WO2022230259A1 - インクセット - Google Patents
インクセット Download PDFInfo
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- WO2022230259A1 WO2022230259A1 PCT/JP2022/001989 JP2022001989W WO2022230259A1 WO 2022230259 A1 WO2022230259 A1 WO 2022230259A1 JP 2022001989 W JP2022001989 W JP 2022001989W WO 2022230259 A1 WO2022230259 A1 WO 2022230259A1
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- ink composition
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- 239000000203 mixture Substances 0.000 claims abstract description 117
- 229920005989 resin Polymers 0.000 claims abstract description 109
- 239000011347 resin Substances 0.000 claims abstract description 107
- 239000000049 pigment Substances 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 50
- 238000007639 printing Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000007641 inkjet printing Methods 0.000 claims abstract description 5
- 239000012463 white pigment Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 38
- 150000007524 organic acids Chemical class 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- 229920005792 styrene-acrylic resin Polymers 0.000 claims description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 229960003237 betaine Drugs 0.000 claims description 7
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 5
- XPALGXXLALUMLE-UHFFFAOYSA-N 2-(dimethylamino)tetradecanoic acid Chemical group CCCCCCCCCCCCC(N(C)C)C(O)=O XPALGXXLALUMLE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical group CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
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- 239000000839 emulsion Substances 0.000 description 37
- -1 malonic acid Chemical class 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 31
- 229920005749 polyurethane resin Polymers 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 125000000129 anionic group Chemical group 0.000 description 15
- 239000002270 dispersing agent Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 150000007514 bases Chemical class 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 12
- 229920005672 polyolefin resin Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 10
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- 238000000576 coating method Methods 0.000 description 9
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- 230000000694 effects Effects 0.000 description 8
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 6
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
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- 125000001165 hydrophobic group Chemical group 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
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- 239000008213 purified water Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- WRVJTXDJDKITNK-XNGFCKKMSA-N (4r,5s,6s)-6-[(1r)-1-hydroxyethyl]-3-[(3s,5s)-5-[(r)-hydroxy-[(3r)-pyrrolidin-3-yl]methyl]pyrrolidin-3-yl]sulfanyl-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid;hydrochloride Chemical compound Cl.C([C@H]1[C@@H](O)[C@H]2NC[C@H](C2)SC=2[C@H](C)[C@@H]3[C@H](C(N3C=2C(O)=O)=O)[C@H](O)C)CNC1 WRVJTXDJDKITNK-XNGFCKKMSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ZUQAPLKKNAQJAU-UHFFFAOYSA-N acetylenediol Chemical compound OC#CO ZUQAPLKKNAQJAU-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
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- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229960003080 taurine Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 150000005215 alkyl ethers Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- 239000012736 aqueous medium Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 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
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- FXWRHZACHXRMCI-UHFFFAOYSA-L strontium;diformate Chemical compound [Sr+2].[O-]C=O.[O-]C=O FXWRHZACHXRMCI-UHFFFAOYSA-L 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 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
- 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
- C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- C09D11/322—Pigment inks
-
- 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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or 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
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6428—Compounds containing aminoxide groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/647—Nitrogen-containing carboxylic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
Definitions
- the present invention relates to an ink set comprising a pretreatment liquid and an ink composition.
- a pretreatment liquid for inkjet recording containing water-insoluble resin fine particles, an organic acid such as malonic acid, a cross-linking agent, and water is known.
- An image obtained by using this pretreatment liquid has no ink bleeding, excellent adhesion, and excellent lamination strength.
- the pretreatment liquid and ink composition are directed to printing for lamination.
- the printed part for such applications exists inside the laminated product and is not located on the outermost layer when the printed matter is used. Therefore, in the invention described in Patent Document 1, it is not intended to improve effects such as abrasion resistance of the printed portion.
- Patent Literature 2 describes that printing is performed with ink for inkjet recording after treating the surface of an object to be printed with an acidic pretreatment liquid. It also describes that various acids can be used to acidify the pretreatment liquid. However, the printed pattern obtained by such printing is limited to images without bleeding.
- the problem to be solved by the present invention is that even in the presence of an acid atmosphere in the vicinity of the ink nozzle or the like, which is generated when a volatile acid is used in the pretreatment liquid, the dot expansibility of the printed portion is good and excellent. To obtain an ink set that forms an image quality.
- the present invention is as follows. 1. a first ink composition containing a white pigment, an alkali-soluble resin having an acid value of 200 mgKOH/g or more or a crosslinked product thereof in an amount of 1.0% by mass or more in the ink composition, and further containing water;
- the ink composition contains 1.0% by mass or more of a coloring pigment, an alkali-soluble resin having an acid value of 200 mgKOH/g or more, or a crosslinked product thereof, for further printing on the printed layer of the first ink composition, further comprising a combination of an amphoteric surfactant, a water-dispersible resin, and a second ink composition containing water; ink set.
- the amphoteric surfactant is betaine alkylaminoacetate and/or alkylamine oxide. 6.
- the ink set according to 5, wherein the alkylaminoacetic acid betaine is lauryldimethylaminoacetic acid. 7. 7. The ink set according to 5 or 6, wherein the alkylamine oxide is lauryldimethylamine oxide. 8. 8. The ink set according to any one of 1 to 7, which is for inkjet printing. 9. 9. The ink set according to any one of 1 to 8, which is for textile printing. 10. The mass ratio of the monomers constituting the alkali-soluble resin having an acid value of 200 mgKOH/g or more, styrene/alkyl ester having 8 or more carbon atoms of radically polymerizable unsaturated carboxylic acid/(meth)acrylic acid 35 to 55.
- alkyl esters of (meth)acrylic acid having less than 8 carbon atoms/acrylic acid/methacrylic acid 50 to 70/13 to 25/15 to 25 1 to 10.
- the ink composition ejected from the nozzle has excellent abrasion resistance in printing and images, has good dot expansion property in the printed portion, and is ejected from the nozzle even in an atmosphere in which a volatile organic acid is present. Since the flight trajectory of the object is not disturbed, the effect of forming excellent image quality (acid resistance) can be exhibited.
- the ink set of the present invention comprises an ink set comprising a combination of a specific first ink composition containing a white pigment and a specific second ink composition, a pretreatment liquid, and the first ink composition. and the second ink composition.
- This ink set will be described in order below.
- the ink composition may be for printing or textile printing.
- the inkjet ink composition is sometimes referred to as "ink composition”.
- the glass transition temperature and weight average molecular weight for the resins herein are defined as follows. ⁇ Glass transition temperature>
- the glass transition temperature of the resin is the theoretical glass transition temperature obtained by thermal analysis, unless the resin is an acrylic copolymer resin.
- a method of thermal analysis according to JIS K7121 (method for measuring the transition temperature of plastics), as an example, using a Pyris1 DSC manufactured by PerkinElmer, a temperature increase rate of 20 ° C./min and a nitrogen gas flow rate of 20 ml/min.
- the glass transition temperature can be measured at
- the weight average molecular weight of the resin in the present invention can be measured by gel permeation chromatography (GPC) method.
- GPC gel permeation chromatography
- PLgel polymer gel
- MIXED-D manufactured by Polymer Laboratories
- tetrahydrofuran as a developing solvent
- column temperature 25 ° C. flow rate 1 ml / min
- RI Chromatography is performed under the conditions of a detector, a sample injection concentration of 10 mg/ml, and an injection amount of 100 microliters, and the polystyrene equivalent weight average molecular weight is obtained.
- the pretreatment liquid in the present invention contains an organic acid having a boiling point of 120° C. or less under 1 atmosphere, and further contains a surfactant.
- Organic acid having a boiling point of 120°C or less under 1 atmosphere As the organic acid having a boiling point of 120° C. or less under 1 atmosphere used in the pretreatment liquid, formic acid (boiling point of 100.8° C. under 1 atmosphere) and/or acetic acid (boiling point of 118° C. under 1 atmosphere) can be used. Available.
- Such an organic acid is preferably contained in the pretreatment liquid in an amount of 5.0% by mass or more, more preferably 8.0% by mass or more.
- the content is preferably 30.0% by mass or less, more preferably 25.0% by mass or less.
- the boiling point and the content of the organic acid are within these ranges, by applying this pretreatment liquid to the surface of the substrate to be printed, a printed portion formed thereon by the first ink composition of the present invention can be obtained.
- the organic acid can exist on the surface of the first ink composition layer through the first ink composition layer.
- the components in the subsequently printed second ink composition then react with the organic acid. This tendency is particularly noticeable during inkjet printing and textile printing by inkjet.
- the content of the organic acid is too low, it may take time to fix the resin in each ink composition layer printed thereon. Also, if it is contained excessively, a large amount of the organic acid remains in the printed layer after printing, so it may take time for the organic acid to evaporate and the free acid in the print or image to disappear. .
- the pretreatment liquid may or may not contain a surfactant.
- surfactants that can be contained anionic surfactants and nonionic surfactants are preferred.
- a cationic surfactant or an amphoteric surfactant is contained, there is a possibility of forming a salt with an organic acid having a boiling point of 120° C. or less under 1 atm.
- the content of the surfactant is, for example, 0 to 1.0% by mass, preferably 0.01 to 1.0% by mass, more preferably 0.1 to 0.7% by mass, relative to the entire pretreatment liquid. is.
- anionic surfactants include phosphate-based surfactants, alkenylsuccinic acid-based surfactants, alkylbenzene sulfonic acid alkali metal salt-based surfactants, taurine-based surfactants, and polyoxyethylene alkylphenyl sulfate alkali metal salt-based surfactants.
- surfactants can be employed.
- Phosphate-based surfactants are preferably phosphate ester-based surfactants, such as Plysurf AL, Plysurf DB-01, Plysurf A219B, Plysurf A208B, and Plysurf 212C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). can be used.
- alkenyl succinic acid surfactant and/or a taurine surfactant can be used together with the phosphate surfactant.
- alkenylsuccinic acid-based surfactant or its salt alkenylsuccinic acid (manufactured by Seiko PMC) and dipotassium alkenylsuccinate (manufactured by Kao Corporation) can be used.
- alkylbenzenesulfonic acid alkali metal salt surfactant sodium dodecylbenzenesulfonate and the like can be used.
- taurine-based surfactants examples include N-acyl taurine salts (manufactured by Nikko Chemicals), LMT (N-lauroylmethyltaurate Na), MMT (N-myristoylmethyltaurate Na), PMT (N-palmitoylmethyltaurate Na), SMT (Na N-stearoylmethyltaurate) can be included.
- N-acyl taurine salts manufactured by Nikko Chemicals
- LMT N-lauroylmethyltaurate Na
- MMT N-myristoylmethyltaurate Na
- PMT N-palmitoylmethyltaurate Na
- SMT Na N-stearoylmethyltaurate
- polyoxyethylene alkylphenyl sulfate alkali metal salt surfactant polyoxyethylene nonylphenyl sodium sulfate or the like can be used.
- nonionic surfactants include one or more selected from silicone surfactants, fluorosurfactants and acetylenic surfactants.
- silicone-based surfactants include BYK-347, BYK-377, and BYK-3455 (BYK-Chemie Japan).
- fluorine-based surfactants examples include F-410, F-444, F-553 (manufactured by DIC Corporation), FS-65, FS-34, FS-35, FS-31, FS-30 (manufactured by , manufactured by DuPont).
- acetylenic surfactants include Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, Surfynol 465 (EVONIK), Dynol 607, Dynol 609, Olfine E1004, Olfine E1010, Olfine E1020, Olfine PD-001, Olfine PD-002W, Olfine PD-004, Olfine PD-005, Olfine EXP. 4001, Olfine EXP. 4200, Olfine EXP. 4123, Olfine EXP.
- One or two or more selected from those commercially available under trade names such as 4300 (Nissin Kagaku Kogyo Co., Ltd.) can be mentioned.
- solvent As a solvent for the pretreatment liquid in the present invention, water alone or a mixed solvent of water and a water-soluble organic solvent can be employed.
- water-soluble organic solvent include monoalcohols, polyhydric alcohols, lower alkyl ethers of polyhydric alcohols, ketones, ethers, esters, and nitrogen-containing compounds. These may be used alone or in combination of two or more.
- Examples of the monoalcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, or these. isomers, cyclopentanol, cyclohexanol, etc., and preferably alcohols having an alkyl group of 1 to 6 carbon atoms can be used.
- polyhydric alcohols examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,2- Hexanediol, 1,6-hexanediol, 1,2-cyclohexanediol, heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol, dipropylene Glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol and the like can be used.
- lower alkyl ethers of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol.
- Isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n-propyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono -n-butyl ether and the like can be used.
- the content of the water-soluble organic solvent is preferably as low as possible, and may be omitted. However, the content when blended is preferably 0 to 10.0% by mass, more preferably 0 to 5.0% by mass in the pretreatment liquid. If it exceeds 10.0% by mass, poor drying and anti-blocking properties will decrease.
- the pretreatment liquid in the present invention may or may not contain a water-soluble polyvalent metal salt as another component.
- the water-soluble polyvalent metal salt is an organic or inorganic acid salt of a polyvalent metal having a solubility of 1 g/100 mL or more, preferably 2 g/100 mL or more, more preferably 20 g/100 mL or more in 100 mL of water at 20°C. be.
- the water-soluble polyvalent metal salt may be a double salt containing a polyvalent metal, or a hydrate.
- polyvalent metals include one or more selected from magnesium, calcium, strontium, zinc, copper, iron, and aluminum.
- organic acid for constituting the water-soluble polyvalent metal salt for example, one or more of fatty acids represented by RCOOH (wherein R is hydrogen and an organic group having 1 to 30 carbon atoms). mentioned.
- organic acids include formic acid, acetic acid, propionic acid, octylic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, 12-hydroxystearic acid, ricinoleic acid, oleic acid, vaccenic acid, Linoleic acid, linolenic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, lactic acid, citric acid, gluconic acid, malic acid, tartaric acid, succinic acid, malonic acid, glutaric acid, maleic acid, fumaric acid acid, glutaconic acid, benzoic acid, ascorbic acid and the like.
- water-soluble polyvalent metal salts that are polyvalent metal salts of organic acids include zinc acetate, calcium acetate, strontium acetate, magnesium acetate, zinc formate, calcium formate, strontium formate, copper (II) formate, magnesium formate, calcium benzoate, magnesium benzoate, zinc benzoate, calcium lactate, magnesium lactate, aluminum lactate, iron (II) lactate, copper lactate, calcium ascorbate, magnesium ascorbate, calcium propionate, magnesium propionate, calcium gluconate, One or more selected from magnesium gluconate, zinc gluconate, copper gluconate, zinc citrate, copper citrate, and hydrates thereof may be used.
- water-soluble polyvalent metal salts that are polyvalent metal salts of inorganic acids include zinc chloride, aluminum chloride, calcium chloride, strontium chloride, iron chloride, copper (II) chloride, nickel chloride, magnesium chloride, chloride manganese (II), zinc bromide, calcium bromide, strontium bromide, iron (II) bromide, copper (II) bromide, magnesium bromide, zinc iodide, calcium iodide, magnesium iodide, aluminum nitrate, Calcium nitrate, Strontium nitrate, Iron(III) nitrate, Copper(II) nitrate, Magnesium nitrate, Zinc sulfate, Aluminum sulfate, Iron(II) sulfate, Iron(III) sulfate, Copper sulfate, Magnesium sulfate, Potassium aluminum sulfate, Phosphorus
- calcium dihydrogen calcium sul
- the blending amount of the water-soluble polyvalent metal salt is not particularly limited and can be appropriately adjusted according to the type of salt and the purpose of blending.
- the lower limit of the content of the water-soluble polyvalent metal salt is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more in terms of solid content in the pretreatment liquid.
- the upper limit of the water-soluble polyvalent metal salt content is, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less in terms of solid content in the pretreatment liquid.
- the content of the water-soluble polyvalent metal salt is, for example, 0.1 to 20% by mass, preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass in terms of solid content in the pretreatment liquid. .
- the ink composition of the present invention contains a pigment of each hue to obtain ink compositions of each color as the first and second ink compositions.
- the first ink composition is a white ink composition containing a white pigment
- the second ink composition is a colored ink composition containing a color pigment other than white.
- pigments pigments conventionally used in ordinary ink compositions can be used without particular limitation.
- White pigments for use in the white ink composition include, for example, titanium oxide and aluminum oxide, preferably titanium oxide surface-treated with various materials such as alumina and silica.
- the coloring pigment used to obtain the colored ink composition is one or more selected from the following organic pigments and black pigments.
- organic pigments examples include dye lake pigments, azo-based, benzimidazolone-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo-based, thioindico-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, Examples include isoindolinone-based, nitro-based, nitroso-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, and indanthrone-based pigments.
- Examples of inorganic pigments include carbon black, titanium oxide, red iron oxide, graphite, iron black, chromium oxide green, and aluminum hydroxide. Specific examples of pigments include the following.
- Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, 213, etc., preferably C.I. I. Pigment Yellow 150, 155, 180, 213 and the like.
- Examples of magenta pigments include C.I. I.
- Examples of cyan pigments include C.I. I.
- Black pigments for use in black ink compositions include, for example, carbon black (C.I. Pigment Black 7).
- the content of the pigment in the ink composition is preferably 1.0 to 20.0% by mass with respect to the total mass of the ink composition. If the pigment content is less than 1% by mass, the image quality of the resulting printed matter tends to deteriorate. On the other hand, if it exceeds 20.0% by mass, it tends to adversely affect the viscosity characteristics of the ink composition.
- the first ink composition in the present invention may contain a pigment dispersant if necessary.
- the pigment dispersant is used to improve the dispersibility of the pigment and the storage stability of the ink composition of the present invention, and conventionally used ones can be used without particular limitation. It is preferred to use agents.
- examples of such pigment dispersants include carbodiimide dispersants, polyesteramine dispersants, fatty acid amine dispersants, modified polyacrylate dispersants, modified polyurethane dispersants, polychain polymer nonionic dispersants, A polymer ion activator and the like can be mentioned. These pigment dispersants can be used alone or in combination of two or more.
- the pigment dispersant When used, it is preferably contained in an amount of 1 to 200 parts by mass based on 100 parts by mass of all pigments used. If the content of the pigment dispersant is less than 1 part by mass, the pigment dispersibility and the storage stability of the ink composition of the present invention may deteriorate. On the other hand, it is possible to contain more than 200 parts by mass, but there are cases where there is no difference in the effect. A more preferable lower limit for the content of the pigment dispersant is 5 parts by mass, and a more preferable upper limit is 60 parts by mass.
- Alkali-soluble resin having an acid value of 200 mgKOH/g or more or a crosslinked product thereof include, for example, acrylic copolymer resins, maleic acid-based copolymer resins, polyester resins obtained by polycondensation reaction, polyurethane resins, etc. or crosslinked products thereof. is mentioned. Materials for synthesizing this alkali-soluble resin are disclosed, for example, in Japanese Patent Application Laid-Open No. 2000-94825. Copolymer resins, polyester resins, polyurethane resins, etc. can be used.
- the said alkali-soluble resin can be used individually or in combination of 2 or more types. Further, an alkali-soluble resin having an acid value of 200 mgKOH/g or less or a crosslinked product thereof can be blended in the first and second ink compositions within a range that does not impair the effects of the present invention.
- an alkali-soluble resin having an acid value of 200 mgKOH/g or more or a crosslinked product thereof is added to each of the first ink composition and the second ink composition. contains.
- the content in the ink composition is preferably 1.3% by mass or more, more preferably 1.5% by mass or more.
- the content of the alkali-soluble resin having an acid value of 200 mgKOH/g or more is 5.0 parts by mass with respect to 100 parts by mass of the pigment from the viewpoint of enhancing the dispersibility of the pigment. It is preferably 15.0 parts by mass or more, more preferably 15.0 parts by mass or more.
- the content of the alkali-soluble resin is preferably 100.0 parts by mass or less and 80.0 parts by mass or less with respect to 100 parts by mass of the pigment. is more preferable, and 60.0 parts by mass or less is even more preferable.
- the content of the alkali-soluble resin having an acid value of 200 mgKOH/g or more is 50.0 parts by mass or more with respect to 100 parts by mass of the pigment from the viewpoint of enhancing the dispersibility of the pigment. It is preferably 100.0 parts by mass or more, more preferably 100.0 parts by mass or more.
- the content of the alkali-soluble resin is preferably 300.0 parts by mass or less and 280.0 parts by mass or less with respect to 100 parts by mass of the pigment. is more preferable, and 250.0 parts by mass or less is even more preferable.
- acrylic copolymer resin for example, a mixture of an anionic group-containing monomer and another copolymerizable monomer is mixed with a usual radical generator (e.g., benzoyl peroxide, tertiarybutyl peroxybenzoate, azo bisisobutyronitrile, etc.) in a solvent, and those obtained by polymerization can be used.
- a radical generator e.g., benzoyl peroxide, tertiarybutyl peroxybenzoate, azo bisisobutyronitrile, etc.
- the anionic group-containing monomer includes, for example, a monomer having at least one anionic group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic acid group. is particularly preferred.
- Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, anhydrous Maleic acid, fumaric anhydride, maleic acid half ester, and the like.
- examples of the monomer having a sulfonic acid group include sulfoethyl methacrylate.
- Examples of the monomer having a phosphonic acid group include phosphonoethyl methacrylate.
- Other monomers copolymerizable with the anionic group-containing monomer preferably include a hydrophobic group-containing monomer from the viewpoint of improving the adsorptivity with the pigment.
- the hydrophobic group-containing monomers include, for example, monomers having a long-chain alkyl group, alkyl esters having 8 or more carbon atoms of a radically polymerizable unsaturated carboxylic acid such as (meth)acrylic acid (e.g.
- monomers having an aromatic hydrocarbon group include styrene-based monomers such as benzyl (meth)acrylate, styrene, ⁇ -methylstyrene and vinyltoluene.
- the hydrophobic group-containing monomers may be used alone or in combination of two or more.
- Other monomers copolymerizable with the anionic group-containing monomer may include hydrophilic group-containing monomers from the viewpoint of suppressing aggregation of the alkali-soluble resin in the aqueous medium.
- hydrophilic group-containing monomer examples include monomers having a (poly)oxyalkylene chain, such as methoxypolyethylene glycol, methoxypolyethylenepolypropyleneglycol, ethoxypolyethyleneglycol, ethoxypolyethylenepolypropyleneglycol, propoxypolyethyleneglycol, and propoxypolyethylene.
- monomers having a (poly)oxyalkylene chain such as methoxypolyethylene glycol, methoxypolyethylenepolypropyleneglycol, ethoxypolyethyleneglycol, ethoxypolyethylenepolypropyleneglycol, propoxypolyethyleneglycol, and propoxypolyethylene.
- Esterification products of single-terminal alkyl-blocked (poly)alkylene glycols such as polypropylene glycol and radically polymerizable unsaturated carboxylic acids such as (meth)acrylic acid, and radically polymerizable unsaturated carboxylic acids such as (meth)acrylic acid ethylene oxide adducts and/or propylene oxide adducts; basic group-containing monomers such as vinylpyrrolidones such as 1-vinyl-2-pyrrolidone and 1-vinyl-3-pyrrolidone; 2-vinylpyridine; -Vinylpyridines such as vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, vinylimidazoles such as 1-vinylimidazole, 1-vinyl-2-methylimidazole, 3-vinylpiperidine , vinyl biperidines such as N-methyl-3-vinylpiperidine, dimethylaminoethyl (me
- a monomer having a hydroxyl group for example, hydroxyethyl (meth) acrylate, hydroxyalkyl esters of (meth)acrylic acid such as hydroxypropyl (meth) acrylate, etc.;
- a monomer having an epoxy group for example, glycidyl (Meth)acrylate and the like.
- the hydrophilic group-containing monomers may be used alone or in combination of two or more.
- copolymerizable monomers other than the hydrophobic group-containing monomer and the hydrophilic group-containing monomer include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, (meth) Alkyl esters of (meth)acrylic acid having less than 8 carbon atoms, such as propyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and cyclohexyl (meth)acrylate mentioned.
- the hydrophobic group-containing monomer and other copolymerizable monomers other than the hydrophilic group-containing monomer can be used alone or in combination of two or more.
- the bifunctional or higher functional cross-linking agent may have two or more reactive functional groups in the molecule in order to react with the functional groups possessed by the alkali cross-linkable resin.
- the reactive functional group include epoxy group, hydroxyl group, isocyanate group, amino group, and aziridine group.
- cross-linking agents that are dispersed, emulsified, dissolved in water or are dispersible, emulsifiable and/or soluble in water are particularly preferred.
- the bifunctional or higher functional cross-linking agents may be used alone or in combination of two or more.
- the acid value of the alkali-soluble resin is 200 mgKOH/g or more, more preferably 210 mgKOH/g or more, and even more preferably 220 mgKOH/g or more, from the viewpoint of enhancing reactivity with the organic acid contained in the pretreatment liquid. Moreover, the acid value of the alkali-soluble resin is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, and even more preferably 240 mgKOH/g or less, from the viewpoint of improving the water resistance of printed matter.
- the acid value was obtained by arithmetically determining the number of mg of potassium hydroxide theoretically required to neutralize 1 g of the alkali-soluble resin, based on the composition of the monomers used for synthesizing the alkali-soluble resin. Theoretical acid number.
- the glass transition temperature of the alkali-soluble resin is preferably 0°C or higher, more preferably 20°C or higher, and even more preferably 40°C or higher, from the viewpoint of improving the blocking resistance of printed matter.
- the glass transition temperature of the alkali-soluble resin is preferably 100° C. or lower, more preferably 80° C. or lower, and still more preferably 60° C. or lower, from the viewpoint of improving the bending resistance of printed matter.
- the weight-average molecular weight of the alkali-soluble resin is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 13,000 or more, from the viewpoint of improving the water resistance of printed matter.
- the weight-average molecular weight of the alkali-soluble resin is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less, from the viewpoint of enhancing solubility in an aqueous medium.
- amphoteric surfactant As the amphoteric surfactant contained in the second ink composition, known surfactants can be employed, among which betaine alkylaminoacetate and/or alkylamine oxide are preferred. As the alkylaminoacetic acid betaine, lauryldimethylaminoacetic acid (lauryldimethylaminoacetic acid betaine) is preferable. A preferred alkylamine oxide is lauryldimethylamine oxide. 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaines can also be employed.
- the content of the amphoteric surfactant in the ink composition of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 0.5% by mass or more relative to the total amount of the ink composition. is more preferred. Moreover, it is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, even more preferably 2.0% by mass or less, and most preferably 1.0% by mass or less, relative to the total amount of the ink composition. If the amphoteric surfactant is not contained, it may be difficult to improve the dot scalability of the printed area, and even if it exceeds 10.0% by mass, no further improvement in the effect can be expected. there is a possibility.
- the first ink composition can also contain an amphoteric surfactant.
- the first and second ink compositions of the present invention may contain any other surfactant to optimize the printing or textile printing process within the range that does not impair the effects of the present invention.
- surfactants such as acetylene diol surfactants and silicone surfactants conventionally used in ink compositions can be used as surfactants. agents, anionic surfactants, etc. may or may not be included to improve jetting stability.
- acetylene diol-based surfactants include Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, and the like.
- EVONIK Olfine E-1004, Olfine E-1010, Olfine E-1020, Olfine PD-001, Olfine PD-002W, Olfine PD-004, Olfine PD-005, Olfine EXP. 4001, Olfine EXP. 4200, Olfine EXP.
- silicone surfactants include polyether-modified silicone oil, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, and the like. Examples of these include BYK-307, BYK-333, BYK-347, BYK-348, BYK-349, BYK-345, BYK-378, BYK-3455 (manufactured by BYK-Chemie) and the like. These can be used singly or in combination of two or more.
- the content of other surfactants in the ink composition of the present invention is preferably 0.005 to 1.0% by mass. If it is less than 0.005% by mass, the surface tension of the ink composition of the present invention may become high, and the ejection stability from an inkjet head may deteriorate. On the other hand, if it exceeds 1.0% by mass, bubbles may increase in the ink composition and the ejection stability may deteriorate.
- Water-dispersible resin for second ink composition
- one or more selected from an acrylic resin emulsion, a styrene-acrylic resin emulsion, a polyurethane resin emulsion, and a polyolefin resin emulsion can be employed.
- the solid content of the water-dispersible resin in the second ink composition of the present invention is preferably 10.0% by mass or more, more preferably 13.0% by mass or more, from the viewpoint of improving print image quality and scratch resistance. is more preferable, and from the viewpoint of improving print image quality, it is preferably 30.0% by mass or less, and more preferably 25.0% by mass or less.
- the ratio of the solid content of the water-dispersible resin to the total amount of the resin and the pigment in the second ink composition of the present invention is 30.0% by mass or more from the viewpoint of improving print image quality and scratch resistance. is preferred, 40.0% by mass or more is more preferred, 50.0% by mass or more is even more preferred, and 60.0% by mass is most preferred.
- the acid value of the water-dispersible resin is preferably 15 mgKOH/g or less, more preferably 10 mgKOH/g or less, even more preferably 5 mgKOH/g or less, most preferably 1 mgKOH/g or less, and 0 mgKOH/g, from the viewpoint of enhancing acid resistance. It may be g.
- the acid value was obtained by arithmetically determining the number of mg of potassium hydroxide theoretically required to neutralize 1 g of the alkali-soluble resin, based on the composition of the monomers used for synthesizing the alkali-soluble resin. Theoretical acid value.
- the acrylic resin emulsion is a polymer obtained by mixing one or more of the following monomers.
- (meth)acrylic acid ester with alcohol having an alkyl group having 1 to 18 carbon atoms 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl ( Meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate and the like can be mentioned.
- (Meth)acrylate is a general term for acrylate and methacrylate.
- ethylenically unsaturated monomers may be used in combination.
- examples include acrylonitrile, vinyl acetate, vinyl propionate, styrene, acrylic acid, methacrylic acid, (meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide and the like.
- a styrene-acrylic resin emulsion is an emulsion in which a styrene-acrylic resin is dispersed in water, and can be produced by emulsion polymerization, dispersion polymerization, suspension polymerization, pulverization or solution/bulk polymerization, followed by post-emulsification. Further information on this method and stabilizers can be found in "Emulsion Polymerization and Emulsion Polymer" (P.A. Lovell, M.S. El-Aasser, John Wiley & Sons Ltd., England, 1977, by citing incorporated herein).
- styrene-acrylic resin emulsions include M6963 (manufactured by Japan Coating Resin Co., Ltd.) J-450, J-734, J-7600, J-352, J-390, J-7100, J-741, J-74J. , J-511, J-840, J-775, HRC-1645, HPD-71, PDX-6102B, JDX-5050 (manufactured by BASF), UC-3900 (manufactured by Toagosei) and the like.
- the polyurethane-based resin emulsion is an emulsion in which a polyurethane resin is dispersed in water, and may be anionic, cationic, or nonionic, but anionic and nonionic are preferred.
- the polyurethane resins include polyether-based polyurethane resins, polyester-based polyurethane resins, polyester/polyether-based polyurethane resins, and polycarbonate-based polyurethane resins.
- the polyurethane-based resin emulsion can be used alone or in combination of two or more.
- Examples of commercially available polyurethane resin emulsions include “Superflex 210" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., anionic polyester polyurethane resin), “NeoRez R967” (manufactured by DSM Coating Resins, polyether polyurethane), “Superflex 130” (Daiichi Kogyo Seiyaku Co., Ltd., anionic polyether polyurethane resin), “Superflex 500M” (Daiichi Kogyo Seiyaku Co., Ltd., nonionic polyester polyurethane resin), “Superflex 460” (Daiichi Kogyo Seiyaku Co., Ltd., nonionic polyester polyurethane resin) Ichi Kogyo Seiyaku Co., Ltd., anionic polycarbonate polyurethane resin), “Impranil DLP1380” (Sumika Covestro Urethane Co., Ltd., anionic polyester polyure
- the polyolefin resin emulsion is an emulsion in which polyolefin resin is dispersed in water.
- the polyolefin resins include polyethylene resins, polypropylene resins, polybutylene resins, and polyolefin resins obtained by copolymerizing two or more of ethylene, propylene, and butylene.
- the polyolefin resin includes a modified polyolefin resin obtained by introducing an amino group, a carboxyl group, a hydroxyl group, an acryloyl group, and other polymer chains into the polyolefin chain; an oxidized polyolefin resin obtained by oxidizing a part of the polyolefin chain; Halogenated polyolefin resin partially treated with halogen may also be used.
- the polyolefin resin emulsion can be used alone or in combination of two or more.
- polyolefin resin emulsions examples include "Chemipearl S100” (manufactured by Mitsui Chemicals, polyethylene resin emulsion), “Chemipearl XEP800H” (manufactured by Mitsui Chemicals, polypropylene resin emulsion), and “Arrowbase TC- 4010” (manufactured by Unitika Ltd., polypropylene-based resin emulsion).
- the resin emulsion includes AP4710 (acrylic-silicon resin emulsion, Showa Emulsion) used for ink compositions other than the acrylic resin emulsion, the styrene acrylic resin emulsion, the polyurethane resin emulsion and the polyolefin resin emulsion. (manufactured by Kobunshi Co., Ltd.), etc. (other resin emulsions) can be included as long as the effects of the present invention are not impaired.
- the other resin emulsions include polyvinyl acetate-based resin emulsions and polyvinyl chloride-based resin emulsions.
- the styrene acrylic resin emulsion and/or the polyurethane resin emulsion is preferably 70% by mass or more, more preferably 80% by mass or more, from the viewpoint of improving coating film resistance such as scratch resistance. 90% by mass or more is more preferable, and 95% by mass or more is most preferable.
- additives can be added to the first and second ink compositions of the present invention, as necessary, in order to develop various functionalities. Specifically, surface conditioners, light stabilizers, surface treatment agents, antioxidants, anti-aging agents, cross-linking accelerators, polymerization inhibitors, plasticizers, preservatives, pH adjusters, antifoaming agents, moisturizing agents etc.
- a resin that functions as a vehicle but is not curable may or may not be blended.
- a solvent may be contained, but it is not necessary to contain it.
- the first and second ink compositions of the present invention may contain a basic compound from the viewpoint of dissolving the alkali-soluble resin.
- the basic compound include inorganic basic compounds such as sodium hydroxide and potassium hydroxide; ammonia, methylamine, ethylamine, monoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, organic basic compounds such as N,N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine;
- the said basic compound can be used individually or in combination of 2 or more types.
- the ratio of the basic compound in the first and/or second ink composition is the alkali-soluble
- the amount may be sufficient as long as it dissolves the resin in the medium, but from the viewpoint of enhancing the dispersion stability of the alkali-soluble resin, it is preferably 0.05% by mass or more, and preferably 0.1% by mass or more. It is more preferably 1% by mass or less, and more preferably 0.5% by mass or less, from the viewpoint of enhancing the water resistance of printed matter.
- the first and second ink compositions of the present invention may further contain known resins, antifungal agents, antirust agents, thickeners, antioxidants, ultraviolet absorbers, and preservability improvers depending on the purpose. , antifoaming agents, pH adjusters, and other additives may be added.
- the pretreatment liquid in the present invention can be prepared by adding predetermined amounts of an organic acid and, if necessary, a surfactant or the like to water in any order.
- the method of preparing (manufacturing) the first and second ink compositions of the present invention is not particularly limited, and the above components may be added in order or at the same time and mixed.
- the following methods (1) and (2) can be adopted.
- a resin-coated pigment is obtained by depositing an alkali-soluble resin on the pigment surface by a method such as depositing an anionic group-containing resin on the pigment surface, and then the obtained resin
- a method of neutralizing a coated pigment with a basic compound redispersing it in water using various dispersing machines (such as a high-speed stirring device), and adding the rest of the ingredients to prepare an ink composition.
- the ink composition in the present invention has an initial viscosity after production of 2.0 to 15.0 mPa ⁇ s, preferably 3.0 to 12.0 mPa ⁇ s.
- the viscosity can be measured, for example, with an E-type viscometer (trade name “RE100L type viscometer”, manufactured by Toki Sangyo Co., Ltd.).
- the printing method using the ink set of the present invention consists of two steps: a step of applying a pretreatment liquid to the surface of a substrate to be printed such as a printing paper or a resin film; and a printing step of printing with an ink composition.
- the step of applying the pretreatment liquid may be performed by inkjet printing or other known methods.
- the step of printing with the ink composition may be performed wet-on-wet in which the applied pretreatment liquid is not dried, or may be performed after drying the applied pretreatment liquid. You can go wet.
- Pretreatment liquid 1 (20 parts by mass of acetic acid, 0.2 parts by mass of Surfynol 440 (acetylene diol-based surfactant, HLB8, manufactured by EVONIK), and purified water were stirred and mixed to make 100 parts by mass)
- Pretreatment liquid 2 (10 parts by mass of acetic acid in pretreatment liquid 1)
- Pretreatment liquid 3 pretreatment liquid 1 in which acetic acid is replaced with lactic acid (an organic acid having a boiling point of over 120°C at 1 atm))
- JR-809 titanium oxide treated with silica and alumina, average particle size 0.23 ⁇ m, DBP oil amount 24 ml / 100 g, manufactured by Tayca
- PF-690 titanium oxide treated with silica, alumina and organic matter, average particle size 0.21 ⁇ m, DBP oil amount 16 ml / 100 g, manufactured by Ishihara Sangyo Co., Ltd.
- HB890 trade name “High Black 890”, average primary particle size 15 nm, DBP oil amount 95 ml/100 g, pH 8.0, manufactured by Orion Engineered Carbons
- PB15:3 Pigment Blue 15:3
- PR122 Pigment Red 122)
- PY14 Pigment Yellow 14
- Alkali-soluble resin varnish 25 parts by mass of alkali-soluble resin 1, sodium hydroxide having a neutralization equivalent of 100%, and purified water were mixed to make 100 parts by mass, and dissolved by heating and stirring at 90° C. to obtain alkali-soluble resin varnish 1. .
- 25 parts by mass of each of the alkali-soluble resins 2 to 5, sodium hydroxide in a mass that gives a neutralization equivalent of 100% for each alkali-soluble resin, and purified water were mixed to make 100 parts by mass. , and dissolved by heating and stirring at 90° C. to obtain alkali-soluble resin varnishes 2 to 5, respectively.
- ⁇ Aqueous each color ink base> As shown in Table 1, after stirring and mixing 50 parts by mass of JR-809, 40 parts by mass of alkali-soluble resin varnish 2, and 10 parts by mass of purified water, kneading was performed in a wet circulation mill to prepare an aqueous white ink base 1. did. Similarly, each pigment, each alkali-soluble resin varnish, and purified water were stirred and mixed as shown in Table 1, and kneaded in a wet circulation mill to prepare water-based ink bases for each color.
- M6963 (trade name “M6963”, styrene-acrylic emulsion (solid content concentration 45% by mass), acid value less than 10 mgKOH / g, manufactured by Japan Coating Resin Co., Ltd.)
- R967 (trade name “NeoRez R-967”, polyether polyurethane emulsion (solid content concentration 40% by mass), acid value 19 mgKOH/g, manufactured by DSM Coating Resins)
- ⁇ Ink composition> Each component was stirred and mixed as shown in Table 2 to obtain an ink composition of each example and comparative example.
- Alkali-soluble resin varnish 2 (post-added) is obtained by adding alkali-soluble resin varnish 2 to the ink composition once obtained.
- Reference examples in Table 2 are examples of pretreatment with pretreatment liquid 1 or 2, followed by printing with each color ink composition containing each color ink base, pigment, solvent, etc., and optionally alkali-soluble resin varnish. is.
- the white ink composition in the present invention corresponds to the first ink composition
- the ink compositions of other colors correspond to the second ink composition.
- Example 1 after pretreatment with pretreatment liquid 1, although not shown in Table 2, the white ink composition used in Reference Example 1 was printed thereon as the first ink composition. Then, each color ink composition described in each example was printed as a second ink composition.
- Comparative Examples 1 to 4 after pretreatment with pretreatment liquid 1 or 3, the white ink composition used in Reference Example 1 was added to the first ink composition although not shown in Table 2. Then, the ink composition of each color described in each comparative example was printed as a second ink composition.
- the print of the nozzle check image is a print obtained by printing a test image preset on the printer side using a dedicated program on the printer side. ⁇ : Even when printing on 20 or more print media, ejection was confirmed from all nozzles when the nozzle check image was printed. ⁇ : After printing started, the nozzle check image was printed within 20 print media. Nozzles with non-ejection or crooked ejection were found during printing.
- Examples 1 to 5 which are examples according to the present invention, images having excellent image quality and coating film resistance can be formed. Furthermore, printing can be performed with a dot diameter of 35 ⁇ m.
- Reference Examples 1 to 10 in which the ink composition does not contain an amphoteric surfactant, images having excellent image quality and coating film resistance can be formed. The dot diameter was as small as 22 ⁇ m.
- Comparative Example 1 which did not contain an alkali-soluble resin having an acid value of 200 mgKOH/g or more and did not contain an amphoteric surfactant, both the image quality and the coating film resistance were poor. Even in Comparative Example 2, in which an organic acid having a boiling point exceeding 120° C.
- the black ink composition contained an alkali-soluble resin with an acid value of 200 mgKOH/g or more
- Comparative Example 3 containing no amphoteric surfactant
- the image quality was not particularly good and the dot diameter was as small as 26 ⁇ m.
- Comparative Example 4 in which the black ink composition contained only a small amount of an alkali-soluble resin having an acid value of 200 mgKOH/g or more and did not contain an amphoteric surfactant, the image quality was not good.
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Abstract
Description
特許文献2には、被印刷物表面を酸性の前処理液で処理した後に、インクジェット記録用インクにより印刷を行うことが記載されている。そして、前処理液を酸性にするために各種の酸を使用できることも記載されている。しかしながら、このような印刷により得られる印字パターンは画像等に滲みがないものに留まる。
すなわち、本発明は以下の通りである。
1.白色顔料、酸価が200mgKOH/g以上のアルカリ可溶性樹脂又はその架橋物をインク組成物中1.0質量%以上含有し、さらに水を含有する第1のインク組成物と、
この第1のインク組成物による印刷層上にさらに印刷するための、着色顔料、酸価が200mgKOH/g以上のアルカリ可溶性樹脂又はその架橋物をインク組成物中1.0質量%以上含有し、さらに両性界面活性剤、水分散性樹脂、及び水を含有する第2のインク組成物の組み合わせを含む、
インクセット。
2.さらに、1気圧下で沸点120℃以下の有機酸を含有する前処理液の組み合わせを含む1に記載のインクセット。
3.第2のインク組成物が、該水分散性樹脂を固形分で10.0~30.0質量%含有する1又は2に記載のインクセット。
4.該水分散性樹脂は、酸価15mgKOH/g以下のアクリル系樹脂及び/又はスチレン-アクリル系樹脂である1~3のいずれか1項に記載のインクセット。
5.両性界面活性剤がアルキルアミノ酢酸ベタイン及び/又はアルキルアミンオキシドである1~4のいずれか1項に記載のインクセット。
6.アルキルアミノ酢酸ベタインがラウリルジメチルアミノ酢酸である5に記載のインクセット。
7.アルキルアミンオキシドがラウリルジメチルアミンオキシドである5又は6に記載のインクセット。
8.インクジェット印刷用である1~7のいずれか1項に記載のインクセット。
9.捺染用である1~8のいずれか1項に記載のインクセット。
10.酸価が200mgKOH/g以上のアルカリ可溶性樹脂が、構成する単量の質量比で、スチレン/ラジカル重合性不飽和カルボン酸の炭素数が8以上のアルキルエステル/(メタ)アクリル酸=35~55/25~35/15~35のもの、又は(メタ)アクリル酸の炭素数が8未満のアルキルエステル/アクリル酸/メタクリル酸=50~70/13~25/15~25のものである1~9のいずれか1項に記載のインクセット。
このインクセットを以下に順に説明する。インク組成物は印刷用でも良く、捺染用であっても良い。本明細書において、インクジェット用インク組成物を場合により「インク組成物」というときがある。
<ガラス転移温度>
本発明における樹脂のガラス転移温度は、樹脂がアクリル系共重合体樹脂の場合、下記のWoodの式により求めた理論ガラス転移温度である。
Woodの式:1/Tg=W1/Tg1+W2/Tg2+W3/Tg3+・・・・・+Wx/Tgx
[式中、Tg1~Tgxは樹脂を構成する単量体1、2、3・・・xのそれぞれの単独重合体のガラス転移温度、W1~Wxは単量体1、2、3・・・xのそれぞれの重合分率、Tgは理論ガラス転移温度を表す。ただし、Woodの式におけるガラス転移温度は絶対温度である。]
本発明における樹脂の重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)法によって測定することができる。一例として、GPC装置としてWater2690(ウォーターズ社製)、カラムとしてPLgel、5μ、MIXED-D(Polymer Laboratories社製)を使用して、展開溶媒としてテトラヒドロフラン、カラム温度25℃、流速1ミリリットル/分、RI検出器、試料注入濃度10ミリグラム/ミリリットル、注入量100マイクロリットルの条件下、クロマトグラフィーを行ない、ポリスチレン換算の重量平均分子量として求める。
本発明中の前処理液は、1気圧下で沸点120℃以下の有機酸を含有し、さらに界面活性剤を含有する。
(1気圧下で沸点120℃以下の有機酸)
前処理液にて使用される1気圧下で沸点120℃以下の有機酸としては、ギ酸(1気圧下で沸点100.8℃)、及び/又は、酢酸(1気圧下で沸点118℃)を使用できる。
このような有機酸は前処理液中に5.0質量%以上含有することが好ましく、8.0質量%以上含有することがより好ましい。また30.0質量%以下含有することが好ましく、25.0質量%以下含有することがより好ましい。
有機酸の沸点及び含有量がこれらの範囲であると、この前処理液を被印刷基材表面に塗布しておくことにより、その上に形成する本発明の第1のインク組成物による印字部の塗膜厚さが、印刷における通常の範囲でれば、この第1のインク組成物層を通じて、上記有機酸が第1のインク組成物層表面に存在できる。そして、続いて印刷をした第2のインク組成物中の成分がその有機酸と反応する。なお、特にインクジェット印刷時、及びインクジェットによる捺染時には、この傾向が顕著である。
有機酸の含有量が少なすぎると、その上に印刷した各インク組成物層中の樹脂の定着に時間を要する可能性がある。また、過剰に含有させると、印刷後の印刷層中に多くの有機酸が残存するため、有機酸が蒸発して印字や画像中の遊離の酸が消滅するまでに時間を要する可能性がある。
前処理液に界面活性剤を含有しても良く、含有しなくても良い。含有できる界面活性剤としては、アニオン系界面活性剤及びノニオン系界面活性剤が好ましい。カチオン系界面活性剤や両性界面活性剤を含有させると、上記1気圧下で沸点120℃以下の有機酸と塩を構成する可能性がある。
界面活性剤の含有量は、例えば、前処理液全体に対して、0~1.0質量%、好ましくは0.01~1.0質量%、より好ましくは0.1~0.7質量%である。
リン酸塩系界面活性剤としては、リン酸エステル系界面活性剤が好ましく、プライサーフAL、プライサーフDB-01、プライサーフA219B、プライサーフA208B、プライサーフ212C(第一工業製薬社製)を使用することができる。リン酸塩系界面活性剤と共に、アルケニルコハク酸系界面活性剤及び/又はタウリン系界面活性剤等を併用できる。
アルケニルコハク酸系界面活性剤又はその塩としては、アルケニルコハク酸(星光PMC社製)、アルケニルコハク酸ジカリウム(花王社製)を使用できる。
アルキルベンゼンスルホン酸アルカリ金属塩類系界面活性剤としては、ドデシルベンゼンスルホン酸ナトリウムなどを使用できる。
タウリン系界面活性剤としては、N-アシルタウリン塩(日光ケミカルズ社製)、LMT(N-ラウロイルメチルタウリンNa)、MMT(N-ミリストイルメチルタウリンNa)、PMT(N-パルミトイルメチルタウリンNa)、SMT(N-ステアロイルメチルタウリンNa)を含有できる。
ポリオキシエチレンアルキルフェニル硫酸アルカリ金属塩系界面活性剤としては、ポリオキシエチレンノニルフェニル硫酸ナトリウム等を使用できる。
シリコーン系界面活性剤としては、BYK-347、BYK-377、BYK-3455(ビックケミー・ジャパン社)などが挙げられる。
本発明中の前処理液は溶媒として、水のみ、又は水と水溶性有機溶媒の混合溶媒を採用できる。
この水溶性有機溶媒としては、例えば、モノアルコール類、多価アルコール類、多価アルコールの低級アルキルエーテル類、ケトン類、エーテル類、エステル類、窒素含有化合物類等を挙げることができる。これらは単独で用いてもよく、2種以上を併用してもよい。
上記モノアルコール類としては、メタノール、エタノール、n-プロパノール、n-ブタノール、イソブタノール、n-ペンタノール、n-ヘキサノール、n-ヘプタノール、n-オクタノール、n-ノニルアルコール、n-デカノール、又はこれらの異性体、シクロペンタノール、シクロヘキサノール等が挙げられ、好ましくはアルキル基の炭素数が1~6のアルコールを使用できる。
上記多価アルコール類としては、エチレングリコール、プロピレングリコール、1,3-ブチレングリコール、1,4-ブチレングリコール、1,2-ペンタンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,2-ヘキサンジオール、1,6-ヘキサンジオール、1,2-シクロヘキサンジオール、ヘプタンジオール、1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、グリセリン、ペンタエリスリトール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、チオジグリコール等を使用できる。
上記多価アルコールの低級アルキルエーテル類としては、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ジメチルエーテル、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ジエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソブチルエーテル、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-n-プロピルエーテル、プロピレングリコールモノブチルエーテル、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-ブチルエーテル等を使用できる。
上記水溶性有機溶媒の含有量としては、極力少なくすることが好ましく、配合しないこともできる。
しかしながら配合する際の含有量は、前処理液中0~10.0質量%が好ましく、さらに好ましくは0~5.0質量%である。10.0質量%を超えるときには乾燥不良や耐ブロッキング性が低下する。
本発明中の前処理液には、その他の成分として水溶性多価金属塩を含有しても良く、含有しなくても良い。
水溶性多価金属塩としては20℃における水100mLに対する溶解度が1g/100mL以上、好ましくは2g/100mL以上、より好ましくは20g/100mL以上である、多価金属の有機酸又は無機酸の塩である。
水溶性多価金属塩は、多価金属を含む複塩であってもよく、水和物であってもよい。
多価金属としては、例えば、マグネシウム、カルシウム、ストロンチウム、亜鉛、銅、鉄、及びアルミニウムから選ばれる1種又は2種以上が挙げられる。
このような有機酸として、ギ酸、酢酸、プロピオン酸、オクチル酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、12-ヒドロキシステアリン酸、リシノール酸、オレイン酸、バクセン酸、リノール酸、リノレン酸、アラキジン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸、メリシン酸、乳酸、クエン酸、グルコン酸、リンゴ酸、酒石酸、コハク酸、マロン酸、グルタル酸、マレイン酸、フマル酸、グルタコン酸、安息香酸、アスコルビン酸等が挙げられる。
無機酸としては、例えば、硝酸、硫酸、塩化水素(塩酸)、臭化水素、ヨウ化水素、塩素酸、臭素酸、炭酸、リン酸から選ばれる1種又は2種以上が挙げられる。
水溶性多価金属塩の含有量の下限は、例えば、前処理液中に固形分換算で0.1質量%以上、好ましくは0.5質量%以上、より好ましくは1質量%以上である。また、水溶性多価金属塩の含有量の上限は、例えば、前処理液中に固形分換算で20質量%以下、好ましくは15質量%以下、より好ましくは10質量%以下である。
水溶性多価金属塩の含有量は、例えば、前処理液中に固形分換算で0.1~20質量%、好ましくは0.5~15質量%、より好ましくは1~10質量%である。
(顔料)
本発明中のインク組成物には、各色相の顔料を含有させて、第1及び第2のインク組成物として各色のインク組成物を得る。第1のインク組成物は白色顔料を含有した白色インク組成物であり、第2のインク組成物は白以外の着色顔料を含有した着色インク組成物である。
このような顔料としては、通常のインク組成物で従来から使用されている顔料を特に制限なく使用できる。
白インク組成物として使用するための白色顔料としては、例えば、酸化チタン、酸化アルミニウム等が挙げられ、好ましくは、アルミナ、シリカ等の種々の材料で表面処理された酸化チタンが挙げられる。
着色インク組成物を得るために使用する着色顔料は、以下の有機顔料及びブラック顔料から選ばれる1種以上である。
そして有機顔料としては、例えば、染料レーキ顔料、アゾ系、ベンズイミダゾロン系、フタロシアニン系、キナクリドン系、アントラキノン系、ジオキサジン系、インジゴ系、チオインジコ系、ペリレン系、ペリノン系、ジケトピロロピロール系、イソインドリノン系、ニトロ系、ニトロソ系、フラバンスロン系、キノフタロン系、ピランスロン系、インダンスロン系の顔料等が挙げられる。無機顔料としては、カーボンブラック、酸化チタン、ベンガラ、黒鉛、鉄黒、酸化クロムグリーン、水酸化アルミニウム等が挙げられる。
また、顔料の具体例としては以下のものが挙げられる。
イエロー顔料としては、例えば、C.I.PigmentYellow1、2、3、12、13、14、16、17、42、73、74、75、81、83、87、93、95、97、98、108、109、114、120、128、129、138、139、150、151、155、166、180、184、185、213等が挙げられ、好ましくは、C.I.PigmentYellow150、155、180、213等が挙げられる。
マゼンタ顔料としては、例えば、C.I.PigmentRed5 、7、12、22、38、48:1、48:2、48:4、49:1、53:1、57、57:1、63:1、101、102、112、122、123、144、146、149、168、177、178、179、180、184、185、190、202、209、224、242、254、255、270、C.I.PigmentViolet19等が挙げられ、好ましくは、C.I.PigmentRed122、202、C.I.PigmentViolet19等が挙げられる。
シアン顔料としては、例えば、C.I.PigmentBlue1、2、3、15、15:1、15:2、15:3、15:4、15:6、16、18、22、27、29、6等で、好ましくは、C.I.PigmentBlue15:4等が挙げられる。
ブラックインク組成物として使用するためのブラック顔料としては、例えば、カーボンブラック(C.I.Pigment Black7)等が挙げられる。
インク組成物における顔料の含有量は、インク組成物の総質量に対して1.0~20.0質量%であることが好ましい。顔料の含有量が1質量%未満では、得られる印刷物の画像品質が低下する傾向がある。一方、20.0質量%を超えると、インク組成物の粘度特性に悪影響を与える傾向がある。
本発明中の第1のインク組成物は、必要に応じて顔料分散剤を含有していてもよい。
顔料分散剤は、顔料の分散性、本発明のインク組成物の保存安定性を向上させるために使用するもので、従来から使用されているものを特に制限なく使用できるが、その中でも高分子分散剤を使用することが好ましい。このような顔料分散剤としては、カルボジイミド系分散剤、ポリエステルアミン系分散剤、脂肪酸アミン系分散剤、変性ポリアクリレート系分散剤、変性ポリウレタン系分散剤、多鎖型高分子非イオン系分散剤、高分子イオン活性剤等が挙げられる。これら顔料分散剤は単独で又は2種以上を混合して使用できる。
上記顔料分散剤を使用する際には、使用する全顔料の量を100質量部としたときに、1~200質量部含有することが好ましい。顔料分散剤の含有量が1質量部未満では、顔料分散性、及び本発明のインク組成物の貯蔵安定性が低下する場合がある。一方、200質量部を超えて含有させることもできるが効果に差がでない場合もある。顔料分散剤の含有量のより好ましい下限は5質量部、より好ましい上限は60質量部である。
酸価が200mgKOH/g以上のアルカリ可溶性樹脂又はその架橋物としては、例えば、アクリル系共重合樹脂、マレイン酸系共重合樹脂、縮重合反応によって得られるポリエステル樹脂、及びポリウレタン樹脂など又はその架橋物が挙げられる。
このアルカリ可溶性樹脂を合成するための材料については、例えば、特開2000-94825号公報に開示されており、該公報に記載されている材料を使用して得られるアクリル系共重合樹脂、マレイン酸系共重合樹脂、ポリエステル系樹脂、ポリウレタン系樹脂などが利用可能である。さらには、これら以外のその他の材料を用いて得られた樹脂も利用可能である。
前記アルカリ可溶性樹脂は単独で、又は2種以上を組み合わせて使用することができる。
また、本発明による効果を毀損しない範囲で、第1及び第2のインク組成物に、酸価が200mgKOH/g以下のアルカリ可溶性樹脂又はその架橋物を配合することもできる。
又は、第1のインク組成物において、前記酸価が200mgKOH/g以上のアルカリ可溶性樹脂の含有量は、前記顔料100質量部に対して、顔料の分散性を高める観点から、5.0質量部以上であることが好ましく、15.0質量部以上であることがより好ましい。前記アルカリ可溶性樹脂の含有量は、前記顔料100質量部に対して、インク組成物の粘度を低下させる観点から、100.0質量部以下であることが好ましく、80.0質量部以下であることがより好ましく、60.0質量部以下であることがさらに好ましい。
第2のインク組成物において、前記酸価が200mgKOH/g以上のアルカリ可溶性樹脂の含有量は、前記顔料100質量部に対して、顔料の分散性を高める観点から、50.0質量部以上であることが好ましく、100.0質量部以上であることがより好ましい。前記アルカリ可溶性樹脂の含有量は、前記顔料100質量部に対して、インク組成物の粘度を低下させる観点から、300.0質量部以下であることが好ましく、280.0質量部以下であることがより好ましく、250.0質量部以下であることがさらに好ましい。
前記疎水性基含有単量体としては、例えば、長鎖アルキル基を有する単量体として、(メタ)アクリル酸などのラジカル重合性不飽和カルボン酸の炭素数が8以上のアルキルエステル類(例えば、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、2-ヒドロキシステアリル(メタ)アクリレートなど)、炭素数が8以上のアルキルビニルエーテル類(例えば、ドデシルビニルエーテルなど)、炭素数が8以上の脂肪酸のビニルエステル類(例えば、ビニル2-エチルヘキサノエート、ビニルラウレート、ビニルステアレートなど);脂環族炭化水素基を有する単量体として、シクロヘキシル(メタ)アクリレートなど;芳香族炭化水素基を有する単量体として、ベンジル(メタ)アクリレート、スチレン、α-メチルスチレン、ビニルトルエンなどのスチレン系単量体などが挙げられる。前記疎水性基含有単量は単独で、又は2種以上を組み合わせて使用することができる。
また好ましくは(メタ)アクリル酸の炭素数が8未満のアルキルエステル/アクリル酸/メタクリル酸=50~70/13~25/15~25、より好ましくはアクリル酸シクロヘキシル/アクリル酸/メタクリル酸=50~70/13~25/15~25である。
前記アルカリ可溶性樹脂は、当該樹脂を適度に架橋して、顔料の凝集を抑制させる観点から、2官能以上の架橋剤を使用してもよく、架橋させなくてもよい。
第2のインク組成物に含有される両性界面活性剤として、公知のものを採用でき、中でもアルキルアミノ酢酸ベタイン及び/又はアルキルアミンオキシドが好ましい。
アルキルアミノ酢酸ベタインとしては、ラウリルジメチルアミノ酢酸(ラウリルジメチルアミノ酢酸ベタイン)が好ましい。
アルキルアミンオキシドとしては、ラウリルジメチルアミンオキシドが好ましい。
また、2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタインも採用できる。
本発明中のインク組成物中の両性界面活性剤の含有量は、インク組成物全量に対して0.1質量%以上が好ましく、0.3質量%以上がより好ましく、0.5質量%以上がさらに好ましい。また、インク組成物全量に対して10.0質量%以下が好ましく、5.0質量%以下がより好ましく、2.0質量%以下がさらに好ましく、1.0質量%以下が最も好ましい。
両性界面活性剤を含有しない場合には、印字部のドット拡張性を良好にすることが困難になる可能性があり、10.0質量%を超えても、それ以上の効果の向上を見込めない可能性がある。
なお第1のインク組成物も同様に両性界面活性剤を含有できる。
本発明中の第1及び第2のインク組成物は、本発明による効果を毀損しない範囲で、印刷や捺染工程を最適化させるために任意のその他の界面活性剤を含有できる。さらにインクジェット用インク組成物にする際には、使用するインクジェットヘッドに応じて、界面活性剤として従来からインク組成物に使用されているアセチレンジオール系界面活性剤やシリコーン系界面活性剤等の界面活性剤、アニオン系界面活性剤等を、吐出安定性を改良するために含有することができ、又は含有しなくても良い。
アセチレンジオール系界面活性剤の具体例としては、サーフィノール104E、サーフィノール104H、サーフィノール104A、サーフィノール104BC、サーフィノール104DPM、サーフィノール104PA、サーフィノール104PG-50、サーフィノール420、サーフィノール440等(EVONIK社製)、オルフィンE-1004、オルフィンE-1010、オルフィンE-1020、オルフィンPD-001、オルフィンPD-002W、オルフィンPD-004、オルフィンPD-005、オルフィンEXP.4001、オルフィンEXP.4200、オルフィンEXP.4123、オルフィンEXP.4300等(日信化学工業社製)が挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。
シリコーン系界面活性剤の具体例としては、ポリエーテル変性シリコーンオイル、ポリエステル変性ポリジメチルシロキサン、ポリエステル変性メチルアルキルポリシロキサン等が挙げられる。これらの例として、BYK-307、BYK-333、BYK-347、BYK-348、BYK-349、BYK-345、BYK-378、BYK-3455(ビックケミー社製)などが挙げられる。これらは単独又は2種以上を併用して用いることができる。
本発明中のインク組成物において、その他の界面活性剤を含有する際の含有量としては、好ましくは0.005~1.0質量%である。0.005質量%未満であると、本発明のインク組成物の表面張力が高くなり、インクジェットヘッドからの吐出安定性が低下する可能性がある。一方、1.0質量%を超えると、インク組成物中に泡が増加し吐出安定性が低下する可能性がある。
第2のインク組成物に含有される水分散性樹脂として、アクリル系樹脂エマルジョン、スチレンアクリル系樹脂エマルジョン、ポリウレタン系樹脂エマルジョン及びポリオレフィン系樹脂エマルジョンから選ばれた1種以上を採用できる。
また本発明中の第2のインク組成物中の樹脂と顔料の合計量に対する、水分散性樹脂の固形分の割合は、印刷画質及び耐擦過性を向上させる観点から、30.0質量%以上が好ましく、40.0質量%以上がより好ましく、50.0質量%以上がさらに好ましく、60.0質量%が最も好ましい。そして、印刷画質を向上させる観点から、93.0質量%以下が好ましく、90.0質量%以下がより好ましい。
また水分散性樹脂の酸価は、耐酸性を高める観点から、15mgKOH/g以下が好ましく、10mgKOH/g以下がより好ましく、5mgKOH/g以下がさらに好ましく、1mgKOH/g以下が最も好ましく、0mgKOH/gでもよい。なお、前記酸価は、アルカリ可溶性樹脂を合成するために用いる単量体の組成に基づいて、アルカリ可溶性樹脂1gを中和するのに理論上要する水酸化カリウムのmg数を算術的に求めた理論酸価である。
アクリル系樹脂エマルジョンは、下記の単量体から1種又は2種以上を混合した重合体である。
例えば、炭素数1~18のアルキル基を有するアルコールとの(メタ)アクリル酸エステル、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、メトキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート、アリル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート等を挙げることができる。なお、(メタ)アクリレートとは、アクリレートとメタクリレートの総称である。また、上記に加えて下記エチレン性不飽和単量体を併用しても良い。例えば、アクリロニトリル、酢酸ビニル、プロピオン酸ビニル、スチレン、アクリル酸、メタクリル酸、(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド等を挙げることができる。
この方法及び安定化剤についての詳しい情報は、“Emulsion Polymerization and Emulsion Polymer”(P.A.Lovell,M.S.El-Aasser,John Wiley & Sons Ltd.,England、1977年、引用することにより本明細書に包含する)に記載されている。
スチレンアクリル系樹脂エマルジョンの市販品としては、M6963(ジャパンコーティングレジン社製)J-450、J-734、J-7600、J-352、J-390、J-7100、J-741、J-74J、J-511、J-840、J-775、HRC-1645、HPD-71、PDX-6102B、JDX-5050(BASF社製)、UC-3900(東亜合成社製)などが挙げられる。
本発明中の第1及び第2のインク組成物には、必要に応じて種々の機能性を発現させるため、各種の添加剤を添加することができる。具体的には、表面調整剤、光安定化剤、表面処理剤、酸化防止剤、老化防止剤、架橋促進剤、重合禁止剤、可塑剤、防腐剤、pH調整剤、消泡剤、保湿剤等が挙げられる。また、ビヒクルとして機能するが硬化性ではない樹脂を配合しても良く、配合しなくても良い。また、溶媒を含有させても良いが、含有しなくても良い。
本発明中の第1及び第2のインク組成物には、アルカリ可溶性樹脂を溶解させる観点から、塩基性化合物を含有しても良い。前記塩基性化合物としては、例えば、水酸化ナトリウム、水酸化カリウムなどの無機塩基性化合物;アンモニア、メチルアミン、エチルアミン、モノエタノールアミン、N、N-ジメチルエタノールアミン、N、N-ジエチルエタノールアミン、N、N-ジブチルエタノールアミン、ジエタノールアミン、N-メチルジエタノールアミン、トリエタノールアミン、モルホリン、N-メチルモルホリン、N-エチルモルホリンなどの有機塩基性化合物などが挙げられる。前記塩基性化合物は単独で、又は2種以上を組み合わせて使用することができる。
本発明中の前処理液は、水に対して、有機酸及び必要に応じて界面活性剤等の所定量を任意の順で添加して調製できる。
本発明中の第1及び第2のインク組成物を調製(製造)する方法としては、特に限定されず、上記の成分を順番に、あるいは同時に添加して、混合すればよい。例えば、下記(1)や(2)の方法を採用できる。
(1)前記塩基性化合物の存在下にアルカリ可溶性樹脂を水に溶解した水性樹脂ワニス、顔料、必要に応じて顔料分散剤などを混合した後、各種分散機、例えばボールミル、アトライター、ロールミル、サンドミル、アジテーターミルなどを利用して顔料分散液(インクベース)を調製し、さらに残りの材料を添加して、インク組成物を調製する方法。
(2)上記の方法で顔料を分散した後、酸析法や、塩基性化合物の存在下にアニオン性基含有樹脂を溶解させた水性溶液に顔料を分散させた後、イオン交換手段を用いて前記水性溶液中の塩基性化合物を除去することにより、顔料表面にアニオン性基含有樹脂を析出させる方法などにより、顔料表面にアルカリ可溶性樹脂を析出させた樹脂被覆顔料を得、次いで得られた樹脂被覆顔料を塩基性化合物で中和し、各種分散機(高速撹拌装置など)を用いて水に再分散し、さらに残りの材料を添加して、インク組成物を調製する方法。
本発明中のインク組成物は、製造後の初期粘度が2.0~15.0mPa・s、好ましくは3.0~12.0mPa・sの範囲である。粘度は、例えば、E型粘度計(商品名「RE100L型粘度計」、東機産業社製)により測定できる。
本発明のインクセットによる印刷方法は、印刷用紙、樹脂フィルム等の被印刷基材表面に対して、前処理液を塗布する工程と、インク組成物により印刷を行う印刷工程の2つの工程からなる。
前処理液を塗布する工程はインクジェット印刷によっても良く、その他の周知の方法により行ってもよい。
この2つの工程に関して、インク組成物により印刷を行う工程は、塗布された前処理液が乾燥してないウエットオンウエットで行ってもよく、塗布された前処理液を乾燥させた後に行うドライオンウェットで行ってもよい。
前処理液1(酢酸20質量部、サーフィノール440(アセチレンジオール系界面活性剤、HLB8、EVONIK社製)を0.2質量部、及び精製水を撹拌混合し、100質量部としたもの)
前処理液2(前処理液1において酢酸を10質量部としたもの)
前処理液3(前処理液1において酢酸を乳酸(1気圧下で沸点が120℃を超える有機酸)に置換したもの)
JR-809(商品名「JR-809」、シリカとアルミナで処理された酸化チタン、平均粒子径0.23μm、DBP給油量24ml/100g、テイカ社製)
PF-690(商品名「PF-690」、シリカとアルミナと有機物で処理された酸化チタン、平均粒子径0.21μm、DBP給油量16ml/100g、石原産業社製)
HB890(商品名「ハイブラック890」、平均一次粒子径15nm、DBP給油量95ml/100g、pH8.0、オリオンエンジニアドカーボンズ社製)
PB15:3(ピグメントブルー15:3)
PR122(ピグメントレッド122)
PY14(ピグメントイエロー14)
アルカリ可溶性樹脂1(重量平均分子量15000、酸価235mgKOH/gの、アクリル酸シクロヘキシル/アクリル酸/メタクリル酸=65/16/19の共重合体)
アルカリ可溶性樹脂2(重量平均分子量9500、酸価235mgKOH/gの、アクリル酸シクロヘキシル/アクリル酸/メタクリル酸=65/16/19の共重合体)
アルカリ可溶性樹脂3(重量平均分子量15800、酸価144mgKOH/gの、スチレン/アクリル酸ラウリル/アクリル酸=51/30/19の共重合体共重合体)
アルカリ可溶性樹脂4(重量平均分子量30000、酸価220mgKOH/gの、スチレン/アクリル酸ラウリル/アクリル酸=40/30/30の共重合体)
アルカリ可溶性樹脂5(重量平均分子量32000、酸価188mgKOH/gの、スチレン/アクリル酸ラウリル/アクリル酸=45/30/25の共重合体)
アルカリ可溶性樹脂1を25質量部と、中和当量100%となる水酸化ナトリウムと、精製水を混合して100質量部とし、90℃で加熱撹拌して溶解させ、アルカリ可溶性樹脂ワニス1とした。
同様にして、アルカリ可溶性樹脂2~5それぞれを25質量部と、それぞれのアルカリ可溶性樹脂に対して中和当量が100%となる質量の水酸化ナトリウムと、精製水を混合して100質量部とし、90℃で加熱撹拌して溶解させ、それぞれアルカリ可溶性樹脂ワニス2~5とした。
表1の通りJR-809を50質量部、アルカリ可溶性樹脂ワニス2を40質量部、及び精製水10質量部を撹拌混合後、湿式サーキュレーションミルで練肉を行い、水性白色インクベース1を調製した。
同様にして、表1の通り各顔料、各アルカリ可溶性樹脂ワニス、及び精製水を撹拌混合後、湿式サーキュレーションミルで練肉を行い、水性各色インクベースを調製した。
M6963(商品名「M6963」、スチレン-アクリル系エマルジョン(固形分濃度45質量%)、酸価10mgKOH/g未満、ジャパンコーティングレジン社製)
R967(商品名「NeoRez R-967」、ポリエーテルポリウレタン系エマルジョン(固形分濃度40質量%)、酸価19mgKOH/g、DSM Coating Resins社製)
アンヒトール20N(固形分35%、花王社製、ラウリルジメチルアミンオキシド水溶液)
NIKKOL AM-301(固形分35%、日光ケミカルズ社製、ラウリルジメチルアミノ酢酸ベタイン水溶液)
<その他の界面活性剤>
E1010(商品名「オルフィンE-1010」、アセチレンジオール系界面活性剤、HLB13、日信化学工業社製)
<溶剤>
グリセリン
プロピレングリコール
表2に示す通り各成分を撹拌混合して、各実施例及び比較例のインク組成物を得た。「アルカリ可溶性樹脂ワニス2(後添)」は、一旦得たインク組成物にさらにアルカリ可溶性樹脂ワニス2を添加したものである。
表2の参考例は、前処理液1又は2で前処理し、次いで各色インクベース、顔料、及び溶媒等を含有し、さらに場合によりアルカリ可溶性樹脂ワニスを含有する各色インク組成物で印刷した例である。
また本発明における白色インク組成物は第1のインク組成物に対応し、その他の色のインク組成物は第2のインク組成物に対応する。実施例1~5においては、前処理液1で前処理した後、その上に表2には記載していないが、参考例1で使用した白色インク組成物を第1のインク組成物として印刷し、次いで各実施例に記載の各色のインク組成物を第2のインク組成物として印刷した。
比較例1~4においては、前処理液1又は3で前処理した後、その上に表2には記載していないが、参考例1で使用した白色インク組成物を第1のインク組成物として印刷し、次いで各比較例に記載の各色のインク組成物を第2のインク組成物として印刷した。
(画質)
綿100%の白色布帛に、参考例、実施例及び比較例の前処理液を、A4サイズあたり10g含浸させた後に加熱乾燥して印刷媒体を得た。加熱乾燥した後であっても前処理液に含有された酸が印刷媒体中に含有されていた。揮発性の有機酸が存在する雰囲気下では、一般にノズルから吐出されたインク組成物の飛翔軌道が乱れる傾向があるところ、そのような飛翔軌道が乱れないときには優れた画質を形成できる効果を発揮できる。
前記印刷媒体に対して、SPECTRA社製ヘッドを搭載した評価用プリンターと、参考例、実施例及び比較例のインク組成物を用いてベタ画像を印字し、続いてノズルチェック画像を印字し、印刷媒体を交換した。その後、画像の印字とノズルチェック画像の印字と印刷媒体の交換を19回繰り返した。
ノズルチェック画像の印字は、プリンター側で予め設定されたテスト用画像を、プリンター側による専用のプログラムにより印刷して得た印字である。
○:印刷媒体20枚以上の印刷媒体に印刷しても、ノズルチェック画像を印刷した際に全てのノズルから吐出が確認された
×:印刷開始後、印刷媒体20枚以内に、ノズルチェック画像を印刷した際に不吐出又は吐出曲がりの発生したノズルが確認された
JIS L0849乾燥条件に従ってII型試験機で試験(200gの荷重で100mmの長さを100回往復摩擦)を行い、変退色グレースケールを用いて評価した。
○:4-5級~5級
△:3-4級~4級
×:3級以下
綿100%の白色布帛に参考例、実施例及び比較例の前処理液を、A4サイズあたり10g含浸させた後に加熱乾燥して印刷媒体を得た。前記印刷媒体に対して、SPECTRA社製ヘッドを搭載した評価用プリンターと、参考例1の白インク組成物を第1のインク組成物として用いて白ベタ画像を印字した。この白ベタ画像の上に、吐出液量を20ピコリットルとした実施例1~5のインク組成物を用いてドットパターンを印字した。得られた画像のドット径を、顕微鏡を用いて測定した。このドット印刷部位のドット100個に対して、顕微鏡によりその直径を測定し、平均値を求めた。この値をドット径とした。
インク組成物が両性界面活性剤を含有しない参考例1~10によれば、画質及び塗膜耐性に優れた画像等を形成できるが、例えば参考例7~10の結果に代表されるように、ドット径が22μmと小さかった。
酸価が200mgKOH/g以上のアルカリ可溶性樹脂を含有させず、かつ両性界面活性剤を含有させなかった比較例1によれば、画質及び塗膜耐性共に良好ではない結果になった。
前処理液中に1気圧下で沸点が120℃を超える有機酸を使用し、インク組成物に両性界面活性剤を含有させなかった比較例2によっても、画質及び塗膜耐性共に良好ではない結果になった。
黒色インク組成物は酸価が200mgKOH/g以上のアルカリ可溶性樹脂を含有するものの、両性界面活性剤を含有しない比較例3によれば、特に画質が良好ではなくドット径が26μmと小さかった。また黒色インク組成物が酸価が200mgKOH/g以上のアルカリ可溶性樹脂を少量のみ含有し、両性界面活性剤を含有しない比較例4によれば画質が良好ではなかった。
Claims (10)
- 白色顔料、酸価が200mgKOH/g以上のアルカリ可溶性樹脂又はその架橋物をインク組成物中1.0質量%以上含有し、さらに水を含有する第1のインク組成物と、
この第1のインク組成物による印刷層上にさらに印刷するための、着色顔料、酸価が200mgKOH/g以上のアルカリ可溶性樹脂又はその架橋物をインク組成物中1.0質量%以上含有し、さらに両性界面活性剤、水分散性樹脂、及び水を含有する第2のインク組成物の組み合わせを含む、
インクセット。 - さらに、1気圧下で沸点120℃以下の有機酸を含有する前処理液の組み合わせを含む請求項1に記載のインクセット。
- 第2のインク組成物が、該水分散性樹脂を固形分で10.0~30.0質量%含有する請求項1又は2に記載のインクセット。
- 該水分散性樹脂は、酸価15mgKOH/g以下のアクリル系樹脂及び/又はスチレン-アクリル系樹脂である請求項1~3のいずれか1項に記載のインクセット。
- 両性界面活性剤がアルキルアミノ酢酸ベタイン及び/又はアルキルアミンオキシドである請求項1~4のいずれか1項に記載のインクセット。
- アルキルアミノ酢酸ベタインがラウリルジメチルアミノ酢酸である請求項5に記載のインクセット。
- アルキルアミンオキシドがラウリルジメチルアミンオキシドである請求項5又は6に記載のインクセット。
- インクジェット印刷用である請求項1~7のいずれか1項に記載のインクセット。
- 捺染用である請求項1~8のいずれか1項に記載のインクセット。
- 酸価が200mgKOH/g以上のアルカリ可溶性樹脂が、構成する単量の質量比で、スチレン/ラジカル重合性不飽和カルボン酸の炭素数が8以上のアルキルエステル/(メタ)アクリル酸=35~55/25~35/15~35のもの、又は(メタ)アクリル酸の炭素数が8未満のアルキルエステル/アクリル酸/メタクリル酸=50~70/13~25/15~25のものである請求項1~9のいずれか1項に記載のインクセット。
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