having a main skeleton such as polydimethylsiloxane agents; fluorine-based surfactants, and the like. You may contain 2 or more types of these. Examples of commercially available surfactants include "BYK (registered trademark)"-302, 333, 3550
- a dispersion machine is used to contain (A) a hydroxyl group- or acid group-containing resin, (B) a coloring agent, (C) a dispersant and (E) an organic solvent.
- a coloring agent dispersion having a high coloring agent concentration is prepared in advance, and (A) a hydroxyl group- or acid group-containing resin, (D) a blocked isocyanate, and, if necessary, an interface
- a method of adding other ingredients such as an activator and stirring is preferred. Filtration of the obtained colored resin composition may be performed as necessary.
- Dispersers used for dispersion treatment include, for example, ball mills, bead mills, sand grinders, three-roll mills, and high-speed impact mills.
- a bead mill is preferable for improving dispersion efficiency and fine dispersion.
- examples of bead mills include coball mills, basket mills, pin mills, and dyno mills.
- Bead mill beads include, for example, titania beads, zirconia beads, and zircon beads.
- the method for producing the colored resin composition of the present invention it is preferable to perform dispersion treatment in multiple stages using a bead mill.
- a bead mill For example, it is preferable to disperse with a bead mill using beads having an average bead diameter of more than 0.1 mm ⁇ , and then to disperse with a bead mill using beads having an average bead diameter of 0.1 mm ⁇ or less.
- a coloring material having a large crystallite size can be efficiently pulverized by dispersing with a bead mill using beads having an average bead diameter larger than 0.1 mm ⁇ .
- the bead mill is preferably provided with a centrifugal separator capable of separating fine beads from the dispersion liquid.
- the average bead diameter refers to the number average value of equivalent circle diameters of beads.
- the beads were photographed at a magnification of 45 times with a stereoscopic microscope, and the longest and shortest diameters of 100 randomly selected beads were measured, and the average value was taken as the circle equivalent diameter, and the number average By calculating the value, the bead diameter can be obtained.
- a colored film can be obtained by curing the colored resin composition of the present invention.
- the light shielding property of the colored film formed in the non-display area of the display is preferably 4.0 or more OD, more preferably 4.5 or more, from the viewpoint of preventing light leakage from the backlight.
- a decorative substrate comprising a substrate and a colored film is obtained by coating a colored resin composition on a substrate and curing it to form a colored film by the following method.
- substrates include transparent glass substrates such as soda glass, non-alkali glass, and aluminosilicate glass; resin substrates such as polycarbonate resin and acrylic resin; film substrates such as PET film and COP film; silicon wafers, ceramics, and gallium arsenide. and the like.
- coating methods include spin coating using a spinner, spray coating, die coating, roll coating, inkjet printing, screen printing, and gravure printing.
- the film thickness of the coating film can be appropriately selected depending on the coating method or the like.
- the film thickness after drying is generally 1 to 150 ⁇ m.
- the obtained coating film is dried to obtain a dry film.
- the drying method include heat drying, air drying, reduced pressure drying, and infrared irradiation.
- heat drying devices include ovens and hot plates.
- the drying temperature is preferably 50 to 150° C., and the drying time is preferably 1 minute to several hours. This drying process is expected to level the coating film and suppress the adhesion of foreign substances. However, this drying process is not necessarily required, and a colored film can be obtained only by the heat treatment described later.
- the resulting coating film is cured by heat treatment (post-baking) to obtain a colored film.
- the heat treatment may be performed in air, in a nitrogen atmosphere, or in a vacuum.
- the heating temperature is preferably 70 to 300°C, more preferably 80 to 180°C.
- the heating temperature can be selected according to the heat resistance temperature of the base material.
- the heating time is preferably 0.25 to 5 hours. During the heat treatment, the heating temperature may be changed continuously or stepwise.
- a decorative substrate comprising a substrate and a colored film made of a cured product of the colored resin composition of the present invention is a decorative substrate in display terminals such as smartphones, tablet PCs, and in-vehicle displays, and is used for driver monitoring in in-vehicle displays and in-vehicle instruments. It can be suitably used for a near-infrared sensor for a gesture sensor, a decorative substrate for concealing a near-infrared camera, a decorative film for concealing a LiDAR sensor, and the like.
- the colored film made of the cured product of the colored resin composition of the present invention can be suitably used as a light-shielding film such as a black matrix of a color filter provided in a liquid crystal display device or the like, a colored partition wall inside an organic EL display, and the like.
- JIS S6050 acceptable product JIS S6050 acceptable product
- the tape While holding one end of the tape and keeping the tape perpendicular to the plate, the tape was momentarily peeled from the colored film. At this time, the ratio of the peeled colored film was evaluated by visually confirming the number of squares of the colored film remaining without peeling from the substrate among the 100 squares of the colored film.
- [Average particle size of coloring material] Set the temperature of a dynamic light scattering particle size distribution meter (UPA-EX150 manufactured by Microtrac Bell Co., Ltd.) to 20 ⁇ 1 ° C., and dilute the coloring material dispersion or colored resin composition 400 times with propylene glycol monomethyl ether acetate. The measured value (D50) obtained by measuring the colorant particles was used as the value of the average particle size of the coloring material particles.
- UPA-EX150 dynamic light scattering particle size distribution meter
- the colored films obtained in Examples and Comparative Examples were measured using a spectrophotometer (CM-2600d; manufactured by Konica Minolta, Inc.) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta, Inc.).
- CM-2600d color temperature 6504K
- viewing angle 2° CIE1976
- atmospheric pressure 20°C
- SCE diffuse reflection chromaticity
- L * was evaluated as an index of the diffuse reflectance of the colored film.
- the colored film formed in the non-display area of the cover lens preferably has a low L * from the viewpoint of design.
- the film thickness of the colored film obtained in each example and comparative example was measured using a contact film thickness gauge Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.).
- a white cotton cloth Koreanakin No. 3
- isopropyl alcohol a test solvent, as a friction element, layered so as to come into contact with the colored film
- a Gakushin type rubbing tester under a constant load condition ( After performing a rubbing test (10 reciprocations) at 300 g/cm 2 ), the film thickness was measured again. From the changes in the thickness of the colored film before and after the rubbing test, the solvent resistance of the colored film was obtained from the following formula.
- Solvent resistance (%) film thickness after rubbing test ( ⁇ m) ⁇ 100/film thickness before rubbing test ( ⁇ m) Evaluation of solvent resistance is performed to quantitatively evaluate the degree of curability during low-temperature baking.
- the hydroxyl value of the resin was measured in mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the resin was acetylated according to JIS K0070 (1992).
- the number of mg of potassium hydroxide required to neutralize 1 g of the resin was measured according to JIS K0070 (1992).
- the weight average molecular weight was measured by polystyrene conversion using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation) using tetrahydrofuran as the carrier.
- the resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mm ⁇ , and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes.
- the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mm ⁇ , and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass.
- a coloring agent dispersion DP-1 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30 was obtained.
- the mixture was stirred for 20 minutes with a mixer to obtain a preliminary dispersion.
- the resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mm ⁇ , and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes.
- the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mm ⁇ , and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , to obtain a coloring agent dispersion DP-2 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30.
- the resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.50 mm ⁇ , and was rotated at a rotation speed of 12 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mm ⁇ , and dispersed at a rotation speed of 8 m/s for 90 minutes until the solid content was 20% by mass. , to obtain a coloring agent dispersion DP-3 having a coloring agent/(resin+dispersant) (mass ratio) of 60/40.
- the mixture was stirred for a minute to obtain a preliminary dispersion.
- the obtained preliminary dispersion is supplied to a paint shaker (Toyo Seiki Seisakusho Co., Ltd.), dispersed for 3 hours using zirconia beads with a bead diameter of 1.0 mm ⁇ , and then filtered through a 5 ⁇ m filter to obtain a solid content concentration of 20.
- the resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mm ⁇ , and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mm ⁇ , and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , to obtain a coloring agent dispersion DP-8 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30. Table 2 shows the compositions, dispersing conditions and conditions of Production Examples 5 to 12.
- Example 1 To 31.43 g of the colorant dispersion (DP-1), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and a blocked isocyanate whose blocking agent is an oxime-based blocking agent, coronate ( Registered trademark) BI-301 (manufactured by Tosoh Corporation, Solvesso (registered trademark) 100 (manufactured by Exxon Chemical Co., Ltd.) 75% by mass solution) is 6.43 g, and a silicone surfactant "BYK (registered trademark)" is used as a surfactant.
- a silicone surfactant "BYK (registered trademark)" is used as a surfactant.
- the resulting colored resin composition PC-1 is placed on an easy-adhesive layer of a polyester film (manufactured by Toray Industries, Inc., Lumirror (registered trademark) U48, film thickness: 100 ⁇ m), and a spinner (1H- DS) to form a coating film.
- the coated film was dried by heating in an oven at 90° C. for 30 minutes to obtain a colored film C-1.
- Table 4 shows the results of evaluating this colored film C-1 by the method described above.
- Example 2 A colored resin composition PC-2 was obtained in the same manner as in Example 1 except that the coloring agent dispersion (DP-2) was used instead of the coloring agent dispersion (DP-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-2. Table 4 shows the results.
- Example 3 To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( Registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation, PGMEA 70% by mass solution) 6.89 g, and a silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) as a surfactant as a PGMEA 10% solution A solution of 0.20 g dissolved in 34.91 g of PGMEA was added to obtain a colored resin composition having a total solid concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solid content PC- got 3. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-3. Table 4 shows the results.
- Example 4 To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate (registered trademark), which is an active methylene blocking agent, is used as a blocking agent.
- DP-2 colorant dispersion
- P-1 hydroxyl group- or acid group-containing resin
- Duranate registered trademark
- Example 5 A colored resin composition PC-5 was obtained in the same manner as in Example 3, except that the hydroxyl- or acid-containing resin (P-2) was used instead of the hydroxyl- or acid-containing resin (P-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-5. Table 4 shows the results.
- Example 6 22.92 g of the colorant dispersion (DP-3), 16.04 g of the colorant dispersion (DP-4), and 6.88 g of the colorant dispersion (DP-5) were added with a hydroxyl- or acid-containing resin.
- Example 7 To 45.83 g of the colorant dispersion (DP-6), 23.27 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 6.67 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 24.03 g of PGMEA was added to obtain a colored resin composition PC-7 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-7. Table 4 shows the results.
- Example 8 A colored resin composition PC-8 was obtained in the same manner as in Example 3 except that the coloring agent dispersion (DP-7) was used instead of the coloring agent dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-8. Table 4 shows the results.
- Example 9 To 18.86 g of the colorant dispersion (DP-2), 33.52 g of a 35% by mass solution of PGMEA of the hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 7.90 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 39.52 g of PGMEA was added to obtain a colored resin composition PC-9 having a total solids concentration of 22% by mass and a coloring material content of 15 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-9. Table 4 shows the results.
- Example 10 To 56.57 g of the colorant dispersion (DP-2), 12.64 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 4.87 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), and 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 25.71 g of PGMEA was added to obtain a colored resin composition PC-10 having a total solids concentration of 22% by mass and a coloring material content of 45 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-10. Table 4 shows the results.
- Example 11 To 12.57 g of the coloring material dispersion (DP-2), 37.00 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 8.41 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Corporation) as a surfactant, A solution dissolved in 41.82 g of PGMEA was added to obtain a colored resin composition PC-11 having a total solids concentration of 22% by mass and a coloring material content of 10 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-11. Table 4 shows the results.
- Example 12 To 62.86 g of the colorant dispersion (DP-2), 9.16 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 4.37 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 23.41 g of PGMEA was added to obtain a colored resin composition PC-12 having a total solids concentration of 22% by mass and a coloring material content of 50 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-12. Table 4 shows the results.
- Example 13 To 31.43 g of the colorant dispersion (DP-2), 17.37 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 11.49 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK Chemie) as a surfactant, A solution dissolved in 39.51 g of PGMEA was added to obtain a colored resin composition PC-13 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-13. Table 4 shows the results.
- Example 14 To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-14 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-14. Table 4 shows the results.
- Example 15 To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-3), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-15 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids.
- Example 16 To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-4), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-16 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids.
- Example 17 To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-5), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-17 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids.
- Example 18 To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-6), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-18 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin
- Example 1 A colored resin composition PC-19 was obtained in the same manner as in Example 3 except that the colorant dispersion (DP-8) was used instead of the colorant dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-19. Table 4 shows the results.
- the colored resin compositions of Examples are excellent in viscosity stability and curability at low-temperature baking, and have high adhesion after the light resistance test and high-temperature, high-humidity test.
- the colored resin composition of Comparative Example 1 has insufficient viscosity stability, and has low adhesion and adhesion after the light resistance test/high temperature and high humidity test.
- the curability at the time of low-temperature firing is also insufficient.
- the colored resin composition of Comparative Example 2 has insufficient viscosity stability and curability during low-temperature baking.
- the colored resin composition of the present invention can be suitably used as a black decorative ink for forming a light-shielding film in the non-display area of the cover lens of an in-vehicle display or the like.
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Abstract
Provided is a colored resin composition comprising (A) a resin containing a hydroxyl group or an acid group, (B) a colorant, (C) a dispersant, and (D) a blocked isocyanate, wherein the dispersant (C) is an acrylic dispersant having a basic group. The colored resin composition can cure at low temperatures and has excellent viscosity stability at ordinary temperature. The colored resin composition, even after a light-resistance test or a high-temperature high-humidity test, retains high adhesiveness.
Description
本発明は、着色樹脂組成物、着色膜、加飾基板に関する。
The present invention relates to colored resin compositions, colored films, and decorative substrates.
スマートフォンや車載ディスプレイなどの各種情報端末におけるタッチパネルは、ユーザーサイドから見て最表層に位置するカバーレンズの非表示領域に遮光膜が形成され、その遮光膜がタッチセンサーの引き回し配線等の電極を隠蔽する役割を担っている。
Touch panels in various information terminals such as smartphones and in-vehicle displays have a light-shielding film formed in the non-display area of the cover lens, which is located on the outermost layer when viewed from the user side, and the light-shielding film hides electrodes such as the lead-out wiring of the touch sensor. have a role to play.
車載ディスプレイやスマートウォッチでは太陽光の紫外線照射下や高温高湿環境においても動作性や意匠性が変化しないといった信頼性が要求され、カバーレンズの遮光膜においてもそのような環境下で密着性が低下しないこと等が求められる。
In-vehicle displays and smartwatches require reliability such that operability and design do not change even under ultraviolet irradiation of sunlight or in high temperature and high humidity environments. It is required that it does not decrease.
また、特に車載ディスプレイにおいては、カバーレンズの材質がポリカーボネート等の樹脂が適用されるケースもある。樹脂への遮光膜の形成方法としては、樹脂にスクリーン印刷、インクジェット印刷、グラビア印刷等でインクを直接印刷する方式や、加飾フィルムのインモールド成型によりカバーレンズを製造する方式等がある。いずれの方式にせよ、基材の耐熱性がガラスよりも低いため、８０～１２０℃の低温焼成で硬化可能なインクが求められる。また、これらの印刷方式では連続印刷性および膜厚再現性の観点から常温で粘度が変化しないことが要求される。
In addition, especially for in-vehicle displays, there are cases where resin such as polycarbonate is used as the cover lens material. As a method of forming a light-shielding film on a resin, there are a method of directly printing ink on the resin by screen printing, inkjet printing, gravure printing, etc., and a method of manufacturing a cover lens by in-mold molding of a decorative film. In either method, since the heat resistance of the base material is lower than that of glass, an ink that can be cured by low-temperature baking at 80 to 120° C. is required. In addition, in these printing methods, it is required that the viscosity does not change at room temperature from the viewpoint of continuous printing properties and film thickness reproducibility.
そこで、例えば特許文献１では、重量平均分子量２００００～３０００００のカルボキシル基含有バインダーポリマーと、ブロックイソシアネートおよびエポキシ樹脂を含む硬化剤を含有するインクジェット印刷用インクが検討されている。また、特許文献２では、非耐熱性の非吸収性媒体に印刷可能であり、低温硬化が可能なインクとして、グリコールエーテル系溶剤および酢酸エステル系溶剤を含有し、ヒドロキシル基を有するアクリル樹脂と低温解離ブロック形イソシアネートを含有するインクジェット印刷用インクが検討されている。
Therefore, Patent Document 1, for example, discusses an inkjet printing ink containing a carboxyl group-containing binder polymer having a weight average molecular weight of 20,000 to 300,000 and a curing agent containing a blocked isocyanate and an epoxy resin. Further, in Patent Document 2, as an ink that can be printed on a non-heat-resistant, non-absorbent medium and that can be cured at a low temperature, an acrylic resin containing a glycol ether-based solvent and an acetate solvent and having a hydroxyl group and a low-temperature Ink jet printing inks containing dissociated blocked isocyanates have been investigated.
しかしながら、特許文献１に記載のインクは、ブロックイソシアネートおよびエポキシ樹脂の両方を用いることで各種の信頼性試験後にも高い密着性を維持することが可能であるが、エポキシ樹脂がポリマーのカルボキシル基等と反応するため、長時間の印刷に用いた場合には膜厚や印刷精度が変化することから粘度安定性が十分ではなかった。また、特許文献２に記載のインクは、低温硬化が可能であり粘度安定性に優れるが、車載規格の厳しい信頼性試験後では密着性が低下し、耐光性・高温高湿耐性の観点からは特性が不足していた。
However, the ink described in Patent Document 1 can maintain high adhesion even after various reliability tests by using both a blocked isocyanate and an epoxy resin. Therefore, when used for long-term printing, the film thickness and printing accuracy change, resulting in insufficient viscosity stability. In addition, the ink described in Patent Document 2 can be cured at a low temperature and has excellent viscosity stability. It lacked features.
そこで、本発明は、低温硬化が可能で常温における粘度安定性に優れており、耐光性試験・高温高湿試験後にも高い密着性を維持する着色樹脂組成物を提供することを目的とする。
Therefore, the object of the present invention is to provide a colored resin composition that can be cured at a low temperature, has excellent viscosity stability at room temperature, and maintains high adhesion even after a light resistance test and a high temperature and high humidity test.
本発明者らは、鋭意検討した結果、着色樹脂組成物に、水酸基または酸基含有樹脂、着色材、分散剤、およびブロックイソシアネートを含有させ、分散剤として塩基性基を有するアクリル系分散剤を適用することにより、上記課題を解決することができることを見出し、本発明を完成した。
As a result of extensive studies, the present inventors have found that a colored resin composition contains a hydroxyl- or acid-containing resin, a coloring agent, a dispersant, and a blocked isocyanate, and an acrylic dispersant having a basic group as a dispersant. The inventors have found that the above problems can be solved by applying the method, and completed the present invention.
すなわち、本発明の目的は、主として以下の構成により達成される。
（Ａ）水酸基または酸基含有樹脂、（Ｂ）着色材、（Ｃ）分散剤、および（Ｄ）ブロックイソシアネートを含有し、前記（Ｃ）分散剤が塩基性基を有するアクリル系分散剤である、着色樹脂組成物。 That is, the object of the present invention is mainly achieved by the following configurations.
(A) a hydroxyl group- or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate, wherein the (C) dispersant is an acrylic dispersant having a basic group. , a colored resin composition.
（Ａ）水酸基または酸基含有樹脂、（Ｂ）着色材、（Ｃ）分散剤、および（Ｄ）ブロックイソシアネートを含有し、前記（Ｃ）分散剤が塩基性基を有するアクリル系分散剤である、着色樹脂組成物。 That is, the object of the present invention is mainly achieved by the following configurations.
(A) a hydroxyl group- or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate, wherein the (C) dispersant is an acrylic dispersant having a basic group. , a colored resin composition.
本発明の着色樹脂組成物は、低温硬化が可能で常温における粘度安定性に優れており、耐光性試験・高温高湿試験後にも高い密着性を維持する着色膜を得ることができる。
The colored resin composition of the present invention can be cured at a low temperature and has excellent viscosity stability at room temperature, so that a colored film that maintains high adhesion even after a light resistance test and a high temperature and high humidity test can be obtained.
以下、本発明をさらに詳細に説明する。
The present invention will be described in further detail below.
本発明の着色樹脂組成物は、（Ａ）水酸基または酸基含有樹脂、（Ｂ）着色材、（Ｃ）分散剤、および（Ｄ）ブロックイソシアネートを含有する。（Ａ）水酸基または酸基含有樹脂は、組成物におけるバインダーとしての作用を有する。（Ｂ）着色材は、可視光を遮蔽する作用を有する。（Ｃ）分散剤は、着色材を均一に分散し、再凝集を防ぐ作用を有する。（Ｄ）ブロックイソシアネートは、加熱焼成時にのみ樹脂に含まれる水酸基または酸基と反応する作用を有する。
The colored resin composition of the present invention contains (A) a hydroxyl group- or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate. (A) The hydroxyl group- or acid group-containing resin acts as a binder in the composition. (B) The coloring agent has the effect of shielding visible light. (C) The dispersing agent has the function of dispersing the coloring material uniformly and preventing reaggregation. (D) The blocked isocyanate has the action of reacting with hydroxyl groups or acid groups contained in the resin only during heating and baking.
本発明は、前記（Ｃ）分散剤が塩基性基を有するアクリル系分散剤であることを特徴とする。アクリル系分散剤は、耐光性、高温高湿耐性等の信頼性に優れる。さらに分散剤が塩基性基を有することにより、分散剤が着色材の表面に吸着し、着色材分散時に着色材を微細に分散し、分散剤同士の立体障害により分散状態を安定化し、経時増粘や再凝集を抑制する作用を有する。また、（Ｄ）ブロックイソシアネートは常温ではブロック剤の機能により反応性を有さず、加熱時のみ反応性を有するため、着色樹脂組成物の粘度安定性を良好に保つことができ、ブロック剤を適切に選定することにより低温でブロック剤が解離し、水酸基または酸基と反応することができる。
The present invention is characterized in that the (C) dispersant is an acrylic dispersant having a basic group. Acrylic dispersants are excellent in reliability such as light resistance and high temperature and high humidity resistance. Furthermore, since the dispersant has a basic group, the dispersant adsorbs to the surface of the coloring agent, finely disperses the coloring agent when dispersing the coloring agent, stabilizes the dispersion state due to steric hindrance between the dispersing agents, and increases over time. It has the effect of suppressing stickiness and reaggregation. In addition, (D) blocked isocyanate does not have reactivity due to the function of the blocking agent at room temperature, and has reactivity only when heated, so that the viscosity stability of the colored resin composition can be maintained well, and the blocking agent is used. With proper selection, the blocking agent can dissociate at low temperatures and react with hydroxyl groups or acid groups.
（Ａ）水酸基または酸基含有樹脂は、水酸基または酸基を有する樹脂である。（Ａ）水酸基または酸基含有樹脂としては、例えば、アクリル樹脂、カルド樹脂、シロキサン樹脂、ポリイミド樹脂、ポリイミド前駆体、ポリウレタン樹脂、ポリエステル樹脂、塩酢ビ樹脂、などが挙げられる。これらを２種以上含有してもよい。これらの中でも、着色樹脂組成物の貯蔵安定性や着色膜の密着性および信頼性の観点から、アクリル樹脂、ポリウレタン樹脂またはポリエステル樹脂が好ましく、特にアクリル樹脂が好ましい。
(A) A hydroxyl- or acid-group-containing resin is a resin having a hydroxyl group or an acid group. (A) Examples of hydroxyl group- or acid group-containing resins include acrylic resins, cardo resins, siloxane resins, polyimide resins, polyimide precursors, polyurethane resins, polyester resins, and vinyl chloride resins. You may contain 2 or more types of these. Among these, acrylic resins, polyurethane resins and polyester resins are preferred, and acrylic resins are particularly preferred, from the viewpoint of storage stability of the colored resin composition and adhesion and reliability of the colored film.
（Ａ）水酸基または酸基含有樹脂は、水酸基価または酸価が１０ｍｇＫＯＨ／ｇ以上であることが、着色樹脂組成物の粘度安定性、硬化速度、着色膜の密着性、および着色膜の信頼性の観点から好ましい。水酸基価は２０～３００ｍｇＫＯＨ／ｇであることが好ましく、９０～２５０ｍｇＫＯＨ／ｇであることがより好ましい。酸価は２０～３００ｍｇＫＯＨ／ｇであることが好ましく、６０～１５０ｍｇＫＯＨ／ｇであることがより好ましい。酸価および水酸基価の合計は８０～３００ｍｇＫＯＨ／ｇであることが好ましく、１００～３００ｍｇＫＯＨ／ｇであることがより好ましい。酸価および水酸基価の合計が８０ｍｇＫＯＨ／ｇより小さい場合、（Ｄ）ブロックイソシアネートと反応する官能基数が減るため、硬化速度の低下や、着色膜の密着性および各種信頼性試験後の密着性悪化が懸念される。また、酸価および水酸基価の合計が８０ｍｇＫＯＨ／ｇより小さい場合、粘度安定性の低下や得られる着色膜の拡散反射率の上昇が確認される。この粘度安定性の低下および着色膜の拡散反射率の上昇は、（Ａ）水酸基または酸基含有樹脂と（Ｄ）ブロックイソシアネートの相溶性が悪化することにより、（Ｄ）ブロックイソシアネートが着色材の分散を阻害するために引き起こされると考えられる。着色膜がカバーレンズの非表示領域に形成される場合、意匠性の観点から拡散反射率が低いことが好ましい。
(A) The hydroxyl or acid group-containing resin has a hydroxyl value or acid value of 10 mgKOH/g or more, and the viscosity stability of the colored resin composition, the curing speed, the adhesion of the colored film, and the reliability of the colored film is preferable from the viewpoint of The hydroxyl value is preferably 20-300 mgKOH/g, more preferably 90-250 mgKOH/g. The acid value is preferably 20-300 mgKOH/g, more preferably 60-150 mgKOH/g. The sum of acid value and hydroxyl value is preferably 80-300 mgKOH/g, more preferably 100-300 mgKOH/g. If the total acid value and hydroxyl value is less than 80 mgKOH/g, the number of functional groups that react with (D) the blocked isocyanate is reduced, resulting in a decrease in curing speed, adhesion of the colored film, and deterioration in adhesion after various reliability tests. is concerned. Moreover, when the total of the acid value and the hydroxyl value is less than 80 mgKOH/g, a decrease in viscosity stability and an increase in the diffuse reflectance of the resulting colored film are observed. The decrease in viscosity stability and the increase in the diffuse reflectance of the colored film are caused by deterioration in compatibility between (A) the hydroxyl- or acid-containing resin and (D) the blocked isocyanate. It is thought to be caused to inhibit dispersion. When the colored film is formed in the non-display area of the cover lens, the diffuse reflectance is preferably low from the viewpoint of design.
水酸基価は、ＪＩＳ Ｋ００７０（１９９２）に従って、（Ａ）水酸基または酸基含有樹脂１ｇをアセチル化させたときに水酸基と結合した酢酸を中和するのに要する水酸化カリウムのｍｇ数を指す（単位：ｍｇＫＯＨ／ｇ）。酸価は、ＪＩＳ Ｋ００７０（１９９２）に従って、（Ａ）水酸基または酸基含有樹脂１ｇを中和するのに要する水酸化カリウムのｍｇ数を指す（単位：ｍｇＫＯＨ／ｇ）。
According to JIS K0070 (1992), the hydroxyl value refers to the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of (A) the hydroxyl- or acid-containing resin is acetylated (unit :mg KOH/g). The acid value refers to the number of mg of potassium hydroxide required to neutralize 1 g of (A) a hydroxyl group- or acid group-containing resin according to JIS K0070 (1992) (unit: mgKOH/g).
（Ａ）水酸基または酸基含有樹脂の重量平均分子量（Ｍｗ）は、５００以上１５０，０００以下であることが好ましい。重量平均分子量は、着色膜の信頼性の観点から、５，０００以上１５０，０００以下が好ましく、１０，０００以上１５０，０００以下がより好ましい。ここで、重量平均分子量（Ｍｗ）とは、テトラヒドロフランをキャリヤーとするゲルパーミエーションクロマトグラフィーにより分析し、標準ポリスチレンによる検量線を用いて換算した値を指す。
(A) The weight average molecular weight (Mw) of the hydroxyl group- or acid group-containing resin is preferably 500 or more and 150,000 or less. From the viewpoint of the reliability of the colored film, the weight average molecular weight is preferably 5,000 or more and 150,000 or less, more preferably 10,000 or more and 150,000 or less. Here, the weight average molecular weight (Mw) refers to a value analyzed by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve.
（Ａ）水酸基または酸基含有樹脂が有する水酸基または酸基としては、ヒドロキシ基、カルボキシル基、無水カルボン酸基、スルホン酸基、リン酸基などが挙げられる。これらを２種以上含有しても良い。これらの中でも塗膜の信頼性試験後の密着性や低温硬化性の観点から、ヒドロキシ基またはカルボキシル基が特に好ましい。
(A) Examples of the hydroxyl group or acid group possessed by the hydroxyl group- or acid group-containing resin include a hydroxyl group, a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, and a phosphoric acid group. You may contain 2 or more types of these. Among these, a hydroxy group or a carboxyl group is particularly preferable from the viewpoint of adhesion after a reliability test of the coating film and low-temperature curability.
（Ａ）水酸基または酸基含有樹脂の含有量は、顔料分散液の保存安定性、着色樹脂組成物の硬化性、および得られる着色膜の基板との密着性の観点から、全固形分１００質量％に対して、１０～９９質量％が好ましく、２５～８５質量％がより好ましい。ここで、固形分とは、組成物に含まれる成分のうち溶媒以外の成分である。固形分は、（Ａ）水酸基または酸基含有樹脂、（Ｂ）着色材、（Ｃ）分散剤、（Ｄ）ブロックイソシアネート、およびその他添加剤を含む。なお、着色樹脂組成物の硬化性および着色膜の基板との密着性は、後述する（Ｄ）ブロックイソシアネートの含有量からも影響を受ける。
(A) The content of the hydroxyl group- or acid group-containing resin is the total solid content of 100 mass from the viewpoint of the storage stability of the pigment dispersion, the curability of the colored resin composition, and the adhesion of the resulting colored film to the substrate. %, preferably 10 to 99% by mass, more preferably 25 to 85% by mass. Here, the solid content is a component other than the solvent among the components contained in the composition. The solid content includes (A) hydroxyl group- or acid group-containing resin, (B) colorant, (C) dispersant, (D) blocked isocyanate, and other additives. The curability of the colored resin composition and the adhesion of the colored film to the substrate are also affected by the content of (D) blocked isocyanate, which will be described later.
（Ｂ）着色材としては、例えば、有機顔料、無機顔料または染料が挙げられる。着色膜の耐熱性、信頼性および耐光性を向上させるためには、有機顔料または無機顔料が好ましい。
(B) Colorants include, for example, organic pigments, inorganic pigments, and dyes. Organic pigments or inorganic pigments are preferred in order to improve the heat resistance, reliability and light resistance of the colored film.
有機顔料としては、例えば、ジケトピロロピロール系顔料；アゾ、ジスアゾ、ポリアゾ等のアゾ系顔料；銅フタロシアニン、ハロゲン化銅フタロシアニン、無金属フタロシアニン等のフタロシアニン系顔料；アミノアントラキノン、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系顔料；キナクリドン系顔料；ジオキサジン系顔料；ペリノン系顔料；ペリレン系顔料；チオインジゴ系顔料；イソインドリン系顔料；イソインドリノン系顔料；キノフタロン系顔料；スレン系顔料；金属錯体系顔料などが挙げられる。
Examples of organic pigments include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine; Anthraquinone pigments such as pyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; quinophthalone-based pigments; threne-based pigments; and metal complex-based pigments.
無機顔料としては、例えば、酸化チタン、亜鉛華、硫化亜鉛、鉛白、炭酸カルシウム、沈降性硫酸バリウム、ホワイトカーボン、アルミナホワイト、カオリンクレー、タルク、ベントナイト、黒色酸化鉄、カドミウムレッド、べんがら、モリブデンレッド、モリブデートオレンジ、クロムバーミリオン、黄鉛、カドミウムイエロー、黄色酸化鉄、チタンイエロー、酸化クロム、ビリジアン、チタンコバルトグリーン、コバルトグリーン、コバルトクロムグリーン、ビクトリアグリーン、群青、紺青、コバルトブルー、セルリアンブルー、コバルトシリカブルー、コバルト亜鉛シリカブルー、マンガンバイオレット、コバルトバイオレットなどが挙げられる。
Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum. Red, molybdate orange, chrome vermillion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, Viridian, titanium cobalt green, cobalt green, cobalt chrome green, victoria green, ultramarine blue, dark blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, and the like.
染料としては、例えば、アゾ染料、アントラキノン染料、縮合多環芳香族カルボニル染料、インジゴイド染料、カルボニウム染料、フタロシアニン染料、メチン染料、ポリメチン染料などが挙げられる。
Dyes include, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine dyes, and polymethine dyes.
黒色の着色材としては、例えば、黒色有機顔料、混色有機顔料、無機顔料等が挙げられる。黒色有機顔料としては、例えば、カーボンブラック、ペリレンブラック、アニリンブラック、ベンゾフラノン系顔料などが挙げられる。混色有機顔料としては、赤、青、緑、紫、黄色、マゼンダ、シアンなどの色を有する２種以上の顔料を混色して疑似黒色化したものが挙げられる。黒色無機顔料としては、例えば、グラファイト；チタン、銅、鉄、マンガン、コバルト、クロム、ニッケル、亜鉛、カルシウム、銀等の金属の微粒子；上記金属の酸化物、複合酸化物、硫化物、窒化物、酸窒化物などが挙げられる。
Examples of black coloring materials include black organic pigments, mixed color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone pigments. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; oxides, composite oxides, sulfides, and nitrides of the above metals. , oxynitrides, and the like.
白色の着色材としては、例えば、二酸化チタン、炭酸バリウム、酸化ジルコニウム、炭酸カルシウム、硫酸バリウム、アルミナホワイト、二酸化珪素などが挙げられる。
Examples of white coloring materials include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, and silicon dioxide.
これらの着色材を２種以上含有してもよい。
Two or more of these coloring materials may be contained.
本発明の着色樹脂組成物における（Ｂ）着色材は微細に分散され、分散が安定化された状態が好ましい。着色材の分散が不十分な場合、得られた着色膜に着色材の粗大粒子が存在することにより膜に粗密が生じるため、耐光性試験や高温高湿試験後の着色膜の密着性が低下する要因になると考えられる。着色樹脂組成物における着色材の平均粒子径は、３０～２００ｎｍが好ましく、３０～１２０ｎｍがより好ましい。着色材の平均粒子径を上記の範囲とする手段としては、分散剤として塩基性基を有するアクリル系分散剤を使用し、樹脂中に着色材を再凝集させることなく微細な状態で安定かつ均一に分散させることが好ましい。より具体的には、着色材をソルトミリング法等により微粒化する方法や、後述するビーズミルにより微細に分散する方法により、着色樹脂組成物を製造する方法などが挙げられる。
The (B) colorant in the colored resin composition of the present invention is preferably finely dispersed and the dispersion is stabilized. If the coloring material is not sufficiently dispersed, the resulting colored film contains coarse particles of the coloring material, resulting in unevenness in the film. It is considered to be a factor to The average particle size of the coloring material in the colored resin composition is preferably 30 to 200 nm, more preferably 30 to 120 nm. As a means for adjusting the average particle size of the colorant to the above range, an acrylic dispersant having a basic group is used as the dispersant, and the colorant is dispersed stably and uniformly in a fine state without reaggregating the colorant in the resin. It is preferable to disperse in More specifically, a method of finely dispersing a coloring agent by a salt milling method or the like, or a method of finely dispersing the coloring agent by a bead mill, which will be described later, can be used to produce a colored resin composition.
本発明の着色樹脂組成物における（Ｂ）着色材の含有量は、固形分の総量１００質量％に対して、１～６０質量％が好ましい。（Ｂ）着色材の含有量を１質量部以上とすることにより、得られる着色膜の可視光遮光性を向上させることができる。また、着色材は硬化時に収縮しない成分であるため、着色材が多い方が膜ストレスが低減し、密着性が向上する。この観点から、着色材の含有量は１３質量％以上がより好ましい。一方、（Ｂ）着色材の含有量が多すぎても、硬化反応を担う樹脂成分が減少するため着色膜の密着性が悪化する。そのため、（Ｂ）着色材の含有量は６０質量％以下が好ましく、４８質量％以下がより好ましい。
The content of the (B) colorant in the colored resin composition of the present invention is preferably 1 to 60% by mass with respect to 100% by mass of the total solid content. By setting the content of the coloring agent (B) to 1 part by mass or more, the resulting colored film can be improved in its ability to block visible light. Further, since the coloring material is a component that does not shrink during curing, the more the coloring material, the less the film stress and the better the adhesion. From this point of view, the content of the coloring material is more preferably 13% by mass or more. On the other hand, if the content of the coloring agent (B) is too large, the resin component responsible for the curing reaction is reduced, resulting in poor adhesion of the colored film. Therefore, the content of the coloring agent (B) is preferably 60% by mass or less, more preferably 48% by mass or less.
本発明の着色樹脂組成物における（Ｃ）分散剤は、塩基性基を有するアクリル系分散剤である。分散剤とは、着色材表面への化学的結合または吸着作用を有する着色材親和性基と、親溶媒性を有する高分子鎖または基とを併せ持つものをいう。アクリル系分散剤とは、（メタ）アクリル基を含むモノマーを共重合してなる主鎖を有する分散剤を指す。主鎖は、ブロック共重合体でも、ランダム共重合体でも良く、グラフト共重合体のような側鎖を有するものがあっても良い。
(C) the dispersant in the colored resin composition of the present invention is an acrylic dispersant having a basic group. A dispersant is a substance having both a colorant affinity group having chemical bonding or adsorption action to the colorant surface and a polymer chain or group having solvent affinity. An acrylic dispersant refers to a dispersant having a main chain obtained by copolymerizing a monomer containing a (meth)acrylic group. The main chain may be a block copolymer or a random copolymer, or may have a side chain such as a graft copolymer.
分散剤は、後述の分散処理において、着色材の分散媒への濡れ性を向上させて着色材の解凝集を促進し、立体障害および／または静電反発効果により着色材の粒度および粘度を安定化させ、さらに、着色樹脂組成物の貯蔵時あるいは塗布時の色分離の発生を抑制する効果を奏する。
The dispersant improves the wettability of the colorant to the dispersion medium in the dispersion treatment described later, promotes disaggregation of the colorant, and stabilizes the particle size and viscosity of the colorant by steric hindrance and/or electrostatic repulsion effects. Furthermore, it has the effect of suppressing the occurrence of color separation during storage or coating of the colored resin composition.
本発明の着色樹脂組成物における（Ｃ）分散剤としては、耐光性、高温高湿耐性等の信頼性に優れるアクリル樹脂を選択する。さらに（Ｃ）分散剤が塩基性基を有することにより、分散剤が着色材の表面に吸着し、着色材分散時に着色材を微細に分散し、分散剤同士の立体障害により分散状態を安定化し、経時増粘や再凝集を抑制する作用を有する。塩基性基としては、例えば、１級アミノ基、２級アミノ基、３級アミノ基、４級アンモニウム塩基、アミド基、イミノ基、イミダゾリン基、ピロール基、イミダゾール基、ベンゾイミダゾール基、ピラゾール基、ピリジン基、ピリミジン基、ピラジン基、ピロリジン基、ピペリジン基、ピペラジン基、インドール基、インドリン基、プリン基、キノリン基、イソキノリン基、キヌクリジン基、およびトリアジン基等が挙げられる。分散剤は、これらの塩基性基を１種または２種以上、有することができる。これらの中でも、着色材への吸着力が良好で、かつ、分散性が高いことから、３級アミノ基および４級アンモニウム塩基の少なくとも１種を含有する分散剤が好ましく、３級アミノ基および４級アンモニウム塩基を両方有する分散剤が特に好ましい。着色材への吸着力が良好な場合、高温高湿試験、耐光性試験の過程で、着色材から脱離することより着色膜中に遊離する分散剤が減少するため、耐光性試験・高温高湿試験後の着色膜の密着性が向上することが考えられる。
As the (C) dispersant in the colored resin composition of the present invention, an acrylic resin with excellent reliability such as light resistance and high temperature and high humidity resistance is selected. Furthermore, since the dispersant (C) has a basic group, the dispersant adsorbs to the surface of the colorant, finely disperses the colorant when the colorant is dispersed, and stabilizes the dispersed state due to steric hindrance between the dispersants. , has the effect of suppressing thickening and reaggregation over time. Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, amide groups, imino groups, imidazoline groups, pyrrole groups, imidazole groups, benzimidazole groups, pyrazole groups, A pyridine group, a pyrimidine group, a pyrazine group, a pyrrolidine group, a piperidine group, a piperazine group, an indole group, an indoline group, a purine group, a quinoline group, an isoquinoline group, a quinuclidine group, a triazine group, and the like. The dispersant can have one or more of these basic groups. Among these, a dispersant containing at least one of a tertiary amino group and a quaternary ammonium base is preferable because it has good adsorptive power to a coloring material and high dispersibility. Dispersants with both ammonium bases are particularly preferred. If the adsorption power to the coloring material is good, the amount of dispersant released into the colored film by desorption from the coloring material will decrease during the high-temperature, high-humidity test and light resistance test. It is considered that the adhesion of the colored film after the wet test is improved.
（Ｃ）分散剤は、アミン価が低すぎると着色材への吸着性が不十分となり、アミン価が高すぎると着色樹脂組成物の保存安定性が低下する。そのため、アミン価は１ｍｇＫＯＨ／ｇ以上２００ｍｇＫＯＨ／ｇ以下が好ましく、２０ｍｇＫＯＨ／ｇ以上１５０ｍｇＫＯＨ／ｇ以下がより好ましい。重量平均分子量（Ｍｗ）は、着色膜の信頼性の観点から５００以上１５０，０００以下が好ましく、５０００以上１５０，０００以下がより好ましい。なお、本発明におけるアミン価とは、分散剤１ｇを中和するのに必要な酸と当量のＫＯＨのｍｇ数を表す。
If the amine value of the dispersant (C) is too low, the adsorption to the coloring material will be insufficient, and if the amine value is too high, the storage stability of the colored resin composition will decrease. Therefore, the amine value is preferably 1 mgKOH/g or more and 200 mgKOH/g or less, more preferably 20 mgKOH/g or more and 150 mgKOH/g or less. From the viewpoint of the reliability of the colored film, the weight average molecular weight (Mw) is preferably 500 or more and 150,000 or less, more preferably 5000 or more and 150,000 or less. The amine value in the present invention represents the number of mg of KOH equivalent to the acid required to neutralize 1 g of the dispersant.
塩基性基を有するアクリル系分散剤としては、例えば、ＤＩＳＰＥＲＢＹＫ（登録商標）－１１２，１１６、１５１、１５５、１５６、１８７、１９０、１９１、１９４Ｎ、１９９、２０００、２００１、２００６、２００８、２００９、２０１０、２０１２、２０１３、２０１５、２０２０、２０２２、２０２５、２０５０、２０５５、２０７０、ＤＩＳＰＥＲＢＹＫ（登録商標）ＬＰＮ６９１９、ＬＰＮ２１１１６、ＬＰＮ２２１０２（以上、いずれもビックケミー社製）が挙げられる。これらの中でも、３級アミノ基および４級アンモニウム塩基の少なくとも１種を含有するアクリル系分散剤としては、例えば、ＤＩＳＰＥＲＢＹＫ（登録商標）－１８７、１９０、１９１、１９４Ｎ、１９９、２０００、２００１、２００６、２００９、２０１０、２０１２、２０１３、２０１５、２０２２、２０２５、２０５０、２０５５、ＤＩＳＰＥＲＢＹＫ（登録商標）ＬＰＮ６９１９、ＬＰＮ２１１１６が挙げられ、３級アミンおよび４級アンモニウム塩の両方を有するアクリル系分散剤としては、例えば、ＤＩＳＰＥＲＢＹＫ（登録商標）ＬＰＮ２１１１６が挙げられる。
Examples of acrylic dispersants having a basic group include DISPERBYK (registered trademark)-112, 116, 151, 155, 156, 187, 190, 191, 194N, 199, 2000, 2001, 2006, 2008, 2009, 2010, 2012, 2013, 2015, 2020, 2022, 2025, 2050, 2055, 2070, DISPERBYK (registered trademark) LPN6919, LPN21116, LPN22102 (all manufactured by BYK-Chemie). Among these, acrylic dispersants containing at least one of a tertiary amino group and a quaternary ammonium base include, for example, DISPERBYK (registered trademark)-187, 190, 191, 194N, 199, 2000, 2001, 2006 , 2009, 2010, 2012, 2013, 2015, 2022, 2025, 2050, 2055, DISPERBYK® LPN6919, LPN21116, and acrylic dispersants having both a tertiary amine and a quaternary ammonium salt, For example, DISPERBYK® LPN21116 may be mentioned.
（Ｃ）分散剤の含有量は、分散安定性を向上させる観点から、前述の（Ｂ）着色材１００質量部に対して、５質量部以上が好ましく、１０質量部以上がより好ましい。一方、分散剤の含有量は、着色膜の密着性や信頼性を向上させる観点から、着色材１００質量部に対して、１００質量部以下が好ましく、６０質量部以下がより好ましい。
From the viewpoint of improving dispersion stability, the content of (C) the dispersant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the coloring material (B). On the other hand, the content of the dispersant is preferably 100 parts by mass or less, more preferably 60 parts by mass or less with respect to 100 parts by mass of the coloring agent, from the viewpoint of improving the adhesion and reliability of the colored film.
（Ｄ）ブロックイソシアネートは、ブロック剤によってブロックされた２以上のイソシアネート基を有する化合物である。加熱によりブロック剤が解離して、イソシアネート基が再生するため、ブロックイソシアネートはポットライフが長く、これを含むインクは粘度安定性に優れる。本発明の着色樹脂組成物では、ブロックイソシアネートは硬化剤として用いられる。ブロックイソシアネートは、比較的低温での加熱によりブロック剤を解離（脱保護）してイソシアネート基を再生する。再生したイソシアネート基が（Ａ）水酸基または酸基含有樹脂の水酸基または酸基と熱反応することで、インクが硬化する。
(D) Blocked isocyanate is a compound having two or more isocyanate groups blocked by a blocking agent. Since the blocking agent is dissociated by heating to regenerate the isocyanate group, the blocked isocyanate has a long pot life and the ink containing it has excellent viscosity stability. A blocked isocyanate is used as a curing agent in the colored resin composition of the present invention. The blocked isocyanate dissociates (deprotects) the blocking agent by heating at a relatively low temperature to regenerate the isocyanate group. The regenerated isocyanate group thermally reacts with the hydroxyl group or acid group of the hydroxyl group- or acid group-containing resin (A) to cure the ink.
イソシアネートの種類としては、特に限定されないが、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネート、ジイソシアネートの変性による２量体または３量体、末端イソシアネート基含有化合物などである。これらを単独で使用しても併用しても良い。芳香族ジイソシアネートとしては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジフェニルメタン－２，４’－ジイソシアネート、ジアニシジンジイソシアネートなどが挙げられる。脂肪族ジイソシアネートとしては、例えば、１，４－テトラメチレンジイソシアネート、１，５－ペンタメチレンジイソシアネート、１，６－ヘキサメチレンジイソシアネート（以下ＨＭＤＩ）、２，２，４－トリメチル－１，６－ヘキサメチレンジイソシアネートなどが挙げられる。脂環族ジイソシアネートとしては、例えば、リジンジイソシアネート、イソホロンジイソシアネート（以下ＩＰＤＩ）、１，３－ビス（イソシアナトメチル）－シクロヘキサン、４，４’－ジシクロヘキシルメタンジイソシアネートなどが挙げられる。さらにこれらジイソシアネートの変性による２量体または３量体が挙げられる。変性の方法としてはビウレット化、イソシアヌレート化等が挙げられる。あるいは前述のジイソシアネート化合物またはポリイソシアネート化合物と例えばエチレングリコール、プロピレングリコール、トリメチロールプロパン、エタノールアミン、ポリエステルポリオール、ポリエーテルポリオール、ポリアミド等の活性水素化合物とを反応させて得られる末端イソシアネート基含有化合物などが挙げられる。
The type of isocyanate is not particularly limited, but includes aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, dimers or trimers obtained by modifying diisocyanates, and compounds containing terminal isocyanate groups. These may be used alone or in combination. Examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate and dianisidine diisocyanate. Aliphatic diisocyanates include, for example, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter referred to as HMDI), 2,2,4-trimethyl-1,6-hexamethylene and diisocyanate. Examples of the alicyclic diisocyanate include lysine diisocyanate, isophorone diisocyanate (hereinafter IPDI), 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate and the like. Dimers or trimers by modification of these diisocyanates are also included. Modification methods include biuret formation, isocyanurate formation, and the like. Alternatively, a terminal isocyanate group-containing compound obtained by reacting the aforementioned diisocyanate compound or polyisocyanate compound with an active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, polyester polyol, polyether polyol, polyamide, etc. is mentioned.
ブロック剤としては、例えば、フェノール、メチルエチルケトオキシム、重亜硫酸ソーダ等の公知のブロック剤が挙げられる。基材としてポリカーボネート、ＰＥＴフィルム等の樹脂を選定する場合には、ブロック剤がより低温で解離してイソシアネート基が遊離するブロックイソシアネートを用いることが好ましい。
Blocking agents include, for example, known blocking agents such as phenol, methyl ethyl ketoxime, and sodium bisulfite. When a resin such as a polycarbonate or a PET film is selected as the base material, it is preferable to use a blocked isocyanate in which the blocking agent dissociates at a lower temperature to liberate the isocyanate group.
この様な、より低温で解離可能なブロック剤としては、活性メチレン化合物またはピラゾール化合物を挙げることができる。活性メチレン化合物としては、メルドラム酸、マロン酸ジアルキル、アセト酢酸アルキル、２－アセトアセトキシエチルメタクリレート、アセチルアセトン、シアノ酢酸エチル等が挙げられる。ピラゾール化合物としては、ピラゾール、３，５－ジメチルピラゾール、３－メチルピラゾール、４－ベンジル－３，５－ジメチルピラゾール、４－ニトロ－３，５－ジメチルピラゾール、４－ブロモ－３，５－ジメチルピラゾール、３－メチル－５－フェニルピラゾール等が挙げられる。中でもマロン酸ジエチル、３，５－ジメチルピラゾール等が好ましい。
Examples of such blocking agents that can be dissociated at lower temperatures include active methylene compounds and pyrazole compounds. Active methylene compounds include Meldrum's acid, dialkyl malonate, alkyl acetoacetate, 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate. Pyrazole compounds include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethyl pyrazole, 3-methyl-5-phenylpyrazole and the like. Among them, diethyl malonate, 3,5-dimethylpyrazole and the like are preferable.
ブロックイソシアネートは、市販品として入手可能である。例えば、コロネート（登録商標）ＡＰステーブルＭ、コロネート（登録商標）２５０３、２５１５、２５０７、２５１３、２５５５、ミリオネートＭＳ－５０（以上、日本ポリウレタン工業（株）製）、デュラネート（登録商標）１７Ｂ－６０ＰＸ、１７Ｂ－６０Ｐ、ＴＰＡ－Ｂ８０Ｘ、ＴＰＡ－Ｂ８０Ｅ、ＭＦ－Ｂ６０Ｘ、ＭＦ－Ｂ６０Ｂ、ＭＦ－Ｋ６０Ｘ、ＭＦ－Ｋ６０Ｂ、Ｅ４０２－Ｂ８０Ｂ、ＳＢＮ－７０Ｄ、ＳＢＢ－７０Ｐ、Ｋ６０００（以上、旭化成ケミカルズ（株）製）、デスモジュールＢＬ１１００、ＢＬ１２６５ ＭＰＡ／Ｘ、ＢＬ３５７５／１、ＢＬ３２７２ＭＰＡ、ＢＬ３３７０ＭＰＡ、ＢＬ３４７５ＢＡ／ＳＮ、ＢＬ５３７５ＭＰＡ、ＶＰＬＳ２０７８／２、ＢＬ４２６５ＳＮ、ＰＬ３４０、ＰＬ３５０、スミジュール（登録商標）ＢＬ３１７５（以上、住化バイエルウレタン（株）製）等を好ましく使用することができる。
"Blocked isocyanate" is available as a commercial product. For example, Coronate (registered trademark) AP Stable M, Coronate (registered trademark) 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate (registered trademark) 17B- 60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, Asahi Kasei Chemicals ), Desmodur BL1100, BL1265 MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Sumidule (registered trademark) BL3175 (Sumika Bayer (manufactured by Urethane Co., Ltd.) and the like can be preferably used.
（Ａ）水酸基または酸基含有樹脂と（Ｄ）ブロックイソシアネートの含有量は、硬化後にそれらの各官能基が消費される様に、それぞれの量を選択することが好ましい。例えば、（Ｄ）ブロックイソシアネートの含有量は、（Ａ）水酸基または酸基含有樹脂の質量を１００質量部として、１～３００質量部が好ましく、５～１５０質量部がより好ましく、１０～１００質量部がさらに好ましい。ブロックイソシアネートの含有量がこれら範囲内にあると、水酸基または酸基含有樹脂を効率よく硬化できるという効果が得られる。
The contents of (A) a hydroxyl group- or acid group-containing resin and (D) a blocked isocyanate are preferably selected so that their respective functional groups are consumed after curing. For example, the content of (D) blocked isocyanate is preferably 1 to 300 parts by mass, more preferably 5 to 150 parts by mass, more preferably 10 to 100 parts by mass, with the mass of (A) hydroxyl group- or acid group-containing resin being 100 parts by mass. Part is more preferred. When the content of the blocked isocyanate is within these ranges, the effect of efficiently curing the hydroxyl group- or acid group-containing resin can be obtained.
本発明の着色樹脂組成物は、塗布性を改善できることから、さらに（Ｅ）有機溶媒を含有することが好ましい。（Ｅ）有機溶媒は、（Ａ）水酸基または酸基含有樹脂、（Ｂ）着色材、（Ｃ）分散剤、および（Ｄ）ブロックイソシアネートなどを均一に溶解または分散する作用を有する。（Ｅ）有機溶媒としては、大気圧下の沸点が１１０～２５０℃の化合物が好ましい。本発明の着色樹脂組成物はスピンコーター、スリットコーター、スクリーン印刷、インクジェット、グラビア印刷またはバーコーター等の印刷方式での塗布が想定されることから、沸点が１１０℃未満であると有機溶媒の乾燥速度が早く、塗布均一性に不具合が生じ易くなる。一方で、沸点が２５０℃を超えると、得られる着色膜に有機溶媒が残存し、着色膜の耐薬品性が悪化することがある。
The colored resin composition of the present invention preferably further contains (E) an organic solvent because it can improve the applicability. (E) The organic solvent has the effect of uniformly dissolving or dispersing (A) the hydroxyl group- or acid group-containing resin, (B) the coloring agent, (C) the dispersant, and (D) the blocked isocyanate. (E) As the organic solvent, a compound having a boiling point of 110 to 250° C. under atmospheric pressure is preferable. Since the colored resin composition of the present invention is assumed to be applied by a printing method such as spin coater, slit coater, screen printing, inkjet, gravure printing or bar coater, if the boiling point is less than 110 ° C., the drying of the organic solvent The speed is high, and problems with coating uniformity are likely to occur. On the other hand, if the boiling point exceeds 250° C., the organic solvent may remain in the resulting colored film and the chemical resistance of the colored film may deteriorate.
（Ｅ）有機溶剤としては、例えば、エーテル類、アセテート類、エステル類、ケトン類、芳香族炭化水素類、アミド類、アルコール類などが挙げられる。
(E) Organic solvents include, for example, ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.
エーテル類としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ－ｎ－プロピルエーテル、エチレングリコールモノ－ｎ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－プロピルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－プロピルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノ－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等が挙げられる。アセテート類としては、例えば、ブチルアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、シクロヘキサノールアセテート、プロピレングリコールジアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート（以下、「ＰＧＭＥＡ」：沸点１４６．４℃）、ジプロピレングリコールメチルエーテルアセテート、３－メトキシ－３－メチル－１－ブチルアセテート、１，４－ブタンジオールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサンジオールジアセテート等が挙げられる。エステル類としては、例えば、２－ヒドロキシプロピオン酸メチル、２－ヒドロキシプロピオン酸エチル等の乳酸アルキルエステル類；２－ヒドロキシ－２－メチルプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、３－メチル－３－メトキシブチルプロピオネート、酢酸エチル、酢酸ｎ－プロピル、酢酸ｉ－プロピル、酢酸ｎ－ブチル、酢酸ｉ－ブチル、蟻酸ｎ－ペンチル、酢酸ｉ－ペンチル、プロピオン酸ｎ－ブチル、酪酸エチル、酪酸ｎ－プロピル、酪酸ｉ－プロピル、酪酸ｎ－ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸ｎ－プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸エチル等が挙げられる。ケトン類としては、例えば、メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等が挙げられる。芳香族炭化水素類としては、例えば、トルエン、キシレンなどが挙げられる。アミド類としては、例えば、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等が挙げられる。アルコール類としては、例えば、ブチルアルコール、イソブチルアルコール、ペンタノ－ル、４－メチル－２－ペンタノール、３－メチル－２－ブタノール、３－メチル－３－メトキシブタノール、ジアセトンアルコール等などが挙げられる。これらを２種以上含有してもよい。
Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl. ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and the like. Acetates include, for example, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (hereinafter referred to as "PGMEA": boiling point 146.4°C), dipropylene glycol methyl ether acetate, 3 -Methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate and the like. Examples of esters include lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate and 3-methoxypropionic acid; ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate , ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and the like. . Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like. Examples of aromatic hydrocarbons include toluene and xylene. Amides include, for example, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and the like. Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol and the like. be done. You may contain 2 or more types of these.
これらの中でも、着色材をより分散安定化させるため、アセテート類が好ましい。（Ｅ）有機溶剤中におけるアセテート類の含有量は、５０～１００質量％が好ましく、７０～１００質量％がより好ましい。
Among these, acetates are preferable in order to further stabilize the dispersion of the coloring material. (E) The content of acetates in the organic solvent is preferably 50 to 100% by mass, more preferably 70 to 100% by mass.
着色樹脂組成物を基板に塗布して着色膜を形成するにあたって、基板の大型化に伴い、ダイコーティング装置による塗布が主流になりつつある。一方、カバーレンズの加飾や、近赤外線センサーおよび近赤外線カメラを隠蔽するための加飾膜として着色膜を形成する際には、小片ガラスに着色膜を形成する必要があり、スクリーン印刷装置もしくはインクジェット装置による塗布が好ましい。これら、ダイコーティング装置、スクリーン印刷装置、およびインクジェット装置による塗布における好適な揮発性や乾燥性を実現する観点から、（Ｅ）有機溶剤を２種以上含有することが好ましい。本発明の着色樹脂組成物から得られる塗布膜の膜厚を均一にし、表面の平滑性および粘着性を向上させる観点と、ダイコーティング装置およびインクジェット装置のノズルにおける乾燥異物を抑制する観点およびスクリーン印刷装置の連続印刷性の観点から、沸点が１５０～２５０℃の有機溶剤を、（Ｅ）有機溶剤中に３～９０質量％含有することが好ましく、１０～７５質量％含有することがより好ましい。
When applying a colored resin composition to a substrate to form a colored film, as the size of the substrate increases, application using a die coating apparatus is becoming mainstream. On the other hand, when forming a colored film as a decorative film for decorating the cover lens or concealing the near-infrared sensor and the near-infrared camera, it is necessary to form the colored film on the small piece of glass. Application by an inkjet device is preferred. From the viewpoint of achieving suitable volatility and drying properties in coating by a die coating device, a screen printing device, and an inkjet device, it is preferable to contain (E) two or more organic solvents. Uniform thickness of the coating film obtained from the colored resin composition of the present invention, the viewpoint of improving the smoothness and adhesiveness of the surface, the viewpoint of suppressing dry foreign matter in the nozzle of the die coating device and the inkjet device and screen printing From the viewpoint of continuous printing performance of the device, the organic solvent (E) preferably contains 3 to 90% by mass, more preferably 10 to 75% by mass, of an organic solvent having a boiling point of 150 to 250°C.
本発明の着色樹脂組成物における、（Ｅ）有機溶剤の含有量は、塗布工程における塗布膜の膜厚均一性の観点から、組成物全体の５０質量％以上が好ましく、７０質量％以上がより好ましい。一方、（Ｅ）有機溶剤の含有量は、顔料沈降を抑制する観点から、組成物全体の９５質量％以下が好ましく、９０質量％以下がより好ましい。
In the colored resin composition of the present invention, the content of the (E) organic solvent is preferably 50% by mass or more of the entire composition from the viewpoint of uniformity of the coating film thickness in the coating step, and more preferably 70% by mass or more. preferable. On the other hand, the content of the (E) organic solvent is preferably 95% by mass or less, more preferably 90% by mass or less, of the entire composition from the viewpoint of suppressing pigment sedimentation.
本発明の着色樹脂組成物は、レベリング剤を含有してもよい。レベリング剤を含有することにより、塗布性や着色膜の表面平滑性を向上させることができる。レベリング剤としては、例えば、ラウリル硫酸アンモニウム、ポリオキシエチレンアルキルエーテル硫酸トリエタノールアミン等の陰イオン界面活性剤；ステアリルアミンアセテート、ラウリルトリメチルアンモニウムクロライド等の陽イオン界面活性剤；ラウリルジメチルアミンオキサイド、ラウリルカルボキシメチルヒドロキシエチルイミダゾリウムベタイン等の両性界面活性剤；ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ソルビタンモノステアレート等の非イオン界面活性剤；ポリジメチルシロキサン等を主骨格とするシリコーン系界面活性剤；フッ素系界面活性剤などが挙げられる。これらを２種以上含有してもよい。界面活性剤の市販品としては、例えば、“ＢＹＫ（登録商標）”－３０２、３３３、３５５０、３９２（以上、いずれもビックケミー社製）が挙げられる。
The colored resin composition of the present invention may contain a leveling agent. By containing a leveling agent, the coatability and the surface smoothness of the colored film can be improved. Examples of leveling agents include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; Amphoteric surfactants such as methylhydroxyethylimidazolium betaine; Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate; Silicone surfactants having a main skeleton such as polydimethylsiloxane agents; fluorine-based surfactants, and the like. You may contain 2 or more types of these. Examples of commercially available surfactants include "BYK (registered trademark)"-302, 333, 3550, and 392 (all of which are manufactured by BYK-Chemie).
本発明の着色樹脂組成物の製造方法としては、例えば、分散機を用いて（Ａ）水酸基または酸基含有樹脂、（Ｂ）着色材、（Ｃ）分散剤および（Ｅ）有機溶剤を含有する樹脂溶液を分散処理することにより、着色材濃度の高い着色材分散液を予め調製しておき、そこにさらに（Ａ）水酸基または酸基含有樹脂や（Ｄ）ブロックイソシアネート、および必要に応じて界面活性剤などの他の成分を添加して撹拌する方法が好ましい。必要に応じて得られた着色樹脂組成物の濾過を行ってもよい。
As a method for producing the colored resin composition of the present invention, for example, a dispersion machine is used to contain (A) a hydroxyl group- or acid group-containing resin, (B) a coloring agent, (C) a dispersant and (E) an organic solvent. By dispersing the resin solution, a coloring agent dispersion having a high coloring agent concentration is prepared in advance, and (A) a hydroxyl group- or acid group-containing resin, (D) a blocked isocyanate, and, if necessary, an interface A method of adding other ingredients such as an activator and stirring is preferred. Filtration of the obtained colored resin composition may be performed as necessary.
分散処理に用いる分散機としては、例えば、ボールミル、ビーズミル、サンドグラインダー、３本ロールミル、高速度衝撃ミルなどが挙げられる。これらの中でも、分散効率化および微分散化のため、ビーズミルが好ましい。ビーズミルとしては、例えば、コボールミル、バスケットミル、ピンミル、ダイノーミルなどが挙げられる。ビーズミルのビーズとしては、例えば、チタニアビーズ、ジルコニアビーズ、ジルコンビーズが挙げられる。
Dispersers used for dispersion treatment include, for example, ball mills, bead mills, sand grinders, three-roll mills, and high-speed impact mills. Among these, a bead mill is preferable for improving dispersion efficiency and fine dispersion. Examples of bead mills include coball mills, basket mills, pin mills, and dyno mills. Bead mill beads include, for example, titania beads, zirconia beads, and zircon beads.
本発明の着色樹脂組成物の製造方法においては、ビーズミルにより多段階で分散処理することが好ましい。例えば、平均ビーズ径が０．１ｍｍφよりも大きいビーズを用いたビーズミルにより分散処理した後、平均ビーズ径が０．１ｍｍφ以下のビーズを用いたビーズミルにより分散処理することが好ましい。平均ビーズ径が０．１ｍｍφよりも大きいビーズを用いたビーズミルにより分散処理することにより、結晶子サイズの大きな着色材を効率的に解砕することができる。その後に平均ビーズ径が０．１ｍｍφ以下の微小なビーズを用いたビーズミルにより分散処理することにより、着色材へ与えるエネルギーを小さくして着色材の表面活性を抑えながら微分散することができる。これにより、着色樹脂組成物中における着色材の再凝集を抑制し、より均一に微細に分散させることができる。この場合、ビーズミルには、微小なビーズと分散液とを分離することが可能な、遠心分離方式によるセパレーターを備えることが好ましい。ここで、平均ビーズ径とは、ビーズの円相当径の数平均値をいう。具体的には、ビーズを実体顕微鏡で４５倍に拡大撮影し、無作為に選んだ１００個のビーズについて、それぞれ最長径と最短径を測定してその平均値を円相当径とし、その数平均値を算出することにより、ビーズ径を求めることができる。
In the method for producing the colored resin composition of the present invention, it is preferable to perform dispersion treatment in multiple stages using a bead mill. For example, it is preferable to disperse with a bead mill using beads having an average bead diameter of more than 0.1 mmφ, and then to disperse with a bead mill using beads having an average bead diameter of 0.1 mmφ or less. A coloring material having a large crystallite size can be efficiently pulverized by dispersing with a bead mill using beads having an average bead diameter larger than 0.1 mmφ. After that, by performing a dispersion treatment using a bead mill using fine beads having an average bead diameter of 0.1 mmφ or less, the energy given to the coloring agent can be reduced, and the coloring agent can be finely dispersed while suppressing the surface activity of the coloring agent. As a result, reaggregation of the colorant in the colored resin composition can be suppressed, and the colorant can be dispersed more uniformly and finely. In this case, the bead mill is preferably provided with a centrifugal separator capable of separating fine beads from the dispersion liquid. Here, the average bead diameter refers to the number average value of equivalent circle diameters of beads. Specifically, the beads were photographed at a magnification of 45 times with a stereoscopic microscope, and the longest and shortest diameters of 100 randomly selected beads were measured, and the average value was taken as the circle equivalent diameter, and the number average By calculating the value, the bead diameter can be obtained.
本発明の着色樹脂組成物を硬化させることにより、着色膜を得ることができる。ディスプレイ非表示領域に形成される着色膜の遮光性としては、バックライトの光漏れを防ぐ観点からＯＤ値４．０以上が好ましく、ＯＤ値４．５以上がより好ましい。
A colored film can be obtained by curing the colored resin composition of the present invention. The light shielding property of the colored film formed in the non-display area of the display is preferably 4.0 or more OD, more preferably 4.5 or more, from the viewpoint of preventing light leakage from the backlight.
次に、本発明の着色樹脂組成物を硬化させて加飾基板を形成する方法について説明する。以下の方法により、着色樹脂組成物を基板上に塗布して、硬化させて着色膜を形成することにより、基板および着色膜を具備する加飾基板を得る。
Next, a method for curing the colored resin composition of the present invention to form a decorative substrate will be described. A decorative substrate comprising a substrate and a colored film is obtained by coating a colored resin composition on a substrate and curing it to form a colored film by the following method.
基板としては、例えば、ソーダガラス、無アルカリガラス、アルミノシリケートガラス等の透明ガラス基板；ポリカーボネート樹脂、アクリル樹脂等の樹脂基板；ＰＥＴフィルム、ＣＯＰフィルム等のフィルム基板；シリコンウエハー、セラミックス類、ガリウムヒ素の基板などが挙げられる。塗布方法としては、例えば、スピンナーを用いた回転塗布、スプレー塗布、ダイコーティング、ロールコーティング、インクジェット印刷、スクリーン印刷、グラビア印刷などが挙げられる。塗布膜の膜厚は、塗布方法等によって適宜選択することができる。乾燥後の膜厚を１～１５０μｍとすることが一般的である。
Examples of substrates include transparent glass substrates such as soda glass, non-alkali glass, and aluminosilicate glass; resin substrates such as polycarbonate resin and acrylic resin; film substrates such as PET film and COP film; silicon wafers, ceramics, and gallium arsenide. and the like. Examples of coating methods include spin coating using a spinner, spray coating, die coating, roll coating, inkjet printing, screen printing, and gravure printing. The film thickness of the coating film can be appropriately selected depending on the coating method or the like. The film thickness after drying is generally 1 to 150 μm.
得られた塗布膜を乾燥して、乾燥膜を得る。乾燥方法としては、例えば、加熱乾燥、風乾、減圧乾燥、赤外線照射等が挙げられる。加熱乾燥装置としては、例えば、オーブン、ホットプレートなどが挙げられる。乾燥温度は５０～１５０℃が好ましく、乾燥時間は１分間～数時間が好ましい。この乾燥工程により、レベリングによる塗布膜の平坦化や異物付着の抑制などが期待されるが、必ずしもこの乾燥工程が必要ではなく、後述の加熱処理のみでも着色膜を得ることができる。
The obtained coating film is dried to obtain a dry film. Examples of the drying method include heat drying, air drying, reduced pressure drying, and infrared irradiation. Examples of heat drying devices include ovens and hot plates. The drying temperature is preferably 50 to 150° C., and the drying time is preferably 1 minute to several hours. This drying process is expected to level the coating film and suppress the adhesion of foreign substances. However, this drying process is not necessarily required, and a colored film can be obtained only by the heat treatment described later.
得られた塗布膜を加熱処理（ポストベーク）することにより硬化させ、着色膜を得ることができる。加熱処理は、空気中、窒素雰囲気下、真空状態のいずれで行ってもよい。加熱温度は７０～３００℃が好ましく、特に８０～１８０℃が好ましい。基材が樹脂の場合には基材の耐熱温度に応じて加熱温度を選択することができ、例えば、基材がポリカーボネートの場合では８０～１２０℃が好ましい。加熱時間は０．２５～５時間が好ましい。加熱処理中、加熱温度を連続的に変化させてもよいし、段階的に変化させてもよい。
The resulting coating film is cured by heat treatment (post-baking) to obtain a colored film. The heat treatment may be performed in air, in a nitrogen atmosphere, or in a vacuum. The heating temperature is preferably 70 to 300°C, more preferably 80 to 180°C. When the base material is a resin, the heating temperature can be selected according to the heat resistance temperature of the base material. The heating time is preferably 0.25 to 5 hours. During the heat treatment, the heating temperature may be changed continuously or stepwise.
基板および本発明の着色樹脂組成物の硬化物からなる着色膜を具備する加飾基板は、スマートフォンやタブレットＰＣや車載ディスプレイなどの表示端末における加飾基板、車載ディスプレイや車載計器における運転者監視やジェスチャーセンサー用の近赤外線センサーおよび近赤外線カメラ隠蔽用の加飾基板、ＬｉＤＡＲセンサー隠蔽用加飾フィルムなどに好適に利用できる。また、本発明の着色樹脂組成物の硬化物からなる着色膜は液晶表示装置等が備えるカラーフィルターのブラックマトリクス等の遮光膜、有機ＥＬディスプレイ内部の着色隔壁などに好適に利用できる。
A decorative substrate comprising a substrate and a colored film made of a cured product of the colored resin composition of the present invention is a decorative substrate in display terminals such as smartphones, tablet PCs, and in-vehicle displays, and is used for driver monitoring in in-vehicle displays and in-vehicle instruments. It can be suitably used for a near-infrared sensor for a gesture sensor, a decorative substrate for concealing a near-infrared camera, a decorative film for concealing a LiDAR sensor, and the like. In addition, the colored film made of the cured product of the colored resin composition of the present invention can be suitably used as a light-shielding film such as a black matrix of a color filter provided in a liquid crystal display device or the like, a colored partition wall inside an organic EL display, and the like.
以下に本発明を実施例および比較例を挙げて詳細に説明するが、本発明の態様はこれらに限定されるものではない。
The present invention will be described in detail below with examples and comparative examples, but the aspects of the present invention are not limited to these.
＜評価方法＞
［密着性］
各実施例および比較例により得られた着色膜について、ＪＩＳ「Ｋ５６００－５－６（制定年月日＝１９９９／０４／２０）」に準じて密着性を評価した。具体的には、着色膜にカッターナイフを用いて、基板の素地に到達するように、直交する縦横１１本ずつの平行な直線を１ｍｍ間隔で引いて、１ｍｍ×１ｍｍのマス目を１００個作製した。切られた着色膜表面にセロハン粘着テープ（幅＝１８ｍｍ、粘着力＝３．７Ｎ／１０ｍｍ）を貼り付け、消しゴム（ＪＩＳ Ｓ６０５０合格品）で擦って、テープと着色膜を密着させた後、テープの一端を持ち、テープが板と直角になるように保ちながら、テープを着色膜から瞬間的に剥離した。このとき、１００個の着色膜のマス目のうち、基板から剥離せずに残存した着色膜のマス目の数を目視によって確認することにより、剥離した着色膜の割合を評価した。マス目の剥離面積により以下のように着色膜の密着性を判定し、４以上を合格とした。
５：剥離面積＝０％
４：剥離面積＝＜５％
３：剥離面積＝５～１４％
２：剥離面積＝１５～３４％
１：剥離面積＝３５％～６４％
０：剥離面積＝６５％～１００％。 <Evaluation method>
[Adhesion]
Adhesion was evaluated for the colored films obtained in each example and comparative example according to JIS "K5600-5-6 (enacted date = 1999/04/20)". Specifically, using a cutter knife on the colored film, draw 11 perpendicular and horizontal parallel straight lines at 1 mm intervals so as to reach the base of the substrate, and prepare 100 squares of 1 mm × 1 mm. did. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is attached to the cut colored film surface, rubbed with an eraser (JIS S6050 acceptable product), and the tape and the colored film are adhered. While holding one end of the tape and keeping the tape perpendicular to the plate, the tape was momentarily peeled from the colored film. At this time, the ratio of the peeled colored film was evaluated by visually confirming the number of squares of the colored film remaining without peeling from the substrate among the 100 squares of the colored film. The adhesiveness of the colored film was determined as follows based on the peeling area of the squares, and 4 or more was regarded as acceptable.
5: Peeling area = 0%
4: Peeling area = <5%
3: Peeling area = 5 to 14%
2: Peeling area = 15 to 34%
1: Peeling area = 35% to 64%
0: Peeling area = 65% to 100%.
［密着性］
各実施例および比較例により得られた着色膜について、ＪＩＳ「Ｋ５６００－５－６（制定年月日＝１９９９／０４／２０）」に準じて密着性を評価した。具体的には、着色膜にカッターナイフを用いて、基板の素地に到達するように、直交する縦横１１本ずつの平行な直線を１ｍｍ間隔で引いて、１ｍｍ×１ｍｍのマス目を１００個作製した。切られた着色膜表面にセロハン粘着テープ（幅＝１８ｍｍ、粘着力＝３．７Ｎ／１０ｍｍ）を貼り付け、消しゴム（ＪＩＳ Ｓ６０５０合格品）で擦って、テープと着色膜を密着させた後、テープの一端を持ち、テープが板と直角になるように保ちながら、テープを着色膜から瞬間的に剥離した。このとき、１００個の着色膜のマス目のうち、基板から剥離せずに残存した着色膜のマス目の数を目視によって確認することにより、剥離した着色膜の割合を評価した。マス目の剥離面積により以下のように着色膜の密着性を判定し、４以上を合格とした。
５：剥離面積＝０％
４：剥離面積＝＜５％
３：剥離面積＝５～１４％
２：剥離面積＝１５～３４％
１：剥離面積＝３５％～６４％
０：剥離面積＝６５％～１００％。 <Evaluation method>
[Adhesion]
Adhesion was evaluated for the colored films obtained in each example and comparative example according to JIS "K5600-5-6 (enacted date = 1999/04/20)". Specifically, using a cutter knife on the colored film, draw 11 perpendicular and horizontal parallel straight lines at 1 mm intervals so as to reach the base of the substrate, and prepare 100 squares of 1 mm × 1 mm. did. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is attached to the cut colored film surface, rubbed with an eraser (JIS S6050 acceptable product), and the tape and the colored film are adhered. While holding one end of the tape and keeping the tape perpendicular to the plate, the tape was momentarily peeled from the colored film. At this time, the ratio of the peeled colored film was evaluated by visually confirming the number of squares of the colored film remaining without peeling from the substrate among the 100 squares of the colored film. The adhesiveness of the colored film was determined as follows based on the peeling area of the squares, and 4 or more was regarded as acceptable.
5: Peeling area = 0%
4: Peeling area = <5%
3: Peeling area = 5 to 14%
2: Peeling area = 15 to 34%
1: Peeling area = 35% to 64%
0: Peeling area = 65% to 100%.
［粘度の測定］
調製直後および３０℃／１週間経時後の着色樹脂組成物について、それぞれＥ型粘度計（東機産業（株）製「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２５」）を用いて２５℃での粘度を測定した。調製直後の粘度を（ａ）、３０℃／１週間経時後の粘度を（ｂ）としたときの、比率（ｂ）／（ａ）に基づいて、着色樹脂組成物の常温における粘度安定性を下記のように判定し、ＡおよびＢを合格とした。Ａが最も優れており、Ｄが最も劣っている。
Ａ：（ｂ）／（ａ）≦１．１
Ｂ：１．１＜（ｂ）／（ａ）≦１．５
Ｃ：１．５＜（ｂ）／（ａ）≦２．０
Ｄ：２．０＜（ｂ）／（ａ）。 [Measurement of viscosity]
The viscosity at 25° C. was measured using an E-type viscometer (“VISCOMETER TV-25” manufactured by Toki Sangyo Co., Ltd.) immediately after preparation and after aging at 30° C./one week. Based on the ratio (b) / (a), where the viscosity immediately after preparation is (a) and the viscosity after aging at 30 ° C. / 1 week is (b), the viscosity stability at room temperature of the colored resin composition Judgments were made as follows, and A and B were regarded as acceptable. A is the best and D is the worst.
A: (b)/(a) ≤ 1.1
B: 1.1<(b)/(a)≤1.5
C: 1.5<(b)/(a)≤2.0
D: 2.0<(b)/(a).
調製直後および３０℃／１週間経時後の着色樹脂組成物について、それぞれＥ型粘度計（東機産業（株）製「ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２５」）を用いて２５℃での粘度を測定した。調製直後の粘度を（ａ）、３０℃／１週間経時後の粘度を（ｂ）としたときの、比率（ｂ）／（ａ）に基づいて、着色樹脂組成物の常温における粘度安定性を下記のように判定し、ＡおよびＢを合格とした。Ａが最も優れており、Ｄが最も劣っている。
Ａ：（ｂ）／（ａ）≦１．１
Ｂ：１．１＜（ｂ）／（ａ）≦１．５
Ｃ：１．５＜（ｂ）／（ａ）≦２．０
Ｄ：２．０＜（ｂ）／（ａ）。 [Measurement of viscosity]
The viscosity at 25° C. was measured using an E-type viscometer (“VISCOMETER TV-25” manufactured by Toki Sangyo Co., Ltd.) immediately after preparation and after aging at 30° C./one week. Based on the ratio (b) / (a), where the viscosity immediately after preparation is (a) and the viscosity after aging at 30 ° C. / 1 week is (b), the viscosity stability at room temperature of the colored resin composition Judgments were made as follows, and A and B were regarded as acceptable. A is the best and D is the worst.
A: (b)/(a) ≤ 1.1
B: 1.1<(b)/(a)≤1.5
C: 1.5<(b)/(a)≤2.0
D: 2.0<(b)/(a).
［高温高湿耐性］
各実施例および比較例により得られた着色膜を、平山製作所製ＰＣ－２４２ＨＳ－Ｅを用いて、１２１℃、２気圧、１００％湿度条件で２４時間処理した後、前記［密着性］の評価を行った。 [High temperature and high humidity resistance]
The colored films obtained in Examples and Comparative Examples were treated using PC-242HS-E manufactured by Hirayama Seisakusho under conditions of 121°C, 2 atm, and 100% humidity for 24 hours, and then the [adhesion] was evaluated. did
各実施例および比較例により得られた着色膜を、平山製作所製ＰＣ－２４２ＨＳ－Ｅを用いて、１２１℃、２気圧、１００％湿度条件で２４時間処理した後、前記［密着性］の評価を行った。 [High temperature and high humidity resistance]
The colored films obtained in Examples and Comparative Examples were treated using PC-242HS-E manufactured by Hirayama Seisakusho under conditions of 121°C, 2 atm, and 100% humidity for 24 hours, and then the [adhesion] was evaluated. did
［耐光性］
各実施例および比較例により得られた着色膜を、Ｑ－Ｌａｂ社製Ｑ－ＳＵＮキセノン試験機Ｘｅ－３を用いて、ＸｅランプＸ－１８００を光源として、波長４２０ｎｍにおける照度が１．２Ｗ／ｍ２となる強度で３００時間、紫外線を照射した後、前記［密着性］の評価を行った。 [Lightfastness]
The colored films obtained in Examples and Comparative Examples were tested using a Q-Sun xenon tester Xe-3 manufactured by Q-Lab, using a Xe lamp X-1800 as a light source, with an illuminance of 1.2 W/ at a wavelength of 420 nm. After irradiating with ultraviolet rays for 300 hours at an intensity of m 2 , the above [adhesion] was evaluated.
各実施例および比較例により得られた着色膜を、Ｑ－Ｌａｂ社製Ｑ－ＳＵＮキセノン試験機Ｘｅ－３を用いて、ＸｅランプＸ－１８００を光源として、波長４２０ｎｍにおける照度が１．２Ｗ／ｍ２となる強度で３００時間、紫外線を照射した後、前記［密着性］の評価を行った。 [Lightfastness]
The colored films obtained in Examples and Comparative Examples were tested using a Q-Sun xenon tester Xe-3 manufactured by Q-Lab, using a Xe lamp X-1800 as a light source, with an illuminance of 1.2 W/ at a wavelength of 420 nm. After irradiating with ultraviolet rays for 300 hours at an intensity of m 2 , the above [adhesion] was evaluated.
［着色材の平均粒子径］
動的光散乱方式の粒度分布計（マイクロトラック・ベル社製ＵＰＡ－ＥＸ１５０）を２０±１℃に温度設定し、着色材分散液または着色樹脂組成物をプロピレングリコールモノメチルエーテルアセテートで４００倍に希釈したものを測定して得られた測定値（Ｄ５０）を着色材粒子の平均粒子径の値とした。 [Average particle size of coloring material]
Set the temperature of a dynamic light scattering particle size distribution meter (UPA-EX150 manufactured by Microtrac Bell Co., Ltd.) to 20 ± 1 ° C., and dilute the coloring material dispersion or colored resin composition 400 times with propylene glycol monomethyl ether acetate. The measured value (D50) obtained by measuring the colorant particles was used as the value of the average particle size of the coloring material particles.
動的光散乱方式の粒度分布計（マイクロトラック・ベル社製ＵＰＡ－ＥＸ１５０）を２０±１℃に温度設定し、着色材分散液または着色樹脂組成物をプロピレングリコールモノメチルエーテルアセテートで４００倍に希釈したものを測定して得られた測定値（Ｄ５０）を着色材粒子の平均粒子径の値とした。 [Average particle size of coloring material]
Set the temperature of a dynamic light scattering particle size distribution meter (UPA-EX150 manufactured by Microtrac Bell Co., Ltd.) to 20 ± 1 ° C., and dilute the coloring material dispersion or colored resin composition 400 times with propylene glycol monomethyl ether acetate. The measured value (D50) obtained by measuring the colorant particles was used as the value of the average particle size of the coloring material particles.
［拡散反射］
各実施例および比較例により得られた着色膜について、白色校正板（ＣＭ－Ａ１４５；コニカミノルタ（株）製）で校正した分光測色計（ＣＭ－２６００ｄ；コニカミノルタ（株）製）を用い、標準光源Ｄ６５（色温度６５０４Ｋ）、視野角２°（ＣＩＥ１９７６）、大気圧下、２０℃の測定条件下で透明基材側から入射させた光に対する拡散反射色度（ＳＣＥ）を測定した。着色膜の拡散反射率の指標として（Ｌ＊）を評価した。カバーレンズの非表示領域に形成される着色膜は意匠性の観点からＬ＊が低いことが好ましい。 [Diffuse reflection]
The colored films obtained in Examples and Comparative Examples were measured using a spectrophotometer (CM-2600d; manufactured by Konica Minolta, Inc.) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta, Inc.). , standard light source D65 (color temperature 6504K), viewing angle 2° (CIE1976), atmospheric pressure, 20°C, diffuse reflection chromaticity (SCE) for light incident from the transparent substrate side was measured. (L * ) was evaluated as an index of the diffuse reflectance of the colored film. The colored film formed in the non-display area of the cover lens preferably has a low L * from the viewpoint of design.
各実施例および比較例により得られた着色膜について、白色校正板（ＣＭ－Ａ１４５；コニカミノルタ（株）製）で校正した分光測色計（ＣＭ－２６００ｄ；コニカミノルタ（株）製）を用い、標準光源Ｄ６５（色温度６５０４Ｋ）、視野角２°（ＣＩＥ１９７６）、大気圧下、２０℃の測定条件下で透明基材側から入射させた光に対する拡散反射色度（ＳＣＥ）を測定した。着色膜の拡散反射率の指標として（Ｌ＊）を評価した。カバーレンズの非表示領域に形成される着色膜は意匠性の観点からＬ＊が低いことが好ましい。 [Diffuse reflection]
The colored films obtained in Examples and Comparative Examples were measured using a spectrophotometer (CM-2600d; manufactured by Konica Minolta, Inc.) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta, Inc.). , standard light source D65 (color temperature 6504K), viewing angle 2° (CIE1976), atmospheric pressure, 20°C, diffuse reflection chromaticity (SCE) for light incident from the transparent substrate side was measured. (L * ) was evaluated as an index of the diffuse reflectance of the colored film. The colored film formed in the non-display area of the cover lens preferably has a low L * from the viewpoint of design.
［耐溶剤性］
各実施例および比較例により得られた着色膜について、膜厚を接触膜厚計サーフコム１４００Ｄ（(株)東京精密製）を用いて測定した。試験用溶剤であるイソプロピルアルコールを十分に染み込ませた綿製の白布（カナキン３号）を摩擦子として、着色膜に接触するよう重ねて、学振型ラビングテスターを用いて、一定荷重条件下（３００ｇ／ｃｍ２）でラビング試験（１０回往復）を行なった後、再び膜厚測定を行った。ラビング試験前後の着色膜の膜厚変化から、下記の式より、着色膜の耐溶剤性を求めた。１００％に近い方が良好であり、８０％以上を合格とした。
耐溶剤性（％）＝ラビング試験後膜厚（μｍ）×１００／ラビング試験前膜厚（μｍ）
耐溶剤性の評価は、低温焼成時の硬化性の度合いを定量的に評価するために行われる。 [Solvent resistance]
The film thickness of the colored film obtained in each example and comparative example was measured using a contact film thickness gauge Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.). Using a white cotton cloth (Kanakin No. 3) sufficiently impregnated with isopropyl alcohol, a test solvent, as a friction element, layered so as to come into contact with the colored film, using a Gakushin type rubbing tester, under a constant load condition ( After performing a rubbing test (10 reciprocations) at 300 g/cm 2 ), the film thickness was measured again. From the changes in the thickness of the colored film before and after the rubbing test, the solvent resistance of the colored film was obtained from the following formula. A value closer to 100% is better, and a value of 80% or more was considered acceptable.
Solvent resistance (%) = film thickness after rubbing test (μm) × 100/film thickness before rubbing test (μm)
Evaluation of solvent resistance is performed to quantitatively evaluate the degree of curability during low-temperature baking.
各実施例および比較例により得られた着色膜について、膜厚を接触膜厚計サーフコム１４００Ｄ（(株)東京精密製）を用いて測定した。試験用溶剤であるイソプロピルアルコールを十分に染み込ませた綿製の白布（カナキン３号）を摩擦子として、着色膜に接触するよう重ねて、学振型ラビングテスターを用いて、一定荷重条件下（３００ｇ／ｃｍ２）でラビング試験（１０回往復）を行なった後、再び膜厚測定を行った。ラビング試験前後の着色膜の膜厚変化から、下記の式より、着色膜の耐溶剤性を求めた。１００％に近い方が良好であり、８０％以上を合格とした。
耐溶剤性（％）＝ラビング試験後膜厚（μｍ）×１００／ラビング試験前膜厚（μｍ）
耐溶剤性の評価は、低温焼成時の硬化性の度合いを定量的に評価するために行われる。 [Solvent resistance]
The film thickness of the colored film obtained in each example and comparative example was measured using a contact film thickness gauge Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.). Using a white cotton cloth (Kanakin No. 3) sufficiently impregnated with isopropyl alcohol, a test solvent, as a friction element, layered so as to come into contact with the colored film, using a Gakushin type rubbing tester, under a constant load condition ( After performing a rubbing test (10 reciprocations) at 300 g/cm 2 ), the film thickness was measured again. From the changes in the thickness of the colored film before and after the rubbing test, the solvent resistance of the colored film was obtained from the following formula. A value closer to 100% is better, and a value of 80% or more was considered acceptable.
Solvent resistance (%) = film thickness after rubbing test (μm) × 100/film thickness before rubbing test (μm)
Evaluation of solvent resistance is performed to quantitatively evaluate the degree of curability during low-temperature baking.
（合成例１ 水酸基または酸基含有樹脂（Ｐ－１）の合成）
１０００ｃｃの４つ口フラスコにイソプロピルアルコールを１００ｇ仕込み、これをオイルバス中で８０℃に保ち、窒素シールし、攪拌を行いながら、モノマーとしてメタクリル酸メチル３０ｇ、スチレン４０ｇおよびメタクリル酸３０ｇと開始剤としてＮ，Ｎ－アゾビスイソブチロニトリル２ｇを混合したものを滴下ロートで３０分かけて滴下した。この後４時間反応を続けた後、ハイドロキノンモノメチルエーテルを１ｇ添加してから常温に戻し、重合を完了した。つぎにこのポリマー溶液にイソプロピルアルコール１００ｇを添加した後、これを７５℃に保ちながらメタクリル酸グリシジル４０ｇとトリエチルベンジルアンモニウムクロライド３ｇを添加し、３時間反応させた。反応終了後、得られた樹脂溶液を精製水で再沈し、濾過および乾燥することにより、重量平均分子量１５，０００、水酸基価０ｍｇＫＯＨ／ｇ、酸価１１０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－１）を得た。なお、樹脂の水酸基価は、ＪＩＳ Ｋ００７０（１９９２）に従って、樹脂１ｇをアセチル化させたときに水酸基と結合した酢酸を中和するのに要する水酸化カリウムのｍｇ数を測定した。樹脂の酸価は、ＪＩＳ Ｋ００７０（１９９２）に従って、樹脂１ｇを中和するのに要する水酸化カリウムのｍｇ数を測定した。重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）「ＨＬＣ－８２２０ＧＰＣ」（東ソー（株）製試験装置）を用いて、キャリヤーをテトラヒドロフランとして、ポリスチレン換算により測定した。 (Synthesis Example 1 Synthesis of hydroxyl group- or acid group-containing resin (P-1))
A 1000 cc four-necked flask was charged with 100 g of isopropyl alcohol, which was kept at 80° C. in an oil bath, sealed with nitrogen, and stirred while adding 30 g of methyl methacrylate as monomers, 40 g of styrene and 30 g of methacrylic acid as initiators. A mixture of 2 g of N,N-azobisisobutyronitrile was added dropwise with a dropping funnel over 30 minutes. After continuing the reaction for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the temperature was returned to room temperature to complete the polymerization. After adding 100 g of isopropyl alcohol to this polymer solution, 40 g of glycidyl methacrylate and 3 g of triethylbenzylammonium chloride were added while maintaining the polymer solution at 75° C., and the mixture was allowed to react for 3 hours. After completion of the reaction, the resulting resin solution was reprecipitated with purified water, filtered and dried to give a hydroxyl- or acid-containing resin (weight-average molecular weight of 15,000, hydroxyl value of 0 mgKOH/g, acid value of 110 mgKOH/g). P-1) was obtained. The hydroxyl value of the resin was measured in mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the resin was acetylated according to JIS K0070 (1992). For the acid value of the resin, the number of mg of potassium hydroxide required to neutralize 1 g of the resin was measured according to JIS K0070 (1992). The weight average molecular weight was measured by polystyrene conversion using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation) using tetrahydrofuran as the carrier.
１０００ｃｃの４つ口フラスコにイソプロピルアルコールを１００ｇ仕込み、これをオイルバス中で８０℃に保ち、窒素シールし、攪拌を行いながら、モノマーとしてメタクリル酸メチル３０ｇ、スチレン４０ｇおよびメタクリル酸３０ｇと開始剤としてＮ，Ｎ－アゾビスイソブチロニトリル２ｇを混合したものを滴下ロートで３０分かけて滴下した。この後４時間反応を続けた後、ハイドロキノンモノメチルエーテルを１ｇ添加してから常温に戻し、重合を完了した。つぎにこのポリマー溶液にイソプロピルアルコール１００ｇを添加した後、これを７５℃に保ちながらメタクリル酸グリシジル４０ｇとトリエチルベンジルアンモニウムクロライド３ｇを添加し、３時間反応させた。反応終了後、得られた樹脂溶液を精製水で再沈し、濾過および乾燥することにより、重量平均分子量１５，０００、水酸基価０ｍｇＫＯＨ／ｇ、酸価１１０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－１）を得た。なお、樹脂の水酸基価は、ＪＩＳ Ｋ００７０（１９９２）に従って、樹脂１ｇをアセチル化させたときに水酸基と結合した酢酸を中和するのに要する水酸化カリウムのｍｇ数を測定した。樹脂の酸価は、ＪＩＳ Ｋ００７０（１９９２）に従って、樹脂１ｇを中和するのに要する水酸化カリウムのｍｇ数を測定した。重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）「ＨＬＣ－８２２０ＧＰＣ」（東ソー（株）製試験装置）を用いて、キャリヤーをテトラヒドロフランとして、ポリスチレン換算により測定した。 (Synthesis Example 1 Synthesis of hydroxyl group- or acid group-containing resin (P-1))
A 1000 cc four-necked flask was charged with 100 g of isopropyl alcohol, which was kept at 80° C. in an oil bath, sealed with nitrogen, and stirred while adding 30 g of methyl methacrylate as monomers, 40 g of styrene and 30 g of methacrylic acid as initiators. A mixture of 2 g of N,N-azobisisobutyronitrile was added dropwise with a dropping funnel over 30 minutes. After continuing the reaction for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the temperature was returned to room temperature to complete the polymerization. After adding 100 g of isopropyl alcohol to this polymer solution, 40 g of glycidyl methacrylate and 3 g of triethylbenzylammonium chloride were added while maintaining the polymer solution at 75° C., and the mixture was allowed to react for 3 hours. After completion of the reaction, the resulting resin solution was reprecipitated with purified water, filtered and dried to give a hydroxyl- or acid-containing resin (weight-average molecular weight of 15,000, hydroxyl value of 0 mgKOH/g, acid value of 110 mgKOH/g). P-1) was obtained. The hydroxyl value of the resin was measured in mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the resin was acetylated according to JIS K0070 (1992). For the acid value of the resin, the number of mg of potassium hydroxide required to neutralize 1 g of the resin was measured according to JIS K0070 (1992). The weight average molecular weight was measured by polystyrene conversion using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation) using tetrahydrofuran as the carrier.
（合成例２ 水酸基または酸基含有樹脂（Ｐ－２）の合成）
１０００ｃｃの４つ口フラスコにイソプロピルアルコールを１００ｇ仕込み、これをオイルバス中で８０℃に保ち、窒素シールし、攪拌を行いながら、モノマーとしてメタクリル酸メチル２５ｇ、スチレン５２ｇおよびメタクリル酸２－ヒドロキシエチル３３ｇと開始剤としてＮ，Ｎ－アゾビスイソブチロニトリル２ｇを混合したものを滴下ロートで３０分かけて滴下した。この後４時間反応を続けた後、ハイドロキノンモノメチルエーテルを１ｇ添加してから常温に戻し、重合を完了した。反応終了後、得られた樹脂溶液を精製水で再沈し、濾過および乾燥することにより、重量平均分子量１３，０００、水酸基価１００ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－２）を得た。 (Synthesis Example 2 Synthesis of hydroxyl- or acid-containing resin (P-2))
A 1000 cc four-necked flask was charged with 100 g of isopropyl alcohol, which was kept at 80° C. in an oil bath, sealed with nitrogen, and stirred while adding 25 g of methyl methacrylate, 52 g of styrene, and 33 g of 2-hydroxyethyl methacrylate as monomers. and 2 g of N,N-azobisisobutyronitrile as an initiator were added dropwise with a dropping funnel over 30 minutes. After continuing the reaction for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the temperature was returned to room temperature to complete the polymerization. After completion of the reaction, the resulting resin solution was reprecipitated with purified water, filtered and dried to give a hydroxyl- or acid-containing resin (with a weight average molecular weight of 13,000, a hydroxyl value of 100 mgKOH/g, and an acid value of 0 mgKOH/g). P-2) was obtained.
１０００ｃｃの４つ口フラスコにイソプロピルアルコールを１００ｇ仕込み、これをオイルバス中で８０℃に保ち、窒素シールし、攪拌を行いながら、モノマーとしてメタクリル酸メチル２５ｇ、スチレン５２ｇおよびメタクリル酸２－ヒドロキシエチル３３ｇと開始剤としてＮ，Ｎ－アゾビスイソブチロニトリル２ｇを混合したものを滴下ロートで３０分かけて滴下した。この後４時間反応を続けた後、ハイドロキノンモノメチルエーテルを１ｇ添加してから常温に戻し、重合を完了した。反応終了後、得られた樹脂溶液を精製水で再沈し、濾過および乾燥することにより、重量平均分子量１３，０００、水酸基価１００ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－２）を得た。 (Synthesis Example 2 Synthesis of hydroxyl- or acid-containing resin (P-2))
A 1000 cc four-necked flask was charged with 100 g of isopropyl alcohol, which was kept at 80° C. in an oil bath, sealed with nitrogen, and stirred while adding 25 g of methyl methacrylate, 52 g of styrene, and 33 g of 2-hydroxyethyl methacrylate as monomers. and 2 g of N,N-azobisisobutyronitrile as an initiator were added dropwise with a dropping funnel over 30 minutes. After continuing the reaction for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the temperature was returned to room temperature to complete the polymerization. After completion of the reaction, the resulting resin solution was reprecipitated with purified water, filtered and dried to give a hydroxyl- or acid-containing resin (with a weight average molecular weight of 13,000, a hydroxyl value of 100 mgKOH/g, and an acid value of 0 mgKOH/g). P-2) was obtained.
（合成例３ 水酸基または酸基含有樹脂（Ｐ－３）の合成）
モノマーとしてメタクリル酸メチル１０ｇ、メタクリル酸１３ｇ、スチレン２１ｇおよびメタクリル酸２－ヒドロキシエチル７２ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１２，５００、水酸基価２３０ｍｇＫＯＨ／ｇ、酸価６０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－３）を得た。 (Synthesis Example 3 Synthesis of hydroxyl group- or acid group-containing resin (P-3))
In the same manner as in Synthesis Example 2, except that 10 g of methyl methacrylate, 13 g of methacrylic acid, 21 g of styrene, and 72 g of 2-hydroxyethyl methacrylate were used as monomers. A hydroxyl group- or acid group-containing resin (P-3) of 60 mg KOH/g was obtained.
モノマーとしてメタクリル酸メチル１０ｇ、メタクリル酸１３ｇ、スチレン２１ｇおよびメタクリル酸２－ヒドロキシエチル７２ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１２，５００、水酸基価２３０ｍｇＫＯＨ／ｇ、酸価６０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－３）を得た。 (Synthesis Example 3 Synthesis of hydroxyl group- or acid group-containing resin (P-3))
In the same manner as in Synthesis Example 2, except that 10 g of methyl methacrylate, 13 g of methacrylic acid, 21 g of styrene, and 72 g of 2-hydroxyethyl methacrylate were used as monomers. A hydroxyl group- or acid group-containing resin (P-3) of 60 mg KOH/g was obtained.
（合成例４ 水酸基または酸基含有樹脂（Ｐ－４）の合成）
モノマーとしてメタクリル酸メチル４４ｇ、メタクリル酸１４ｇおよびスチレン４２ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１４，０００、水酸基価０ｍｇＫＯＨ／ｇ、酸価７０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－４）を得た。 (Synthesis Example 4 Synthesis of hydroxyl- or acid-containing resin (P-4))
In the same manner as in Synthesis Example 2 except that 44 g of methyl methacrylate, 14 g of methacrylic acid and 42 g of styrene were used as the monomers, hydroxyl or acid groups having a weight average molecular weight of 14,000, a hydroxyl value of 0 mgKOH/g and an acid value of 70 mgKOH/g were prepared. A containing resin (P-4) was obtained.
モノマーとしてメタクリル酸メチル４４ｇ、メタクリル酸１４ｇおよびスチレン４２ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１４，０００、水酸基価０ｍｇＫＯＨ／ｇ、酸価７０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－４）を得た。 (Synthesis Example 4 Synthesis of hydroxyl- or acid-containing resin (P-4))
In the same manner as in Synthesis Example 2 except that 44 g of methyl methacrylate, 14 g of methacrylic acid and 42 g of styrene were used as the monomers, hydroxyl or acid groups having a weight average molecular weight of 14,000, a hydroxyl value of 0 mgKOH/g and an acid value of 70 mgKOH/g were prepared. A containing resin (P-4) was obtained.
（合成例５ 水酸基または酸基含有樹脂（Ｐ－５）の合成）
モノマーとしてメタクリル酸メチル４３ｇ、スチレン４２ｇおよびメタクリル酸２－ヒドロキシエチル２３ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１５，０００、水酸基価７０ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－５）を得た。 (Synthesis Example 5 Synthesis of hydroxyl group- or acid group-containing resin (P-5))
In the same manner as in Synthesis Example 2 except that 43 g of methyl methacrylate, 42 g of styrene and 23 g of 2-hydroxyethyl methacrylate were used as the monomers, a mixture having a weight average molecular weight of 15,000, a hydroxyl value of 70 mgKOH/g and an acid value of 0 mgKOH/g was prepared. A hydroxyl group- or acid group-containing resin (P-5) was obtained.
モノマーとしてメタクリル酸メチル４３ｇ、スチレン４２ｇおよびメタクリル酸２－ヒドロキシエチル２３ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１５，０００、水酸基価７０ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－５）を得た。 (Synthesis Example 5 Synthesis of hydroxyl group- or acid group-containing resin (P-5))
In the same manner as in Synthesis Example 2 except that 43 g of methyl methacrylate, 42 g of styrene and 23 g of 2-hydroxyethyl methacrylate were used as the monomers, a mixture having a weight average molecular weight of 15,000, a hydroxyl value of 70 mgKOH/g and an acid value of 0 mgKOH/g was prepared. A hydroxyl group- or acid group-containing resin (P-5) was obtained.
（合成例６ 水酸基または酸基含有樹脂（Ｐ－６）の合成）
モノマーとしてメタクリル酸メチル４７ｇ、メタクリル酸５ｇ、スチレン４２ｇおよびメタクリル酸２－ヒドロキシエチル１０ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１４５，０００、水酸基価３０ｍｇＫＯＨ／ｇ、酸価４０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－６）を得た。
合成例１～６の水酸基価および酸価を表１に示す。 (Synthesis Example 6 Synthesis of hydroxyl group- or acid group-containing resin (P-6))
In the same manner as in Synthesis Example 2, except that 47 g of methyl methacrylate, 5 g of methacrylic acid, 42 g of styrene, and 10 g of 2-hydroxyethyl methacrylate were used as monomers. A hydroxyl group- or acid group-containing resin (P-6) of 40 mg KOH/g was obtained.
Table 1 shows the hydroxyl values and acid values of Synthesis Examples 1-6.
モノマーとしてメタクリル酸メチル４７ｇ、メタクリル酸５ｇ、スチレン４２ｇおよびメタクリル酸２－ヒドロキシエチル１０ｇを用いたこと以外は合成例２と同様にして、重量平均分子量１４５，０００、水酸基価３０ｍｇＫＯＨ／ｇ、酸価４０ｍｇＫＯＨ／ｇの水酸基または酸基含有樹脂（Ｐ－６）を得た。
合成例１～６の水酸基価および酸価を表１に示す。 (Synthesis Example 6 Synthesis of hydroxyl group- or acid group-containing resin (P-6))
In the same manner as in Synthesis Example 2, except that 47 g of methyl methacrylate, 5 g of methacrylic acid, 42 g of styrene, and 10 g of 2-hydroxyethyl methacrylate were used as monomers. A hydroxyl group- or acid group-containing resin (P-6) of 40 mg KOH/g was obtained.
Table 1 shows the hydroxyl values and acid values of Synthesis Examples 1-6.
（製造例１ 赤色顔料ＰＲ１７７－１の製造）
２００ｇのＢＡＳＦ（株）製“Ｃｒｏｍｏｐｈｔａｌ（登録商標） Ｒｅｄ Ａ３Ｂ”、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥して赤色顔料ＰＲ１７７－１を得た。 (Production Example 1 Production of red pigment PR177-1)
200 g of "Cromophtal (registered trademark) Red A3B" manufactured by BASF Corporation, 2400 g of sodium chloride and 400 g of diethylene glycol were charged into a kneader (S type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded at 70 ° C. Kneaded for 8 hours. Next, this kneaded product is put into about 10 L of hot water, stirred with a high speed mixer for 1 hour while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a red pigment PR177-1.
２００ｇのＢＡＳＦ（株）製“Ｃｒｏｍｏｐｈｔａｌ（登録商標） Ｒｅｄ Ａ３Ｂ”、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥して赤色顔料ＰＲ１７７－１を得た。 (Production Example 1 Production of red pigment PR177-1)
200 g of "Cromophtal (registered trademark) Red A3B" manufactured by BASF Corporation, 2400 g of sodium chloride and 400 g of diethylene glycol were charged into a kneader (S type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded at 70 ° C. Kneaded for 8 hours. Next, this kneaded product is put into about 10 L of hot water, stirred with a high speed mixer for 1 hour while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a red pigment PR177-1.
（製造例２ 青色顔料ＰＢ１５：６－１の製造）
２００ｇのトーヨーカラー（株）製“ＬＩＯＮＯＬ（登録商標） ＢＬＵＥ ＥＳ”、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥して青色顔料ＰＢ１５：６－１を得た。 (Production Example 2 Production of blue pigment PB15:6-1)
200 g of "LIONOL (registered trademark) BLUE ES" manufactured by Toyocolor Co., Ltd., 2400 g of sodium chloride and 400 g of diethylene glycol were put into a kneader (S type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and heated to 70°C. and kneaded for 8 hours. Next, this kneaded product is put into about 10 L of hot water, stirred for 1 hour with a high speed mixer while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a blue pigment PB15:6-1.
２００ｇのトーヨーカラー（株）製“ＬＩＯＮＯＬ（登録商標） ＢＬＵＥ ＥＳ”、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥して青色顔料ＰＢ１５：６－１を得た。 (Production Example 2 Production of blue pigment PB15:6-1)
200 g of "LIONOL (registered trademark) BLUE ES" manufactured by Toyocolor Co., Ltd., 2400 g of sodium chloride and 400 g of diethylene glycol were put into a kneader (S type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and heated to 70°C. and kneaded for 8 hours. Next, this kneaded product is put into about 10 L of hot water, stirred for 1 hour with a high speed mixer while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a blue pigment PB15:6-1.
（製造例３ 黄色顔料ＰＹ１５０－１の製造）
２００ｇのランクセス（株）製“Ｅ－４ＧＮ”、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥して黄色顔料ＰＹ１５０－１を得た。 (Production Example 3 Production of yellow pigment PY150-1)
200 g of "E-4GN" manufactured by Lanxess Co., Ltd., 2400 g of sodium chloride and 400 g of diethylene glycol were put into a kneader (S type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded at 70° C. for 8 hours. . Next, this kneaded product is put into about 10 L of hot water, stirred with a high speed mixer for 1 hour while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a yellow pigment PY150-1.
２００ｇのランクセス（株）製“Ｅ－４ＧＮ”、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥して黄色顔料ＰＹ１５０－１を得た。 (Production Example 3 Production of yellow pigment PY150-1)
200 g of "E-4GN" manufactured by Lanxess Co., Ltd., 2400 g of sodium chloride and 400 g of diethylene glycol were put into a kneader (S type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded at 70° C. for 8 hours. . Next, this kneaded product is put into about 10 L of hot water, stirred with a high speed mixer for 1 hour while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a yellow pigment PY150-1.
（製造例４ ビスベンゾフラン系顔料Ｂｋ－１の製造）
ビスベンゾフラン系顔料として２００ｇのＢＡＳＦ（株）製“Ｉｒｇａｐｈｏｒ（登録商標）”Ｂｌａｃｋ Ｓ０１００ＣＦ、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥してビスベンゾフラン系顔料Ｂｋ－１を得た。 (Production Example 4 Production of bisbenzofuran pigment Bk-1)
200 g of "Irgaphor (registered trademark)" Black S0100CF manufactured by BASF Corporation as a bisbenzofuran-based pigment, 2400 g of sodium chloride and 400 g of diethylene glycol were put into a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneader (trade name)). and kneaded at 70° C. for 8 hours. Next, this kneaded product is put into about 10 L of hot water, stirred with a high speed mixer for 1 hour while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a bisbenzofuran pigment Bk-1.
ビスベンゾフラン系顔料として２００ｇのＢＡＳＦ（株）製“Ｉｒｇａｐｈｏｒ（登録商標）”Ｂｌａｃｋ Ｓ０１００ＣＦ、２４００ｇの塩化ナトリウムおよび４００ｇのジエチレングリコールをニーダー（（株）森山製作所製、Ｓ型ニーダー（商品名））に投入し、７０℃で８時間混練した。次に、この混練物を約１０Ｌの温水に投入し、４０℃に加熱しながらハイスピードミキサーで１時間撹拌してスラリー状とした後、濾過し、水洗して塩化ナトリウムおよびジエチレングリコールを除き、８０℃で２４時間真空乾燥してビスベンゾフラン系顔料Ｂｋ－１を得た。 (Production Example 4 Production of bisbenzofuran pigment Bk-1)
200 g of "Irgaphor (registered trademark)" Black S0100CF manufactured by BASF Corporation as a bisbenzofuran-based pigment, 2400 g of sodium chloride and 400 g of diethylene glycol were put into a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneader (trade name)). and kneaded at 70° C. for 8 hours. Next, this kneaded product is put into about 10 L of hot water, stirred with a high speed mixer for 1 hour while heating to 40 ° C. to make a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol, and 80 ℃ for 24 hours to obtain a bisbenzofuran pigment Bk-1.
（製造例５ 着色材分散液（ＤＰ－１）の製造）
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液を１７９ｇ、塩基性基として３級アミノ基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ６９１９（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート２０質量％溶液）を６３ｇ、およびＰＧＭＥＡ５８４ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．３０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度９ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度１１ｍ／ｓで９０分間分散を行い、固形分濃度２５質量％、着色材／（樹脂＋分散剤）（質量比）＝７０／３０の着色材分散液ＤＰ－１を得た。 (Production Example 5 Production of Colorant Dispersion (DP-1))
175 g of high resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and 3 as basic groups. 63 g of "DISPERBYK (registered trademark)" LP N6919 (manufactured by BYK-Chemie, 20% by mass solution of propylene glycol monomethyl ether acetate) as an acrylic dispersant having a class amino group and 584 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer. to obtain a preliminary dispersion. The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , a coloring agent dispersion DP-1 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30 was obtained.
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液を１７９ｇ、塩基性基として３級アミノ基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ６９１９（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート２０質量％溶液）を６３ｇ、およびＰＧＭＥＡ５８４ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．３０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度９ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度１１ｍ／ｓで９０分間分散を行い、固形分濃度２５質量％、着色材／（樹脂＋分散剤）（質量比）＝７０／３０の着色材分散液ＤＰ－１を得た。 (Production Example 5 Production of Colorant Dispersion (DP-1))
175 g of high resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and 3 as basic groups. 63 g of "DISPERBYK (registered trademark)" LP N6919 (manufactured by BYK-Chemie, 20% by mass solution of propylene glycol monomethyl ether acetate) as an acrylic dispersant having a class amino group and 584 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer. to obtain a preliminary dispersion. The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , a coloring agent dispersion DP-1 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30 was obtained.
（製造例６ 着色材分散液（ＤＰ－２）の製造）
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液を１７９ｇ、塩基性基として３級アミノ基および４級アンモニウム塩基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ２１１１６（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート４０質量％溶液）を３１ｇ、およびＰＧＭＥＡ６１５ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．３０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度９ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度１１ｍ／ｓで９０分間分散を行い、固形分濃度２５質量％、着色材／（樹脂＋分散剤）（質量比）＝７０／３０の着色材分散液ＤＰ－２を得た。 (Production Example 6 Production of Colorant Dispersion (DP-2))
175 g of high resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and 3 as basic groups. 31 g of "DISPERBYK (registered trademark)" LP N21116 (manufactured by BYK-Chemie, propylene glycol monomethyl ether acetate 40% by mass solution) as an acrylic dispersant having a primary amino group and a quaternary ammonium base, and 615 g of PGMEA were charged into a tank, and homogenized. The mixture was stirred for 20 minutes with a mixer to obtain a preliminary dispersion. The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , to obtain a coloring agent dispersion DP-2 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30.
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液を１７９ｇ、塩基性基として３級アミノ基および４級アンモニウム塩基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ２１１１６（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート４０質量％溶液）を３１ｇ、およびＰＧＭＥＡ６１５ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．３０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度９ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度１１ｍ／ｓで９０分間分散を行い、固形分濃度２５質量％、着色材／（樹脂＋分散剤）（質量比）＝７０／３０の着色材分散液ＤＰ－２を得た。 (Production Example 6 Production of Colorant Dispersion (DP-2))
175 g of high resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and 3 as basic groups. 31 g of "DISPERBYK (registered trademark)" LP N21116 (manufactured by BYK-Chemie, propylene glycol monomethyl ether acetate 40% by mass solution) as an acrylic dispersant having a primary amino group and a quaternary ammonium base, and 615 g of PGMEA were charged into a tank, and homogenized. The mixture was stirred for 20 minutes with a mixer to obtain a preliminary dispersion. The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , to obtain a coloring agent dispersion DP-2 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30.
（製造例７ 着色材分散液（ＤＰ－３）の製造）
前記赤色顔料ＰＲ１７７－１ １２０ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液１７１ｇ、塩基性基として３級アミノ基および４級アンモニウム塩基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ２１１１６（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート４０質量％溶液）５０ｇおよびＰＧＭＥＡ６５９ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．５０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度１２ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度８ｍ／ｓで９０分間分散を行い、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－３を得た。 (Production Example 7 Production of Colorant Dispersion (DP-3))
120 g of the red pigment PR177-1, 171 g of a 35% by mass solution of the acrylic resin (P-1) in propylene glycol monomethyl ether acetate (PGMEA) obtained in Synthesis Example 1, a tertiary amino group and a quaternary ammonium base as basic groups "DISPERBYK (registered trademark)" LP N21116 (manufactured by BYK-Chemie Co., Ltd., 40% by mass solution of propylene glycol monomethyl ether acetate) 50 g and PGMEA 659 g are charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion liquid. got The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.50 mmφ, and was rotated at a rotation speed of 12 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 8 m/s for 90 minutes until the solid content was 20% by mass. , to obtain a coloring agent dispersion DP-3 having a coloring agent/(resin+dispersant) (mass ratio) of 60/40.
前記赤色顔料ＰＲ１７７－１ １２０ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液１７１ｇ、塩基性基として３級アミノ基および４級アンモニウム塩基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ２１１１６（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート４０質量％溶液）５０ｇおよびＰＧＭＥＡ６５９ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．５０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度１２ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度８ｍ／ｓで９０分間分散を行い、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－３を得た。 (Production Example 7 Production of Colorant Dispersion (DP-3))
120 g of the red pigment PR177-1, 171 g of a 35% by mass solution of the acrylic resin (P-1) in propylene glycol monomethyl ether acetate (PGMEA) obtained in Synthesis Example 1, a tertiary amino group and a quaternary ammonium base as basic groups "DISPERBYK (registered trademark)" LP N21116 (manufactured by BYK-Chemie Co., Ltd., 40% by mass solution of propylene glycol monomethyl ether acetate) 50 g and PGMEA 659 g are charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion liquid. got The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.50 mmφ, and was rotated at a rotation speed of 12 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 8 m/s for 90 minutes until the solid content was 20% by mass. , to obtain a coloring agent dispersion DP-3 having a coloring agent/(resin+dispersant) (mass ratio) of 60/40.
（製造例８ 着色材分散液（ＤＰ－４）の製造）
赤色顔料ＰＲ１７７－１の代わりに、青色顔料ＰＢ１５：６－１を用いた以外は製造例７と同様にして、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－４を得た。 (Production Example 8 Production of Colorant Dispersion (DP-4))
In the same manner as in Production Example 7 except that the blue pigment PB15:6-1 was used instead of the red pigment PR177-1, the solid content concentration was 20% by mass, and the colorant/(resin + dispersant) (mass ratio) = A 60/40 colorant dispersion DP-4 was obtained.
赤色顔料ＰＲ１７７－１の代わりに、青色顔料ＰＢ１５：６－１を用いた以外は製造例７と同様にして、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－４を得た。 (Production Example 8 Production of Colorant Dispersion (DP-4))
In the same manner as in Production Example 7 except that the blue pigment PB15:6-1 was used instead of the red pigment PR177-1, the solid content concentration was 20% by mass, and the colorant/(resin + dispersant) (mass ratio) = A 60/40 colorant dispersion DP-4 was obtained.
（製造例９ 着色材分散液（ＤＰ－５）の製造）
赤色顔料ＰＲ１７７－１の代わりに、黄色顔料ＰＹ１５０－１を用いた以外は製造例７と同様にして、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－５を得た。 (Production Example 9 Production of colorant dispersion (DP-5))
In the same manner as in Production Example 7 except that the yellow pigment PY150-1 was used instead of the red pigment PR177-1, the solid content concentration was 20% by mass, the colorant / (resin + dispersant) (mass ratio) = 60/ 40 colorant dispersions DP-5 were obtained.
赤色顔料ＰＲ１７７－１の代わりに、黄色顔料ＰＹ１５０－１を用いた以外は製造例７と同様にして、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－５を得た。 (Production Example 9 Production of colorant dispersion (DP-5))
In the same manner as in Production Example 7 except that the yellow pigment PY150-1 was used instead of the red pigment PR177-1, the solid content concentration was 20% by mass, the colorant / (resin + dispersant) (mass ratio) = 60/ 40 colorant dispersions DP-5 were obtained.
（製造例１０ 着色材分散液（ＤＰ－６）の製造）
赤色顔料ＰＲ１７７－１の代わりに、ビスベンゾフラノン系顔料Ｂｋ－１を用いた以外は製造例７と同様にして、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－６を得た。 (Production Example 10 Production of colorant dispersion (DP-6))
In the same manner as in Production Example 7 except that the bisbenzofuranone pigment Bk-1 was used instead of the red pigment PR177-1, the solid content concentration was 20% by mass, and the colorant/(resin + dispersant) (mass ratio) = 60/40 colorant dispersion DP-6 was obtained.
赤色顔料ＰＲ１７７－１の代わりに、ビスベンゾフラノン系顔料Ｂｋ－１を用いた以外は製造例７と同様にして、固形分濃度２０質量％、着色材／（樹脂＋分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－６を得た。 (Production Example 10 Production of colorant dispersion (DP-6))
In the same manner as in Production Example 7 except that the bisbenzofuranone pigment Bk-1 was used instead of the red pigment PR177-1, the solid content concentration was 20% by mass, and the colorant/(resin + dispersant) (mass ratio) = 60/40 colorant dispersion DP-6 was obtained.
（製造例１１ 着色材分散液（ＤＰ－７）の製造）
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液１７９ｇ、塩基性基として３級アミノ基および４級アンモニウム塩基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ２１１１６（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート４０質量％溶液）３１ｇおよびＰＧＭＥＡ６１５ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ペイントシェーカー（株式会社東洋精機製作所）に得られた予備分散液を供給し、ビーズ径１．０ｍｍφのジルコニアビーズを用いて３時間分散を行った後に、５μｍのフィルターでろ過し、固形分濃度２０質量％、着色材／（樹脂＋高分子分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－７を得た。 (Production Example 11 Production of Colorant Dispersion (DP-7))
175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and a tertiary basic group As an acrylic dispersant having an amino group and a quaternary ammonium base, 31 g of "DISPERBYK (registered trademark)" LP N21116 (manufactured by BYK-Chemie, propylene glycol monomethyl ether acetate 40% by mass solution) and 615 g of PGMEA were charged into a tank, and 20 g of PGMEA were charged in a homomixer. The mixture was stirred for a minute to obtain a preliminary dispersion. The obtained preliminary dispersion is supplied to a paint shaker (Toyo Seiki Seisakusho Co., Ltd.), dispersed for 3 hours using zirconia beads with a bead diameter of 1.0 mmφ, and then filtered through a 5 μm filter to obtain a solid content concentration of 20. A coloring material dispersion liquid DP-7 having a mass % of coloring material/(resin+polymer dispersant) (mass ratio)=60/40 was obtained.
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液１７９ｇ、塩基性基として３級アミノ基および４級アンモニウム塩基を有するアクリル系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”ＬＰ Ｎ２１１１６（ビックケミー社製、プロピレングリコールモノメチルエーテルアセテート４０質量％溶液）３１ｇおよびＰＧＭＥＡ６１５ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ペイントシェーカー（株式会社東洋精機製作所）に得られた予備分散液を供給し、ビーズ径１．０ｍｍφのジルコニアビーズを用いて３時間分散を行った後に、５μｍのフィルターでろ過し、固形分濃度２０質量％、着色材／（樹脂＋高分子分散剤）（質量比）＝６０／４０の着色材分散液ＤＰ－７を得た。 (Production Example 11 Production of Colorant Dispersion (DP-7))
175 g of high-resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and a tertiary basic group As an acrylic dispersant having an amino group and a quaternary ammonium base, 31 g of "DISPERBYK (registered trademark)" LP N21116 (manufactured by BYK-Chemie, propylene glycol monomethyl ether acetate 40% by mass solution) and 615 g of PGMEA were charged into a tank, and 20 g of PGMEA were charged in a homomixer. The mixture was stirred for a minute to obtain a preliminary dispersion. The obtained preliminary dispersion is supplied to a paint shaker (Toyo Seiki Seisakusho Co., Ltd.), dispersed for 3 hours using zirconia beads with a bead diameter of 1.0 mmφ, and then filtered through a 5 μm filter to obtain a solid content concentration of 20. A coloring material dispersion liquid DP-7 having a mass % of coloring material/(resin+polymer dispersant) (mass ratio)=60/40 was obtained.
（製造例１２ 着色材分散液（ＤＰ－８）の製造）
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液１７９ｇ、ウレタン系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”１６７（ビックケミー社製、酢酸ブチル５２質量％溶液）２４ｇおよびＰＧＭＥＡ６２２ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．３０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度９ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度１１ｍ／ｓで９０分間分散を行い、固形分濃度２５質量％、着色材／（樹脂＋分散剤）（質量比）＝７０／３０の着色材分散液ＤＰ－８を得た。
製造例５～１２の組成、分散条件およびを表２に示す。 (Production Example 12 Production of Colorant Dispersion (DP-8))
175 g of high resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and a urethane dispersant " DISPERBYK (registered trademark)"167 (manufactured by BYK-Chemie, 52% by mass solution of butyl acetate) and 622 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , to obtain a coloring agent dispersion DP-8 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30.
Table 2 shows the compositions, dispersing conditions and conditions of Production Examples 5 to 12.
高抵抗カーボンブラックＴＰＫ１２２７Ｒ（キャボット（株）製）を１７５ｇ、合成例１により得られたアクリル樹脂（Ｐ－１）のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）３５質量％溶液１７９ｇ、ウレタン系分散剤として“ＤＩＳＰＥＲＢＹＫ（登録商標）”１６７（ビックケミー社製、酢酸ブチル５２質量％溶液）２４ｇおよびＰＧＭＥＡ６２２ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。ビーズ径０．３０ｍｍφのジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した寿工業（株）製分散機ウルトラアペックスミルＵＡＭ０１５に、得られた予備分散液を供給し、回転速度９ｍ／ｓで２０分間分散を行った。続いて、分散処理後の液を、ビーズ径０．０５ｍｍφのジルコニアビーズを７５体積％充填したウルトラアペックスミルＵＡＭ０１５に供給し、回転速度１１ｍ／ｓで９０分間分散を行い、固形分濃度２５質量％、着色材／（樹脂＋分散剤）（質量比）＝７０／３０の着色材分散液ＤＰ－８を得た。
製造例５～１２の組成、分散条件およびを表２に示す。 (Production Example 12 Production of Colorant Dispersion (DP-8))
175 g of high resistance carbon black TPK1227R (manufactured by Cabot Corporation), 179 g of a 35% by mass solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), and a urethane dispersant " DISPERBYK (registered trademark)"167 (manufactured by BYK-Chemie, 52% by mass solution of butyl acetate) and 622 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The resulting preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and was rotated at a rotation speed of 9 m / s. Dispersion was carried out for 20 minutes. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersed at a rotation speed of 11 m/s for 90 minutes to obtain a solid concentration of 25% by mass. , to obtain a coloring agent dispersion DP-8 having a coloring agent/(resin+dispersant) (mass ratio) of 70/30.
Table 2 shows the compositions, dispersing conditions and conditions of Production Examples 5 to 12.
（実施例１）
３１．４３ｇの着色材分散液（ＤＰ－１）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロック剤がオキシム系ブロック剤であるブロックイソシアネートとしてコロネート（登録商標）ＢＩ－３０１（東ソー（株）製、ソルベッソ（登録商標）１００（エクソン化学（株）製）７５質量％溶液）を６．４３ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３６．９８ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１を得た。 (Example 1)
To 31.43 g of the colorant dispersion (DP-1), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and a blocked isocyanate whose blocking agent is an oxime-based blocking agent, coronate ( Registered trademark) BI-301 (manufactured by Tosoh Corporation, Solvesso (registered trademark) 100 (manufactured by Exxon Chemical Co., Ltd.) 75% by mass solution) is 6.43 g, and a silicone surfactant "BYK (registered trademark)" is used as a surfactant. A solution of 0.20 g of a 10% by mass PGMEA solution of Trademark) "333 (manufactured by BYK-Chemie Co., Ltd.) dissolved in 36.98 g of PGMEA was added to obtain a coloring material with a total solid concentration of 22% by mass and a total solid content of 100 parts by mass. A colored resin composition PC-1 having a content of 25 parts by mass was obtained.
３１．４３ｇの着色材分散液（ＤＰ－１）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロック剤がオキシム系ブロック剤であるブロックイソシアネートとしてコロネート（登録商標）ＢＩ－３０１（東ソー（株）製、ソルベッソ（登録商標）１００（エクソン化学（株）製）７５質量％溶液）を６．４３ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３６．９８ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１を得た。 (Example 1)
To 31.43 g of the colorant dispersion (DP-1), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and a blocked isocyanate whose blocking agent is an oxime-based blocking agent, coronate ( Registered trademark) BI-301 (manufactured by Tosoh Corporation, Solvesso (registered trademark) 100 (manufactured by Exxon Chemical Co., Ltd.) 75% by mass solution) is 6.43 g, and a silicone surfactant "BYK (registered trademark)" is used as a surfactant. A solution of 0.20 g of a 10% by mass PGMEA solution of Trademark) "333 (manufactured by BYK-Chemie Co., Ltd.) dissolved in 36.98 g of PGMEA was added to obtain a coloring material with a total solid concentration of 22% by mass and a total solid content of 100 parts by mass. A colored resin composition PC-1 having a content of 25 parts by mass was obtained.
得られた着色樹脂組成物ＰＣ－１を、ポリエステルフィルム（東レ（株）製、ルミラー（登録商標）Ｕ４８、膜厚：１００μｍ）の易接着剤層上に、ミカサ（株）製スピンナー（１Ｈ－ＤＳ）を用いて塗布し、塗布膜を形成した。塗布膜を９０℃のオーブンで３０分間加熱乾燥して着色膜Ｃ－１を得た。この着色膜Ｃ－１について、前述の方法により評価した結果を表４に示す。
The resulting colored resin composition PC-1 is placed on an easy-adhesive layer of a polyester film (manufactured by Toray Industries, Inc., Lumirror (registered trademark) U48, film thickness: 100 μm), and a spinner (1H- DS) to form a coating film. The coated film was dried by heating in an oven at 90° C. for 30 minutes to obtain a colored film C-1. Table 4 shows the results of evaluating this colored film C-1 by the method described above.
（実施例２）
着色材分散液（ＤＰ－１）の代わりに着色材分散液（ＤＰ－２）を用いた以外は実施例１と同様にして、着色樹脂組成物ＰＣ－２を得た。得られた着色樹脂組成物ＰＣ－２を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 2)
A colored resin composition PC-2 was obtained in the same manner as in Example 1 except that the coloring agent dispersion (DP-2) was used instead of the coloring agent dispersion (DP-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-2. Table 4 shows the results.
着色材分散液（ＤＰ－１）の代わりに着色材分散液（ＤＰ－２）を用いた以外は実施例１と同様にして、着色樹脂組成物ＰＣ－２を得た。得られた着色樹脂組成物ＰＣ－２を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 2)
A colored resin composition PC-2 was obtained in the same manner as in Example 1 except that the coloring agent dispersion (DP-2) was used instead of the coloring agent dispersion (DP-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-2. Table 4 shows the results.
（実施例３）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製、ＰＧＭＥＡ７０質量％溶液）を６．８９ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３４．９１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－３を得た。得られた着色樹脂組成物ＰＣ－３を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 3)
To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( Registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation, PGMEA 70% by mass solution) 6.89 g, and a silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) as a surfactant as a PGMEA 10% solution A solution of 0.20 g dissolved in 34.91 g of PGMEA was added to obtain a colored resin composition having a total solid concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solid content PC- got 3. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-3. Table 4 shows the results.
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製、ＰＧＭＥＡ７０質量％溶液）を６．８９ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３４．９１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－３を得た。得られた着色樹脂組成物ＰＣ－３を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 3)
To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( Registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation, PGMEA 70% by mass solution) 6.89 g, and a silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) as a surfactant as a PGMEA 10% solution A solution of 0.20 g dissolved in 34.91 g of PGMEA was added to obtain a colored resin composition having a total solid concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solid content PC- got 3. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-3. Table 4 shows the results.
（実施例４）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロック剤が活性メチレン系ブロック剤であるデュラネート（登録商標）ＭＦ－Ｋ６０Ｂ（旭化成（株）製、酢酸ｎ－ブチル／ｎ－ブタノール６０質量％溶液）を８．０４ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３３．７７ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－４を得た。得られた着色樹脂組成物ＰＣ－４を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 4)
To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate (registered trademark), which is an active methylene blocking agent, is used as a blocking agent. ) 8.04 g of MF-K60B (manufactured by Asahi Kasei Corporation, n-butyl acetate / n-butanol 60% by mass solution), and a silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK Chemie Co., Ltd.) as a surfactant ) of 0.20 g of a 10% by mass solution of PGMEA dissolved in 33.77 g of PGMEA is added to obtain a total solid concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. A colored resin composition PC-4 was obtained. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-4. Table 4 shows the results.
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロック剤が活性メチレン系ブロック剤であるデュラネート（登録商標）ＭＦ－Ｋ６０Ｂ（旭化成（株）製、酢酸ｎ－ブチル／ｎ－ブタノール６０質量％溶液）を８．０４ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３３．７７ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－４を得た。得られた着色樹脂組成物ＰＣ－４を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 4)
To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate (registered trademark), which is an active methylene blocking agent, is used as a blocking agent. ) 8.04 g of MF-K60B (manufactured by Asahi Kasei Corporation, n-butyl acetate / n-butanol 60% by mass solution), and a silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK Chemie Co., Ltd.) as a surfactant ) of 0.20 g of a 10% by mass solution of PGMEA dissolved in 33.77 g of PGMEA is added to obtain a total solid concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. A colored resin composition PC-4 was obtained. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-4. Table 4 shows the results.
（実施例５）
水酸基または酸基含有樹脂（Ｐ－１）の代わりに水酸基または酸基含有樹脂（Ｐ－２）を用いた以外は実施例３と同様にして、着色樹脂組成物ＰＣ－５を得た。得られた着色樹脂組成物ＰＣ－５を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 5)
A colored resin composition PC-5 was obtained in the same manner as in Example 3, except that the hydroxyl- or acid-containing resin (P-2) was used instead of the hydroxyl- or acid-containing resin (P-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-5. Table 4 shows the results.
水酸基または酸基含有樹脂（Ｐ－１）の代わりに水酸基または酸基含有樹脂（Ｐ－２）を用いた以外は実施例３と同様にして、着色樹脂組成物ＰＣ－５を得た。得られた着色樹脂組成物ＰＣ－５を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 5)
A colored resin composition PC-5 was obtained in the same manner as in Example 3, except that the hydroxyl- or acid-containing resin (P-2) was used instead of the hydroxyl- or acid-containing resin (P-1). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-5. Table 4 shows the results.
（実施例６）
２２．９２ｇの着色材分散液（ＤＰ－３）、１６．０４ｇの着色材分散液（ＤＰ－４）、および６．８８ｇの着色材分散液（ＤＰ－５）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２３．２７ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を６．６７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２４．０３ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－６を得た。得られた着色樹脂組成物ＰＣ－６を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 6)
22.92 g of the colorant dispersion (DP-3), 16.04 g of the colorant dispersion (DP-4), and 6.88 g of the colorant dispersion (DP-5) were added with a hydroxyl- or acid-containing resin. 23.27 g of a 35% by mass solution of PGMEA (P-1), 6.67 g of Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation) as a blocked isocyanate in which the blocking agent is a pyrazole-based blocking agent, and a surfactant As a solution, 0.20 g of a 10% by mass solution of PGMEA of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) was dissolved in 24.03 g of PGMEA, and the total solid content concentration was 22% by mass. , to obtain a colored resin composition PC-6 having a coloring material content of 25 parts by mass with respect to 100 parts by mass of the total solid content. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-6. Table 4 shows the results.
２２．９２ｇの着色材分散液（ＤＰ－３）、１６．０４ｇの着色材分散液（ＤＰ－４）、および６．８８ｇの着色材分散液（ＤＰ－５）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２３．２７ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を６．６７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２４．０３ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－６を得た。得られた着色樹脂組成物ＰＣ－６を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 6)
22.92 g of the colorant dispersion (DP-3), 16.04 g of the colorant dispersion (DP-4), and 6.88 g of the colorant dispersion (DP-5) were added with a hydroxyl- or acid-containing resin. 23.27 g of a 35% by mass solution of PGMEA (P-1), 6.67 g of Duranate (registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation) as a blocked isocyanate in which the blocking agent is a pyrazole-based blocking agent, and a surfactant As a solution, 0.20 g of a 10% by mass solution of PGMEA of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie) was dissolved in 24.03 g of PGMEA, and the total solid content concentration was 22% by mass. , to obtain a colored resin composition PC-6 having a coloring material content of 25 parts by mass with respect to 100 parts by mass of the total solid content. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-6. Table 4 shows the results.
（実施例７）
４５．８３ｇの着色材分散液（ＤＰ－６）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２３．２７ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を６．６７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２４．０３ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－７を得た。得られた着色樹脂組成物ＰＣ－７を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 7)
To 45.83 g of the colorant dispersion (DP-6), 23.27 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 6.67 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 24.03 g of PGMEA was added to obtain a colored resin composition PC-7 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-7. Table 4 shows the results.
４５．８３ｇの着色材分散液（ＤＰ－６）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２３．２７ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を６．６７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２４．０３ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－７を得た。得られた着色樹脂組成物ＰＣ－７を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 7)
To 45.83 g of the colorant dispersion (DP-6), 23.27 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 6.67 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 24.03 g of PGMEA was added to obtain a colored resin composition PC-7 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-7. Table 4 shows the results.
（実施例８）
着色材分散液（ＤＰ－２）の代わりに着色材分散液（ＤＰ－７）を用いた以外は実施例３と同様にして、着色樹脂組成物ＰＣ－８を得た。得られた着色樹脂組成物ＰＣ－８を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 8)
A colored resin composition PC-8 was obtained in the same manner as in Example 3 except that the coloring agent dispersion (DP-7) was used instead of the coloring agent dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-8. Table 4 shows the results.
着色材分散液（ＤＰ－２）の代わりに着色材分散液（ＤＰ－７）を用いた以外は実施例３と同様にして、着色樹脂組成物ＰＣ－８を得た。得られた着色樹脂組成物ＰＣ－８を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 8)
A colored resin composition PC-8 was obtained in the same manner as in Example 3 except that the coloring agent dispersion (DP-7) was used instead of the coloring agent dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-8. Table 4 shows the results.
（実施例９）
１８．８６ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を３３．５２ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を７．９０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３９．５２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が１５質量部の着色樹脂組成物ＰＣ－９を得た。得られた着色樹脂組成物ＰＣ－９を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 9)
To 18.86 g of the colorant dispersion (DP-2), 33.52 g of a 35% by mass solution of PGMEA of the hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 7.90 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 39.52 g of PGMEA was added to obtain a colored resin composition PC-9 having a total solids concentration of 22% by mass and a coloring material content of 15 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-9. Table 4 shows the results.
１８．８６ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を３３．５２ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を７．９０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３９．５２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が１５質量部の着色樹脂組成物ＰＣ－９を得た。得られた着色樹脂組成物ＰＣ－９を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 9)
To 18.86 g of the colorant dispersion (DP-2), 33.52 g of a 35% by mass solution of PGMEA of the hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 7.90 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 39.52 g of PGMEA was added to obtain a colored resin composition PC-9 having a total solids concentration of 22% by mass and a coloring material content of 15 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-9. Table 4 shows the results.
（実施例１０）
５６．５７ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を１２．６４ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を４．８７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２５．７１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が４５質量部の着色樹脂組成物ＰＣ－１０を得た。得られた着色樹脂組成物ＰＣ－１０を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 10)
To 56.57 g of the colorant dispersion (DP-2), 12.64 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 4.87 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), and 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 25.71 g of PGMEA was added to obtain a colored resin composition PC-10 having a total solids concentration of 22% by mass and a coloring material content of 45 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-10. Table 4 shows the results.
５６．５７ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を１２．６４ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を４．８７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２５．７１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が４５質量部の着色樹脂組成物ＰＣ－１０を得た。得られた着色樹脂組成物ＰＣ－１０を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 10)
To 56.57 g of the colorant dispersion (DP-2), 12.64 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 4.87 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), and 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 25.71 g of PGMEA was added to obtain a colored resin composition PC-10 having a total solids concentration of 22% by mass and a coloring material content of 45 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-10. Table 4 shows the results.
（実施例１１）
１２．５７ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を３７．００ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を８．４１ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、４１．８２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が１０質量部の着色樹脂組成物ＰＣ－１１を得た。得られた着色樹脂組成物ＰＣ－１１を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 11)
To 12.57 g of the coloring material dispersion (DP-2), 37.00 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 8.41 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Corporation) as a surfactant, A solution dissolved in 41.82 g of PGMEA was added to obtain a colored resin composition PC-11 having a total solids concentration of 22% by mass and a coloring material content of 10 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-11. Table 4 shows the results.
１２．５７ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を３７．００ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を８．４１ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、４１．８２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が１０質量部の着色樹脂組成物ＰＣ－１１を得た。得られた着色樹脂組成物ＰＣ－１１を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 11)
To 12.57 g of the coloring material dispersion (DP-2), 37.00 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 8.41 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Corporation) as a surfactant, A solution dissolved in 41.82 g of PGMEA was added to obtain a colored resin composition PC-11 having a total solids concentration of 22% by mass and a coloring material content of 10 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-11. Table 4 shows the results.
（実施例１２）
６２．８６ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を９．１６ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を４．３７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２３．４１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が５０質量部の着色樹脂組成物ＰＣ－１２を得た。得られた着色樹脂組成物ＰＣ－１２を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 12)
To 62.86 g of the colorant dispersion (DP-2), 9.16 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 4.37 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 23.41 g of PGMEA was added to obtain a colored resin composition PC-12 having a total solids concentration of 22% by mass and a coloring material content of 50 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-12. Table 4 shows the results.
６２．８６ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を９．１６ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を４．３７ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、２３．４１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が５０質量部の着色樹脂組成物ＰＣ－１２を得た。得られた着色樹脂組成物ＰＣ－１２を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 12)
To 62.86 g of the colorant dispersion (DP-2), 9.16 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 4.37 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Corporation), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 23.41 g of PGMEA was added to obtain a colored resin composition PC-12 having a total solids concentration of 22% by mass and a coloring material content of 50 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-12. Table 4 shows the results.
（実施例１３）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を１７．３７ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を１１．４９ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３９．５１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１３を得た。得られた着色樹脂組成物ＰＣ－１３を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 13)
To 31.43 g of the colorant dispersion (DP-2), 17.37 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 11.49 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK Chemie) as a surfactant, A solution dissolved in 39.51 g of PGMEA was added to obtain a colored resin composition PC-13 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-13. Table 4 shows the results.
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を１７．３７ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を１１．４９ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３９．５１ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１３を得た。得られた着色樹脂組成物ＰＣ－１３を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 13)
To 31.43 g of the colorant dispersion (DP-2), 17.37 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 11.49 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK Chemie) as a surfactant, A solution dissolved in 39.51 g of PGMEA was added to obtain a colored resin composition PC-13 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-13. Table 4 shows the results.
（実施例１４）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１４を得た。得られた着色樹脂組成物ＰＣ－１４を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 14)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-14 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-14. Table 4 shows the results.
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１４を得た。得られた着色樹脂組成物ＰＣ－１４を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 14)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-1), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-14 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-14. Table 4 shows the results.
（実施例１５）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－３）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１５を得た。得られた着色樹脂組成物ＰＣ－１５を用いて、実施例１と同様の評価をした。結果を表４に示す。
（実施例１６）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－４）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１６を得た。得られた着色樹脂組成物ＰＣ－１６を用いて、実施例１と同様の評価をした。結果を表４に示す。
（実施例１７）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－５）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１７を得た。得られた着色樹脂組成物ＰＣ－１７を用いて、実施例１と同様の評価をした。結果を表４に示す。
（実施例１８）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－６）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１８を得た。得られた着色樹脂組成物ＰＣ－１８を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 15)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-3), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-15 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-15. Table 4 shows the results.
(Example 16)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-4), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-16 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-16. Table 4 shows the results.
(Example 17)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-5), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-17 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-17. Table 4 shows the results.
(Example 18)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-6), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-18 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-18. Table 4 shows the results.
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－３）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１５を得た。得られた着色樹脂組成物ＰＣ－１５を用いて、実施例１と同様の評価をした。結果を表４に示す。
（実施例１６）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－４）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１６を得た。得られた着色樹脂組成物ＰＣ－１６を用いて、実施例１と同様の評価をした。結果を表４に示す。
（実施例１７）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－５）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１７を得た。得られた着色樹脂組成物ＰＣ－１７を用いて、実施例１と同様の評価をした。結果を表４に示す。
（実施例１８）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－６）のＰＧＭＥＡ３５質量％溶液を３５．７５ｇ、ブロック剤がピラゾール系ブロック剤であるブロックイソシアネートとしてデュラネート（登録商標）ＳＢＢ－７０Ｐ（旭化成（株）製）を２．３０ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３０．３２ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－１８を得た。得られた着色樹脂組成物ＰＣ－１８を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Example 15)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-3), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-15 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-15. Table 4 shows the results.
(Example 16)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-4), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-16 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-16. Table 4 shows the results.
(Example 17)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-5), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-17 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-17. Table 4 shows the results.
(Example 18)
To 31.43 g of the colorant dispersion (DP-2), 35.75 g of a 35% by mass solution of PGMEA of a hydroxyl group- or acid group-containing resin (P-6), and Duranate ( 2.30 g of registered trademark) SBB-70P (manufactured by Asahi Kasei Co., Ltd.), 0.20 g of a PGMEA 10% by mass solution of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, A solution dissolved in 30.32 g of PGMEA was added to obtain a colored resin composition PC-18 having a total solids concentration of 22% by mass and a coloring material content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-18. Table 4 shows the results.
（比較例１）
着色材分散液（ＤＰ－２）の代わりに着色材分散液（ＤＰ－８）を用いた以外は実施例３と同様にして、着色樹脂組成物ＰＣ－１９を得た。得られた着色樹脂組成物ＰＣ－１９を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Comparative example 1)
A colored resin composition PC-19 was obtained in the same manner as in Example 3 except that the colorant dispersion (DP-8) was used instead of the colorant dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-19. Table 4 shows the results.
着色材分散液（ＤＰ－２）の代わりに着色材分散液（ＤＰ－８）を用いた以外は実施例３と同様にして、着色樹脂組成物ＰＣ－１９を得た。得られた着色樹脂組成物ＰＣ－１９を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Comparative example 1)
A colored resin composition PC-19 was obtained in the same manner as in Example 3 except that the colorant dispersion (DP-8) was used instead of the colorant dispersion (DP-2). The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-19. Table 4 shows the results.
（比較例２）
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロックイソシアネートの代わりにエポキシ樹脂の“テクモア”ＶＧ－３１０１Ｌ（（株）プリンテック製）を４．８３ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３６．９８ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－２０を得た。得られた着色樹脂組成物ＰＣ－２０を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Comparative example 2)
To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA containing a hydroxyl group- or acid group-containing resin (P-1), and an epoxy resin "Tecmore" VG-3101L instead of the blocked isocyanate. 4.83 g of (manufactured by Printec Co., Ltd.), 0.20 g of a 10% by mass solution of PGMEA of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK Chemie) as a surfactant, and 36.98 g of PGMEA was added to obtain a colored resin composition PC-20 having a total solid concentration of 22% by mass and a coloring agent content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-20. Table 4 shows the results.
３１．４３ｇの着色材分散液（ＤＰ－２）に、水酸基または酸基含有樹脂（Ｐ－１）のＰＧＭＥＡ３５質量％溶液を２６．５６ｇ、ブロックイソシアネートの代わりにエポキシ樹脂の“テクモア”ＶＧ－３１０１Ｌ（（株）プリンテック製）を４．８３ｇ、界面活性剤としてシリコーン系界面活性剤“ＢＹＫ（登録商標）”３３３（ビックケミー社製）のＰＧＭＥＡ１０質量％溶液０．２０ｇを、３６．９８ｇのＰＧＭＥＡに溶解した溶液を添加して、全固形分濃度２２質量％、全固形分１００質量部に対する着色材の含有量が２５質量部の着色樹脂組成物ＰＣ－２０を得た。得られた着色樹脂組成物ＰＣ－２０を用いて、実施例１と同様の評価をした。結果を表４に示す。 (Comparative example 2)
To 31.43 g of the colorant dispersion (DP-2), 26.56 g of a 35% by mass solution of PGMEA containing a hydroxyl group- or acid group-containing resin (P-1), and an epoxy resin "Tecmore" VG-3101L instead of the blocked isocyanate. 4.83 g of (manufactured by Printec Co., Ltd.), 0.20 g of a 10% by mass solution of PGMEA of silicone surfactant "BYK (registered trademark)" 333 (manufactured by BYK Chemie) as a surfactant, and 36.98 g of PGMEA was added to obtain a colored resin composition PC-20 having a total solid concentration of 22% by mass and a coloring agent content of 25 parts by mass per 100 parts by mass of the total solids. The same evaluation as in Example 1 was performed using the obtained colored resin composition PC-20. Table 4 shows the results.
実施例の着色樹脂組成物は、粘度安定性および低温焼成時の硬化性に優れ、耐光性試験・高温高湿試験後の密着性が高いことがわかる。一方、比較例１の着色樹脂組成物は、粘度安定性が不十分であり、密着性および耐光性試験・高温高湿試験後の密着性が低いことがわかる。低温焼成時の硬化性も不十分であることもわかる。また、比較例２の着色樹脂組成物は、粘度安定性および低温焼成時の硬化性が不十分であることがわかる。
It can be seen that the colored resin compositions of Examples are excellent in viscosity stability and curability at low-temperature baking, and have high adhesion after the light resistance test and high-temperature, high-humidity test. On the other hand, it can be seen that the colored resin composition of Comparative Example 1 has insufficient viscosity stability, and has low adhesion and adhesion after the light resistance test/high temperature and high humidity test. It can also be seen that the curability at the time of low-temperature firing is also insufficient. In addition, it can be seen that the colored resin composition of Comparative Example 2 has insufficient viscosity stability and curability during low-temperature baking.
本発明の着色樹脂組成物は、車載ディスプレイ等のカバーレンズにおける非表示領域の遮光膜を形成する黒色加飾インクとして好適に利用できる。
The colored resin composition of the present invention can be suitably used as a black decorative ink for forming a light-shielding film in the non-display area of the cover lens of an in-vehicle display or the like.
Claims (10)
- （Ａ）水酸基または酸基含有樹脂、（Ｂ）着色材、（Ｃ）分散剤、および（Ｄ）ブロックイソシアネート、を含有し、前記（Ｃ）分散剤が塩基性基を有するアクリル系分散剤である、着色樹脂組成物。 (A) a hydroxyl group- or acid group-containing resin, (B) a coloring agent, (C) a dispersant, and (D) a blocked isocyanate, wherein the (C) dispersant is an acrylic dispersant having a basic group A colored resin composition.
- 前記（Ｃ）分散剤が、３級アミノ基および４級アンモニウム塩基の少なくとも１種を含有する、請求項１に記載の着色樹脂組成物。 2. The colored resin composition according to claim 1, wherein the (C) dispersant contains at least one of a tertiary amino group and a quaternary ammonium base.
- 前記（Ｂ）着色材が、着色樹脂組成物中における平均粒子径が３０～１２０ｎｍである、請求項１～２のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 and 2, wherein the coloring agent (B) has an average particle size of 30 to 120 nm in the colored resin composition.
- 前記（Ａ）水酸基または酸基含有樹脂が、酸価および水酸基価の合計が８０～３００ｍｇＫＯＨ／ｇである、請求項１～３のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 3, wherein (A) the hydroxyl or acid group-containing resin has a total acid value and hydroxyl value of 80 to 300 mgKOH/g.
- 前記（Ｄ）ブロックイソシアネートが活性メチレン化合物およびピラゾール化合物から選択される少なくとも１種のブロック剤を含む、請求項１～４のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 4, wherein the (D) blocked isocyanate comprises at least one blocking agent selected from active methylene compounds and pyrazole compounds.
- 前記（Ｄ）ブロックイソシアネートの含有量が、前記（Ａ）水酸基または酸基含有樹脂の含有量１００質量部に対して５質量部以上１５０質量部以下である、請求項１～５のいずれか１項に記載の着色樹脂組成物。 Any one of claims 1 to 5, wherein the content of (D) the blocked isocyanate is 5 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the content of the (A) hydroxyl group- or acid group-containing resin. The colored resin composition according to the item.
- 前記（Ｂ）着色材の含有量が全固形分１００質量％中の１３～４８質量％である、請求項１～６のいずれか１項に記載の着色樹脂組成物。 The colored resin composition according to any one of claims 1 to 6, wherein the content of the coloring agent (B) is 13 to 48% by weight based on 100% by weight of the total solid content.
- さらに（Ｅ）有機溶剤を含有する、請求項１～７のいずれか１項に記載の着色樹脂組成物。 Further (E) containing an organic solvent, the colored resin composition according to any one of claims 1 to 7.
- 請求項１～８のいずれか１項に記載の着色樹脂組成物の硬化物からなる着色膜。 A colored film comprising a cured product of the colored resin composition according to any one of claims 1 to 8.
- 基板および請求項９に記載の着色膜を具備する、加飾基板。 A decorative substrate comprising a substrate and the colored film according to claim 9 .
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| JP2022504576A JPWO2022163449A1 (en) | 2021-01-28 | 2022-01-19 | |
| CN202280007802.8A CN116568762A (en) | 2021-01-28 | 2022-01-19 | Colored resin composition, colored film, and decorative substrate |
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| CN116568762A (en) | 2023-08-08 |
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