WO2022211030A1 - 非水性インク組成物、インクセット、それを用いた記録方法、記録物の製造方法、記録物、及びインクジェット記録装置 - Google Patents
非水性インク組成物、インクセット、それを用いた記録方法、記録物の製造方法、記録物、及びインクジェット記録装置 Download PDFInfo
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XFTIKWYXFSNCQF-UHFFFAOYSA-N N,N-dipropylformamide Chemical compound CCCN(C=O)CCC XFTIKWYXFSNCQF-UHFFFAOYSA-N 0.000 description 1
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- PNXNSVYZNGNYIN-UHFFFAOYSA-N acetic acid;butanoic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O.CCCC(O)=O PNXNSVYZNGNYIN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- FYTRVXSHONWYNE-UHFFFAOYSA-N delta-octanolide Chemical compound CCCC1CCCC(=O)O1 FYTRVXSHONWYNE-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- TUEYHEWXYWCDHA-UHFFFAOYSA-N ethyl 5-methylthiadiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=NSC=1C TUEYHEWXYWCDHA-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- IFYYFLINQYPWGJ-VIFPVBQESA-N gamma-Decalactone Natural products CCCCCC[C@H]1CCC(=O)O1 IFYYFLINQYPWGJ-VIFPVBQESA-N 0.000 description 1
- OALYTRUKMRCXNH-QMMMGPOBSA-N gamma-Nonalactone Natural products CCCCC[C@H]1CCC(=O)O1 OALYTRUKMRCXNH-QMMMGPOBSA-N 0.000 description 1
- PHXATPHONSXBIL-JTQLQIEISA-N gamma-Undecalactone Natural products CCCCCCC[C@H]1CCC(=O)O1 PHXATPHONSXBIL-JTQLQIEISA-N 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- IPBFYZQJXZJBFQ-UHFFFAOYSA-N gamma-octalactone Chemical compound CCCCC1CCC(=O)O1 IPBFYZQJXZJBFQ-UHFFFAOYSA-N 0.000 description 1
- 229940020436 gamma-undecalactone Drugs 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XTIGOJREHGWIKM-UHFFFAOYSA-N n,n-dibutyl-3-methoxypropanamide Chemical compound CCCCN(CCCC)C(=O)CCOC XTIGOJREHGWIKM-UHFFFAOYSA-N 0.000 description 1
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- ARCMPHHHUFVAOI-UHFFFAOYSA-N n,n-dipropylpropanamide Chemical compound CCCN(CCC)C(=O)CC ARCMPHHHUFVAOI-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004804 winding Methods 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
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- 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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- 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
- C09D11/02—Printing inks
- C09D11/14—Printing inks based on carbohydrates
-
- 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
Definitions
- the present invention relates to a non-aqueous ink composition, an ink set, a recording method using the same, a method for producing a recorded matter, a recorded matter, and an inkjet recording apparatus.
- an aqueous ink composition in which a coloring material is dissolved or dispersed in water or a mixture of water and an organic solvent, or a non-aqueous ink composition in which a coloring material is dissolved or dispersed in an organic solvent that does not contain water. is widely used.
- Patent Document 1 describes an aqueous pigment containing a perinone-based pigment and an azo compound as pigments, and an aqueous ink composition for inkjet recording using the same.
- Patent Document 1 describes that the non-aqueous ink composition contains a perinone-based pigment and an azo compound, thereby having good storage stability.
- Patent Document 2 discloses a non-aqueous ink composition containing a pigment containing a diketopyrrolopyrrole pigment as a pigment, an organic solvent, and an inorganic metal, wherein the non-aqueous ink composition contains a predetermined amount of a metal element. disclosed. According to Patent Document 1, it is described that this non-aqueous ink composition has excellent chroma in the obtained recorded matter and has excellent storage stability.
- Patent Document 3 discloses an ink composition for inkjet recording containing a copper complex dye (copper phthalocyanine), wherein the concentration of free copper ions in the ink composition is 10 ppm or less.
- a copper complex dye copper phthalocyanine
- JP 2012-172070 A JP 2017-132891 A JP-A-2000-355665
- ink compositions containing perinone-based pigments are particularly suitable for producing recorded matter for outdoor use.
- the ink composition when the ink composition is ejected through an inkjet head during ejection by the inkjet method, clogging may occur in the nozzles of the inkjet head due to solid components such as resins contained in the non-aqueous ink composition.
- the inkjet recording apparatus is equipped with a cleaning recovery function that eliminates nozzle clogging in such inkjet heads.
- cleaning recoverability the ability to eliminate nozzle clogging in an inkjet head by the cleaning recovery function is referred to as cleaning recoverability.
- halogenated phthalocyanine pigments in which some of the hydrogen atoms in a pigment having a phthalocyanine structure are substituted with halogens. Halogenation of the phthalocyanine pigment results in a green pigment.
- a green ink that contains a green pigment in addition to the usual four color inks, the saturation is improved compared to the case of reproducing green with two colors of yellow ink and cyan ink. Reproducibility can be improved.
- phthalocyanine-based pigments have higher weather resistance than yellow-based pigments generally used in yellow inks. Therefore, by using a green ink containing a halogenated phthalocyanine pigment, it is possible to improve the weather resistance of a printed matter as compared with the case where two colors of yellow ink and cyan ink are used.
- non-aqueous ink compositions containing halogenated phthalocyanine pigments tend to precipitate in the non-aqueous ink composition, resulting in poor storage stability.
- a non-aqueous ink composition having poor storage stability even if an attempt is made to eliminate clogging of the nozzles in the inkjet head by the cleaning recovery function of the inkjet recording apparatus, it may not be possible to sufficiently eliminate the clogging of the nozzles. be.
- An object of the present invention is to provide a non-aqueous ink composition containing a perinone pigment that can be suitably used as a non-aqueous ink composition ejected by an inkjet method. .
- Another object of the present invention is to provide a non-aqueous ink composition that has high storage stability and high cleaning recovery even if it contains a diketopyrrolopyrrole pigment.
- Another object of the present invention is to provide a non-aqueous ink composition containing a halogenated phthalocyanine pigment that exhibits high storage stability, color tone stability, and cleaning recovery.
- the inventors of the present invention conducted intensive studies to solve the above problems, and found that the above problems can be solved by a non-aqueous ink composition containing a diketopyrrolopyrrole pigment within a predetermined pH range. The discovery led to the completion of the present invention.
- the inventors of the present invention conducted intensive studies to solve the above problems, and found that the above problems can be solved by a non-aqueous ink composition containing a halogenated phthalocyanine pigment and a predetermined organic solvent.
- the discovery led to the completion of the present invention.
- the present invention provides the following.
- the pigment contains at least one of a pigment A1 represented by the following formula (1-1) or a pigment A2 represented by the following formula (1-2),
- the pH of the pigments A1 and A2 is in the range of 3 or more and 9 or less.
- each of X1 to X12 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , phthalimido group in which hydrogen atom may be substituted, phthalimidomethyl group, or a heterocyclic compound, and M + indicates a cation.
- each of X1 to X10 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3
- Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
- Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
- the pigment A3 according to any one of (5) to (8), wherein the pigment A3 is at least one selected from the group consisting of chlorinated phthalocyanine pigments, brominated phthalocyanine pigments, and chlorine brominated phthalocyanine pigments.
- Non-aqueous ink composition Non-aqueous ink composition.
- the alkylamide solvent (b1) contains at least one selected from the group consisting of N,N-diethylformamide, N,N-diethylpropanamide, and N,N-diethylacetamide (14 ).
- the non-aqueous ink composition according to any one of (1) to (28), which is used in an inkjet recording apparatus provided with a valve mechanism for adjusting a flow path of the non-aqueous ink composition.
- a recording method comprising ejecting the non-aqueous ink composition according to any one of (1) to (29) onto the surface of a substrate by an inkjet method.
- (31) A method for producing a recorded matter, wherein the non-aqueous ink composition according to any one of (1) to (29) is ejected onto the surface of a substrate by an inkjet method.
- An ink set comprising at least the non-aqueous ink composition according to any one of (1) to (29).
- An inkjet recording apparatus for ejecting the non-aqueous ink composition according to any one of (1) to (29) by an inkjet method, comprising a storage mechanism for storing the non-aqueous ink composition, and an inkjet ejection port. and a tube through which the non-aqueous ink composition flows, wherein the tube is connected to the storage mechanism and the inkjet ejection port, and includes a valve mechanism that adjusts the flow path of the non-aqueous ink composition.
- An inkjet recording device for ejecting the non-aqueous ink composition according to any one of (1) to (29) by an inkjet method, comprising a storage mechanism for storing the non-aqueous ink composition, and an inkjet ejection port. and a tube through which the non-aqueous ink composition flows, wherein the tube is connected to the storage mechanism and the inkjet ejection port, and includes a valve mechanism that adjusts the flow path of the non-aqueous ink composition.
- the non-aqueous ink composition of the present invention can be suitably used as a non-aqueous ink composition ejected by an inkjet method even when a pigment containing a perinone pigment is used.
- non-aqueous ink composition of the present invention has high storage stability and high cleaning recovery even when a pigment containing a diketopyrrolopyrrole pigment is used.
- non-aqueous ink composition of the present invention has high storage stability, color tone stability, and recovery from cleaning even if it contains a halogenated phthalocyanine pigment.
- a non-aqueous ink composition of one embodiment of the present invention contains a pigment, a pigment dispersant, and an organic solvent. It is a non-aqueous ink composition ejected by an inkjet method.
- non-aqueous ink composition refers to an ink composition containing an organic solvent produced without intentionally containing water, unlike an aqueous ink composition containing water as a main component. means to be a thing.
- the ink composition according to the present embodiment produces a printed matter by drying (volatilizing) the organic solvent. It is preferably an ink composition that can be obtained. Specifically, in such an ink composition, a volatile component such as an organic solvent contained in the ink composition dries (volatilizes), and the residue deposits on the surface of the substrate to form a recorded matter. do.
- This ink composition is different from an active energy ray-curable ink composition that polymerizes and cures on a substrate upon irradiation with an active energy ray such as ultraviolet rays.
- An active energy ray-curable ink composition contains a polymerizable compound as an essential component, but an ink composition capable of obtaining a recorded matter by drying (volatilizing) an organic solvent contains an organic solvent. It is not necessary to contain a polymerizable compound as an essential component, and it may contain a polymerizable compound or may not contain a polymerizable compound.
- the pigment contained in the non-aqueous ink composition contains at least one of pigment A1 represented by formula (1-1) below or pigment A2 represented by formula (1-2) below, and pigment A1 and
- the pH of A2 is characterized by being in the range of 3 or more and 9 or less.
- X1 to X12 are substituents containing hydrogen.
- X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, Aromatic hydrocarbon groups optionally substituted with hydrogen atoms, cyano groups, nitro groups, amino groups, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , hydrogen atoms represents an optionally substituted phthalimido group, phthalimidomethyl group, or heterocyclic compound, and M + represents a cation.
- each of X1 to X10 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M +
- the non-aqueous ink composition of one embodiment of the present invention is a non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, and an organic solvent.
- the pigment contained in this non-aqueous ink composition contains a halogenated phthalocyanine pigment A3, and the organic solvent contains an organic solvent B described below.
- Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
- a non-aqueous ink composition of a first embodiment according to the present embodiment is a non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, and an organic solvent.
- the “non-aqueous ink composition” means an ink composition containing an organic solvent produced without intentionally containing water, unlike an aqueous ink composition containing water as a main component. means.
- the pigment contained in this non-aqueous ink composition is characterized in that it contains a pigment A1 represented by the following formula (1-1), and the pH of the pigment A1 is within the range of 3 or more and 9 or less.
- X1 to X12 are substituents containing hydrogen.
- X1 to X12 are each independently hydrogen, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, Aromatic hydrocarbon groups optionally substituted with hydrogen atoms, cyano groups, nitro groups, amino groups, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , hydrogen atoms represents an optionally substituted phthalimido group, phthalimidomethyl group, or heterocyclic compound, and M + represents a cation.
- the pigment A1 whose pH is controlled within the range of 3 or more and 9 or less, it is possible to suppress the aggregation of the pigments in the non-aqueous ink composition. This satisfies various properties required in a non-aqueous ink composition ejected by an inkjet method.
- Pigment A1 having a pH of 3 or more and 9 or less is treated, for example, by washing the pigment A1 with a solution (acid solution, alkaline solution, or neutral solution), or by treating the surface of the pigment with formula (1-1) It can be obtained by changing the type of substituents (X1 to X12) in the benzene ring in the structure of or by treating both.
- a method of changing the type of substituents (X1 to X12) in the benzene ring includes a method of dispersing the pigment in an organic solvent and introducing a desired substituent with an additive capable of introducing a specific substituent.
- the pH of the pigment can be adjusted by the method described in Japanese Patent No. 2993392.
- the positions at which the substituents X1 to X12 are substituted are within the range of pH 3 or more and 9 or less of the benzene ring. Any one of the 12 substitution positions is not particularly limited, and the number of substituents is also not particularly limited.
- the pH of Pigment A1 is the pH measured by the test method of JIS K5101-17-1:2004. The same applies to the method for measuring the pH of Pigment A2, which will be described later.
- the upper limit of the pH of Pigment A1 is preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less.
- the lower limit of the pH of Pigment A1 is preferably 3 or higher, more preferably 5 or higher.
- the pH of the pigment A1 is 9 or less, the pigment dispersant is more likely to adhere, so aggregation of the pigment A1 in the non-aqueous ink composition can be more effectively suppressed. This can improve the ejection stability and color tone stability of the non-aqueous ink composition.
- the water content in the non-aqueous ink composition according to the present embodiment is preferably 5.0% by mass or less, preferably 1.0% by mass or less, and 0% by mass of the total amount of the non-aqueous ink composition. 0.5 mass or less is more preferable.
- Pigment A1 is highly hydrophobic, a non-aqueous inkjet composition containing this pigment tends to deteriorate dispersibility of the pigment and storage stability relatively easily due to contact with water. By reducing the water content in the non-aqueous ink composition so that it contains as little water as possible (intentionally avoiding water), storage stability, recovery from cleaning, etc. are improved. becomes possible. The same applies to non-aqueous ink compositions of second and third embodiments described later.
- the average particle size of the pigment A1 is not particularly limited, but the upper limit of the volume-based cumulative 90% particle size (D90) is preferably 500 nm or less, preferably 450 nm or less, and more preferably 400 nm. . As a result, aggregation of the pigment A1 in the non-aqueous ink composition can be more effectively suppressed, and the non-aqueous ink composition can be more preferably used as a non-aqueous ink composition ejected by an inkjet method.
- the lower limit of the volume-based cumulative 90% particle diameter (D90) is preferably 50 nm or more, more preferably 100 nm or more.
- volume-based cumulative 50% particle diameter (D50) means a particle diameter at which the cumulative volume calculated from the small diameter side is 50%.
- volume-based cumulative 50% particle size (D50) may also be referred to as “volume average particle size D50” or “median (median) size”.
- Volume-based cumulative 90% particle diameter (D90) means a particle diameter at which the cumulative volume calculated from the small diameter side is 90%.
- Volume-based cumulative 50% particle size (D50)” and “Volume-based cumulative 90% particle size (D90)” are measured using a particle size distribution measuring device (Microtrack Bell Co., Ltd. particle size analyzer NANOTRACWAVE). can be done. The same applies to non-aqueous ink compositions of second and third embodiments described later.
- the content of the pigment A1 is not particularly limited, but the lower limit of the content of the pigment A1 is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total amount of the non-aqueous ink composition. More preferably, it is 0.5% by mass or more.
- the upper limit of the content of Pigment A1 is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and even more preferably 5.0% by mass or less.
- the content of pigment A1 is 8.0% by mass or less in the total amount of the non-aqueous ink composition, it is possible to relatively increase the content of other additives, and further increase the content of pigment A1. Since it is possible to suppress an increase in viscosity due to this, it is possible to suppress clogging of the nozzles of the inkjet head.
- Pigment A1 represented by formula (1-1) may be mentioned.
- Pigment A1 represented by formula (1-1) may be synthesized, for example, commercially available C.I. I. Pigment Orange 43 is washed with a solution (acid solution, alkaline solution, or neutral solution) to treat the surface of the pigment or remove the substituent ( It may be obtained by changing the type of X1 to X12) or by performing both treatments.
- a solution as the type of X1 to X12
- Commercially available products include A-76 manufactured by Arimoto Chemical Co., Ltd., Hostaperm Orange GR and PV Gast Orange GRL manufactured by Clariant, Fasogen Super Orange 6200 manufactured by DIC, and Lionogen Orange GR-F manufactured by Toyo Ink. be done.
- non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the pigment A1 described above.
- coloring materials include pigments and dyes of hues similar to pigment A1 (eg, orange, magenta, yellow, red).
- organic pigments other than the above-mentioned pigment A1 are exemplified by the color index (C.I.) number, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, C.I. I.
- a dispersing aid (pigment derivative), which will be described later, may be used together with the pigment dispersant. Thereby, the dispersion stability of the pigment can be improved.
- Organic solvent is capable of dispersing or dissolving each component contained in the non-aqueous ink composition according to this embodiment.
- the organic solvent is not particularly limited, but organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( b2) and at least one selected from the group consisting of a lactone solvent (b3)).
- alkylamide-based solvent (b1) the cyclic amide-based solvent (b2), and the lactone-based solvent (b3) contained in the organic solvent B are described below.
- alkylamide-based solvent those having, for example, the following structures can be preferably used.
- R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms
- R 2 and R 3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R 2 and R 3 in formula (2) are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 2 to 4 carbon atoms.
- alkylamide solvents include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-diethylpropanamide, N , N-dipropylpropanamide, N-ethylformamide, N-ethylacetamide and the like.
- the content of the alkylamide solvent (b1) is not particularly limited, but the lower limit of the content of the alkylamide solvent (b1) is preferably in the range of 1% by mass or more based on the total amount of the non-aqueous ink composition.
- the range of 5% by mass or more is more preferable, and the range of 8% by mass or more is even more preferable.
- the upper limit of the content of the alkylamide solvent (b1) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous ink composition. More preferred.
- Cyclic amide solvent (b2) is a solvent having a cyclic structure and a —C( ⁇ O)—N— group in the cyclic structure.
- a cyclic amide solvent having, for example, the following structure can be preferably used.
- R 4 is an alkylene group having 3 to 5 carbon atoms
- R 5 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.
- cyclic amide solvent (b2) examples include N-methylcaprolactam, N-acetylcaprolactam, ⁇ -caprolactam, N-vinylcaprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl- 2-pyrrolidone, N-propyl-2-pyrrolidone, N-ethyl- ⁇ -caprolactam, N-propyl- ⁇ -caprolactam, N-methyl- ⁇ -caprolactam and the like.
- the content of the cyclic amide-based solvent (b2) is not particularly limited, but the lower limit of the content of the cyclic amide-based solvent (b2) is preferably in the range of 1% by mass or more based on the total amount of the non-aqueous ink composition.
- the range of 5% by mass or more is more preferable, and the range of 8% by mass or more is even more preferable.
- the upper limit of the content of the cyclic amide solvent (b2) is preferably 90% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the non-aqueous ink composition. More preferred.
- Lactone Solvent is a solvent having a cyclic ester structure.
- a lactone-based solvent having, for example, the following structure can be preferably used.
- R 6 is an alkylene group having 3 to 5 carbon atoms
- R 7 represents hydrogen or an alkyl group having 1 to 2 carbon atoms.
- R 6 has 4 carbon atoms.
- An alkylene group having 5 or less is more preferable, and an alkylene group having 5 carbon atoms is more preferable.
- Lactone-based solvents (b3) include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ - nonalactone, ⁇ -decalactone, ⁇ -undecalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, ⁇ -undecalactone and the like.
- ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -caprolactone and ⁇ -valerolactone are more preferable, and ⁇ -caprolactone is more preferable.
- the content of the lactone-based solvent (b3) is not particularly limited, but the lower limit of the content of the lactone-based solvent (b3) is preferably in the range of 1% by mass or more in the total amount of the non-aqueous ink composition, and 5% by mass. % or more, more preferably 8 mass % or more.
- the upper limit of the content of the lactone-based solvent (b3) is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less in the total amount of the non-aqueous ink composition. .
- the organic solvents B "containing an alkylamide solvent (b1)” or “containing a cyclic amide solvent (b2)” is preferable, and among them, "containing an alkylamide solvent (b1) ' is more preferred.
- the pigment containing the pigment A1 can be dispersed more effectively, and the storage stability and cleaning recovery of the non-aqueous ink composition can be improved.
- the non-aqueous ink composition has a high surface drying property on the base material, resulting in less blurring of the print and clearer print.
- the organic solvent B contains at least one of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the effect is sufficiently exhibited.
- the lower limit of the total content of the organic solvent B is preferably in the range of 1% by mass or more, more preferably 5% by mass or more in the total amount of the non-aqueous ink composition. Preferably, it is more preferably in the range of 10% by mass or more.
- the upper limit of the total content of the organic solvent B is preferably 90% by mass or less in the total amount of the non-aqueous ink composition.
- the non-aqueous ink composition according to this embodiment may contain an organic solvent other than the organic solvent B described above.
- organic solvents include glycol ether dialkyl in which OH groups at both ends of glycol are alkyl-substituted, glycol ether monoalkyl in which OH groups on one side of glycol are alkyl-substituted, and ester carbonates.
- Glycol ether-based solvents include glycol ether dialkyl in which OH groups at both ends of glycol are alkyl-substituted, and glycol ether monoalkyl in which one OH group of glycol is alkyl-substituted.
- Glycol ether solvents include, for example, those containing at least one of glycol ether dialkyl and glycol ether monoalkyl represented by the following formula (5).
- R 8 (—OR 9 ) n —OR 10 (5)
- R 8 and R 10 are each independently hydrogen or an optionally branched alkyl group having 1 to 8 carbon atoms, and R 9 is a branched group having 1 to 4 carbon atoms. (n represents an integer of 1 or more and 6 or less).
- glycol ether solvents examples include ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, Propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol Monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhexyl
- diethylene glycol dimethyl ether diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether.
- triethylene glycol dimethyl ether triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl- 2-ethylhexyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol dipropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol ethyl methyl ether, etc. , are preferred.
- glycol ether solvents having different flash points it is preferable to combine two or more types of glycol ether solvents having different flash points among these glycol ether solvents.
- a glycol ether solvent with a high flash point for example, a flash point of 70° C. or higher
- a non-aqueous ink composition having high recovery from cleaning can be obtained.
- a glycol ether solvent with a low flash point for example, a flash point of less than 70° C.
- a non-aqueous ink composition with high surface drying property on a substrate can be obtained.
- glycol ether solvent may contain other solvents than the glycol ether solvent.
- carbonic acid esters such as propylene carbonate and ethylene carbonate
- oxazolidinone solvents such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, and N-vinylmethyloxazolidinone
- triethylene glycol butyl ether acetate and ethylene Acetate solvents such as glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propyl acetate, and 3-methoxy Propanamide, 3-butoxypropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide, N,
- the content of the other organic solvent is not particularly limited, but the lower limit of the content of the other organic solvent is preferably in the range of 10% by mass or more, and more preferably in the range of 20% by mass or more. , 30% by mass or more.
- the upper limit of the content of other organic solvents is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.
- a dispersant may be used as necessary in the non-aqueous ink composition according to the present embodiment. Any dispersant used in non-aqueous ink compositions can be used as the dispersant.
- a polymer dispersant is preferably used as the dispersant. Such a dispersant has a main chain of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain. is.
- polyacrylic dispersants for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131 , 9132, 9133, 9151 (manufactured by Vic Chemie), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), TREPLUS D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are used.
- Polycaprolactone-based dispersants include, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemicals Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J10 TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) and the like are used.
- the non-aqueous ink composition according to the present embodiment containing the pigment A1 having a pH of 3 or more and 9 or less it is preferable to use a pigment dispersant having a basic group among the above. Since the pH of Pigment A1 is within the range of 3 or more and 9 or less, aggregation of Pigment A1 in the non-aqueous ink composition can be more effectively suppressed by using a pigment dispersant having a basic group. can. The same applies to the later-described non-aqueous ink composition containing the pigment A2 having a pH of 3 or more and 9 or less.
- the pigment dispersant having a basic group is more likely to adhere to the surface of the pigment A1, so the aggregation of the pigment A1 in the non-aqueous ink composition is more effective. can be suppressed to
- a pigment dispersant having an amine value in the range of 20 mgKOH/g to 100 mgKOH/g and 20 mgKOH/g to 100 mgKOH/g. Aggregation of Pigment A1 in the non-aqueous ink composition can be more effectively suppressed.
- the pH of the pigment A1 is 8 or less
- the pigment dispersant having an amine value within a predetermined range is more likely to adhere to the surface of the pigment A1, so the aggregation of the pigment A1 in the non-aqueous ink composition is further effective. can be effectively suppressed.
- the content of the pigment dispersant is not particularly limited. It is more preferably 20 parts by mass or more, more preferably 20 parts by mass or more.
- the upper limit of the content of the pigment dispersant is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the pigment in the non-aqueous ink composition. It is even more preferable to have
- a dispersing aid may be used as necessary in the non-aqueous ink composition according to the present embodiment.
- the dispersing aid is adsorbed on the surface of the coloring material (pigment), and the functional group increases the affinity with the organic solvent and dispersant in the non-aqueous ink composition, thereby improving the dispersion stability.
- the pigment derivatives described above are preferable, and known pigment derivatives having functional groups such as acidic groups, basic groups, and neutral groups in the organic pigment residue can be used. The same applies to non-aqueous ink compositions of second and third embodiments described later.
- the non-aqueous ink composition according to the present embodiment may contain no resin, but may contain a resin.
- the fixability, water resistance and stretchability of the recording layer formed from the non-aqueous ink composition can be improved. Furthermore, the glossiness of the obtained recorded matter can be improved. The same applies to non-aqueous ink compositions of second and third embodiments described later.
- resins include, but are not limited to, acrylic resins, polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, polyurethane resins, and rosin-modified resins.
- Resins, acrylamide-based resins, epoxy-based resins, or copolymer resins or mixtures thereof can be used.
- those containing acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins are preferable.
- the acrylic resin is not particularly limited as long as it is contained as a main component of the monomers that make up the (meth)acrylic acid ester monomer.
- the acrylic resin may be a homopolymer of one kind of radically polymerizable monomer, or may be a copolymer of two or more kinds of selected radically polymerizable monomers.
- a preferred acrylic resin for the non-aqueous ink composition according to the embodiment is a polymer of methyl methacrylate, or selected from the group consisting of methyl methacrylate, butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate.
- the vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer using two or more selected polymerizable monomers.
- copolymers of vinyl chloride resins include vinyl chloride-vinyl acetate copolymer resins.
- a vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer.
- Vinyl chloride-vinyl acetate copolymer resins include, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, vinyl chloride/vinyl acetate / hydroxyalkyl acrylate copolymers, etc., and mixtures thereof.
- the vinyl chloride-vinyl acetate copolymer resins include "SOLBIN C", “SOLBIN CL”, “SOLBIN CNL”, “SOLBIN CLL”, “SOLBIN CLL2", and "SOLBIN C5R" from Nissin Chemical Industry Co., Ltd. ”, “SOLBIN TA2”, “SOLBIN TA3”, “SOLBIN A”, “SOLBIN AL”, “SOLBIN TA5R”, “SOLBIN M5” and the like.
- a vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing a vinyl chloride monomer and a vinyl acetate monomer.
- a conventionally known polymerization method may be used as the polymerization method.
- the polymerization method is preferably emulsion polymerization or suspension polymerization, more preferably suspension polymerization.
- a cellulose-based resin is a resin with a cellulose skeleton that is obtained by biologically or chemically introducing functional groups using cellulose as a raw material.
- cellulose-based resins include cellulose acetate butyrate resins, cellulose acetate propionate resins, cellulose acetate alkylate resins such as cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. mentioned.
- the cellulose resins include "CAB551-0.01”, “CAB551-0.2", “CAB553-0.4", "CAB531-1", “CAB381-0.1” and “CAB381-0.1” available from EASTMAN. 5”, “CAB381-2”, “CAB381-20”, “CAP504”, “CAP482-0.5” and the like.
- a polyester resin contains at least a structural unit obtained by polycondensation of an alcohol component and a carboxylic acid component.
- the polyester-based resin may include a modified polyester-based resin.
- As the polyester resin Toyobo's "VYLON226", “VYLON270", “VYLON560”, “VYLON600”, “VYLON630”, “VYLON660”, “VYLON885", “VYLONGK250”, “VYLONGK810”, “VYLONGK890”, etc. It can be obtained and used under trade names such as “elitleUE-3200”, “elitleUE-3285", “elitleUE-3320”, “elitleUE-9800” and “elitleUE-9885” manufactured by Unitika.
- a polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component.
- Polyurethane-based resins may include polyurethane-based resins modified with polyester, polyether, or caprolactone. Examples of the polyurethane-based resins include "Uriano KL-424", “Uriano KL-564", “Uriano KL-593", and “Uriano 3262” available from Arakawa Chemical Industries, Ltd., and "Pandex 372E” and "Uriano 372E” available from DIC.
- acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, but it is preferable to use two of them in combination. It is more preferable to use a resin in which a resin and a vinyl chloride resin are mixed.
- the content ratio of the acrylic resin and the vinyl chloride resin can be controlled so as to meet the requirements for the non-aqueous ink composition, such as color development, drying property, coating properties, printability, and the like.
- the mixing ratio is not particularly limited and can be changed as appropriate.
- the resin contained in the non-aqueous ink composition is not particularly limited, but it is preferably contained in the range of 0.05% by mass or more, and contained in the range of 0.1% by mass or more, based on the total amount of the non-aqueous ink composition. is more preferable, and it is even more preferable to contain in the range of 0.5% by mass or more. This can further improve the surface drying property of the obtained recorded matter.
- the resin contained in the non-aqueous ink composition is preferably contained in a range of 20.0% by mass or less, more preferably 15.0% by mass or less, based on the total amount of the non-aqueous ink composition. It is more preferable to contain in the range of 10.0% by mass or less. This makes it possible to more effectively eliminate clogging in the nozzles of the inkjet head and improve the storage stability of the non-aqueous ink composition.
- the resin contained in the non-aqueous ink composition according to the present embodiment preferably has a resin having an intrinsic viscosity of 90 mL/g or more at 25°C in a range of 5% by mass or less in the total amount of the resin.
- the non-aqueous ink composition according to the present embodiment has high storage stability and high cleaning recovery by containing a perinone pigment within a predetermined pH range, and further has an intrinsic viscosity of 90 mL.
- /g or more is in the range of 5% by mass or less in the total amount of the resin, clogging in the nozzles of the inkjet head is more effectively eliminated, and the storage stability of the non-aqueous ink composition, recovery from cleaning, and Discharge stability can be significantly improved.
- the intrinsic viscosity is the specific viscosity after the target resin is dispersed in a developing solvent and the molecules contained in the resin are separated by a column filled with granular gel in GPC (gel permeation chromatography) [ ⁇ SP ](( ⁇ 0 )/ ⁇ 0 ( ⁇ 0 : solvent viscosity, ⁇ : solution viscosity)) and concentration C are calculated, and the concentration C is set to 0 in the formula Lim ([ ⁇ SP ]/C). It can be obtained by interpolation (C ⁇ 0).
- the developing solvent is not particularly limited, for example, tetrahydrofuran can be used. The same applies to non-aqueous ink compositions of second and third embodiments described later.
- the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C is preferably in the range of 5.0% by mass or less, more preferably 4.0% by mass or less, based on the total amount of the resin.
- the range of 3.0% by mass or less is even more preferable.
- Non-aqueous ink composition for the purpose of suppressing volatilization of the non-aqueous ink composition in devices such as nozzles and tubes, preventing solidification, and resolubility when solidified,
- a surfactant for the purpose of reducing the surface tension and improving the wettability with the recording medium (substrate), for the purpose of suppressing bleeding of the ink composition on the substrate, and for improving the abrasion resistance of the coating film.
- a surfactant may be added for the purpose and for the purpose of further improving the glossiness of the recorded matter. The same applies to non-aqueous ink compositions of second and third embodiments described later.
- the surfactant preferably contains a surfactant having a siloxane skeleton.
- Pigment A1 tends to aggregate easily in a non-aqueous ink composition and tends to have a large volume average particle size. As a result, the glossiness of the obtained recorded matter may be lowered.
- a surfactant having a siloxane skeleton in the non-aqueous ink composition according to the present embodiment, it is possible to improve the glossiness of the resulting recorded matter even when the pigment A1 is included.
- a non-aqueous ink containing a surfactant having a siloxane skeleton printed matter is less likely to bleed and a recorded matter with improved abrasion resistance can be obtained.
- polyester-modified silicone or polyether-modified silicone As the surfactant having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500 and 3510. , 3530, 3570 (both manufactured by BYK-Chemie Japan) and the like can be used.
- the non-aqueous ink composition according to the present embodiment may contain a surfactant different from the surfactant having a siloxane skeleton.
- a surfactant different from the surfactant having a siloxane skeleton.
- Surfactants are not limited to those described above, and any of anionic, cationic, amphoteric or nonionic surfactants can be used.
- the non-aqueous ink composition according to the present embodiment may contain these surfactants together with a surfactant having a siloxane skeleton, or may contain these surfactants without containing a surfactant having a siloxane skeleton. It may contain an agent.
- the content of the surfactant is not particularly limited, but the lower limit of the content of the surfactant is preferably in the range of 0.01% by mass or more. It is preferably in the range of 0.05% by mass or more, more preferably in the range of 0.1% by mass or more.
- the lower limit of the surfactant content is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and 3.0% by mass or less. is more preferred.
- the non-aqueous ink composition according to the present embodiment includes stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicone, etc.), and erasers.
- stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicone, etc.), and erasers.
- Known additives such as foaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents, and wetting agents may be included as optional components.
- Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like.
- Specific examples include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol).
- a benzophenone-based compound or a benzotriazole-based compound can be used as the ultraviolet absorber.
- Specific examples of the epoxidized product include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate, and specific examples include ADEKA CIZER O-130P and ADEKA CIZER O-180A (manufactured by ADEKA). exemplified.
- Specific examples of polycarboxylic acids include citric acid and maleic acid.
- a non-aqueous ink composition according to a second embodiment of the present invention is a non-aqueous ink composition ejected by an inkjet method containing a pigment, a pigment dispersant, and an organic solvent.
- the pigment contained in this non-aqueous ink composition is characterized in that it contains a pigment A2 represented by the following formula (1-2), and the pH of the pigment A2 is within the range of 3 or more and 9 or less.
- each of X1 to X10 is independently a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, an optionally substituted aromatic hydrocarbon hydrogen group, cyano group, nitro group, amino group, -OH, -COOH, -COO - M + , -SO 3 H, -SO 3 - M + , phthalimido group in which hydrogen atom may be substituted, phthalimidomethyl group, or a heterocyclic compound, and M + indicates a cation.
- the pigment A2 whose pH is controlled within the range of 3 or more and 9 or less, it is possible to suppress the aggregation of the pigments in the non-aqueous ink composition, and it is possible to improve the storage stability and cleaning recovery property. .
- Pigment A2 with a pH of 3 or more and 9 or less is washed with a solution in the same manner as Pigment A1 described above, to treat the surface of the pigment, or to remove a substituent in the benzene ring in the structure of formula (1-2) It can be obtained by changing the types of (X1 to X10), or by performing both treatments.
- the method for changing the type of substituents (X1 to X10) in the benzene ring is the same as for Pigment A1 described above.
- the positions at which the substituents X1 to X10 are substituted are not particularly limited as long as the pH of the pigment A2 is within the range of 3 or more and 9 or less, and any of the 10 substitution positions on the benzene ring may be used. is not particularly limited.
- the upper limit of the pH of Pigment A2 is preferably 9 or less, more preferably 8 or less, even more preferably 7 or less, and even more preferably 6 or less.
- the lower limit of the pH of Pigment A2 is preferably 3 or higher, more preferably 4 or higher.
- the pH of the pigment A2 is 9 or less, the pigment dispersant is more likely to adhere, so aggregation of the pigment A2 in the non-aqueous ink composition can be more effectively suppressed. This can improve the ejection stability and color tone stability of the non-aqueous ink composition.
- the preferable range of the water content and the average particle size of the pigment A2 in the non-aqueous ink composition according to the present embodiment is the same as the preferable range of the water content and the pigment It is the same as the preferred range of the average particle size of A1.
- the preferred range of the content of the pigment A2 contained in the non-aqueous ink composition according to the present embodiment is the same as the preferred range of the content of the pigment A1 in the non-aqueous ink composition of the first embodiment described above. .
- the content of the pigment A2 is 8.0% by mass or less in the total amount of the non-aqueous ink composition, aggregation of the pigment A2 in the non-aqueous ink composition can be more effectively suppressed.
- pigment A2 represented by formula (1-2) C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 270, C.I. I. Pigment Red 272, C.I. I. Pigment Red 283, C.I. I. Pigment Red 291, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73, C.I. I. Pigment Orange 81 etc. can be mentioned.
- the pigment A2 represented by formula (1-2) may be synthesized, for example, by washing a commercially available diketopyrrolopyrrole pigment with a solution (acid solution, alkaline solution, or neutral solution). obtained by treating the surface of the pigment, changing the type of substituents (X1 to X10) in the benzene ring in the structure of formula (1-2), or performing both treatments.
- a solution acid solution, alkaline solution, or neutral solution
- may Commercially available products include IRGAPHR RED BT-CF manufactured by BASF, CROMOPHTAL DPP Red BP (both C.I. Pigment Red 254), Chromofine Red 6156EC manufactured by Dainichiseika Kogyo Co., Ltd. (both C.I. Pigment Red 254), Pigment Red 254 (C.I.
- Pigment Red 254 manufactured by Tokyo Chemical Industry Co., Ltd., Cinilex DPP Red SR-2P (C.I. Pigment Red 254) manufactured by CINIC, CROMOPHTAL DPP ORANGE manufactured by BASF TR, IRAGIN ORANGE D2905, (C.I. Pigment Orange 71), BASF's Irgazin Orange L 2990 HD (C.I. Pigment Orange 73), and the like.
- the non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the pigment A2 described above.
- coloring materials include pigments and dyes of hues similar to pigment A2 (eg, orange, magenta, yellow, red).
- C.I. color index
- a dispersing aid (pigment derivative), which will be described later, may be used together with the pigment dispersant. Thereby, the dispersion stability of the pigment can be improved.
- Organic solvent is capable of dispersing or dissolving each component contained in the non-aqueous ink composition according to this embodiment.
- the organic solvent is not particularly limited, but organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( b2) and at least one selected from the group consisting of a lactone solvent (b3)).
- the affinity between the glycol ether solvent and “pigment A2” is poor, so pigment A2 aggregates in the non-aqueous ink composition, resulting in recovery from cleaning. sexuality may worsen. Therefore, by including organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)), pigment A2 aggregates. It is possible to effectively suppress the deterioration of the cleaning recoverability due to this. Therefore, the organic solvent contained in the non-aqueous ink composition of the present invention is not particularly limited. By containing at least one selected from the group consisting of the solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the non-aqueous solvent has high storage stability and high cleaning recovery. It becomes an ink composition.
- Preferred types of solvents in the alkylamide-based solvent (b1), the cyclic amide-based solvent (b2), and the lactone-based solvent (b3) are the alkylamide-based solvent (b1) in the non-aqueous ink composition of the first embodiment described above. , cyclic amide solvent (b2), and lactone solvent (b3).
- the content of the cyclic amide-based solvent (b2) is not particularly limited, but the lower limit of the content of the cyclic amide-based solvent (b2) is preferably in the range of 1% by mass or more based on the total amount of the non-aqueous ink composition.
- the range of 10% by mass or more is more preferable, and the range of 15% by mass or more is even more preferable.
- the content ranges are the same as those of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3) in the non-aqueous ink composition of the first embodiment.
- organic solvents B "containing an alkylamide solvent (b1)” or “containing a cyclic amide solvent (b2)” is preferable, and among them, "containing an alkylamide solvent (b1) ' is more preferred.
- the organic solvent B contains at least one of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the effect is sufficiently exhibited. You may mix two or more types from. When two or more organic solvents B are mixed, the preferred range of the total content of the organic solvents B contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
- the non-aqueous ink composition according to this embodiment may contain an organic solvent other than the organic solvent B described above.
- organic solvent other than the organic solvent B described above.
- glycol ether dialkyl in which the OH groups at both ends of the glycol are alkyl-substituted
- glycol ether monoalkyl in which one OH group of the glycol is alkyl-substituted, carbonate esters, and other solvents
- oxazolidinone-based solvents, acetate-based Solvents, amide-based solvents different from alkylamide-based solvents (b1) and cyclic amide-based solvents (b2) alkyl alcohols, ketones or keto-alcohols, ethers, oxyethylene or oxypropylene copolymers, diols, 4 alcohols, alkanolamines, etc.
- Preferred types of other organic solvents are the same as the glycol ether dialkyl, glycol ether monoalkyl, and carbonate in the non-aqueous ink composition of the first embodiment described above.
- the preferred range of the total content of other organic solvents contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
- a dispersant may be used as necessary in the non-aqueous ink composition according to the present embodiment.
- a preferred type of pigment dispersant is the same as the pigment dispersant in the non-aqueous ink composition of the first embodiment described above.
- the non-aqueous ink composition according to the present embodiment containing the pigment A2 having a pH of 3 or more and 9 or less it is preferable to use a pigment dispersant having a basic group among the above.
- a pigment dispersant having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less it is preferable to use a pigment dispersant having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less.
- the preferred range of the content of the pigment dispersant contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
- a dispersing aid may be used as necessary in the non-aqueous ink composition according to the present embodiment.
- the non-aqueous ink composition according to the present embodiment may contain no resin, but may contain a resin.
- Preferred resin types are the same as the resins in the non-aqueous ink composition of the first embodiment described above.
- the content of the resin contained in the non-aqueous ink composition and the preferred range of the resin having an intrinsic viscosity of 90 mL/g or more at 5° C. are the same as those of the non-aqueous ink composition of the first embodiment.
- a surfactant may be added to the non-aqueous ink composition according to the present embodiment.
- surfactants include polyoxyalkylene alkyl ethers such as nonionic P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S -207, S-215, A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (Kao ( Co., Ltd.), Floren G-70, D-90, TG-740W (Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (Riken Vitamin Co., Ltd.), Adekatol NP-620, NP-650, NP- 660, NP-675, NP-683, NP-686, Adekacol CS-141E, TS-230E (manufactured by Adeka Co., Ltd.), Solgen 30V, 40, TW-20, TW-80, Neugen C
- a fluorine-modified polymer such as Ichi Kogyo Seiyaku Co., Ltd.
- a specific example is BYK-340 (manufactured by BYK-Chemie Japan), a silicon-based silicone having a siloxane skeleton.
- the surfactant it is preferable to use polyester-modified silicone or polyether-modified silicone.
- acetylene glycol-based surfactants include Surfynol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan), Olfin (registered trademark) STG, E1010 (both manufactured by Nissin Kagaku Co., Ltd.), and the like.
- the surfactant is not limited to the above, and any anionic, cationic, amphoteric or nonionic surfactant can be used.
- the surfactant preferably contains a surfactant having a siloxane skeleton.
- a non-aqueous ink containing a surfactant having a siloxane skeleton can reduce print bleeding and provide a recorded matter with improved abrasion resistance. The same applies to the non-aqueous ink composition of the third embodiment which will be described later.
- the content range of the surfactant contained in the non-aqueous ink composition is the same as that of the non-aqueous ink composition of the first embodiment described above.
- the non-aqueous ink composition according to this embodiment may optionally contain other components.
- the types of other components contained in the non-aqueous ink composition are the same as those of the non-aqueous ink composition of the first embodiment described above.
- Non-Aqueous Ink Composition of Third Embodiment>> is a non-aqueous ink composition that contains a pigment, a pigment dispersant, and an organic solvent and is ejected by an inkjet method.
- the pigment contained in this non-aqueous ink composition is characterized by containing the halogenated phthalocyanine pigment A3, and the organic solvent contains the following organic solvent B.
- Organic solvent B at least one selected from the group consisting of alkylamide solvents (b1), cyclic amide solvents (b2), and lactone solvents (b3)
- the halogenated phthalocyanine pigment A3 is a compound in which at least part of the hydrogen atoms on the benzene ring in the phthalocyanine skeleton are substituted with halogen atoms (fluorine, chlorine, bromine, iodine).
- X1 to X16 each independently represent a halogen atom or a hydrogen atom.
- M represents two hydrogen atoms or a metal atom which may have a ligand.
- a halogenated phthalocyanine pigment is a pigment having a structure in which a maximum of 16 halogen atoms are bonded per phthalocyanine molecule.
- phthalocyanine pigments generally have higher weather resistance than yellow pigments. For this reason, by using a green ink containing a halogenated phthalocyanine pigment, the weather resistance of the obtained recorded matter is improved compared to the case of using a yellow pigment and a blue pigment as in the methods (II) and (III). can be improved.
- the halogenated phthalocyanine pigment A3 is substituted with a halogen element, the overall density of the pigment (weight per unit volume) is high, and it is difficult to disperse it in a non-aqueous ink composition for a long period of time. Become. Therefore, when a non-aqueous ink composition containing a halogenated phthalocyanine pigment is stored for a long period of time, the pigment precipitates in the non-aqueous ink composition, resulting in deterioration of storage stability, color tone stability, and recovery from cleaning. was clarified by the research of the present inventors.
- an organic solvent B at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3)
- an organic solvent B at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3)
- storage stability and Color tone stability and recovery from cleaning can be improved.
- the preferred range of water content in the non-aqueous ink composition according to the present embodiment is the same as the preferred range of water content in the non-aqueous ink composition of the first embodiment described above. Since the pigment A3 is highly hydrophobic, a non-aqueous inkjet composition containing this pigment tends to deteriorate dispersibility of the pigment relatively easily due to contact with water, and storage stability tends to deteriorate. In addition to containing the organic solvent B, by reducing the water content in the non-aqueous ink composition so that it contains as little water as possible (intentionally avoiding water), halogen Precipitation of the phthalocyanine pigment A3 can be more effectively suppressed, and storage stability and ejection stability can be more effectively improved.
- the pigment contained in the non-aqueous ink composition according to this embodiment contains the halogenated phthalocyanine pigment A3.
- Halogenated phthalocyanine pigment A3 is a compound having a phthalocyanine skeleton represented by the following formula.
- X1 to X16 each independently represent a halogen atom or a hydrogen atom.
- M represents two hydrogen atoms or a metal atom which may have a ligand.
- a halogenated phthalocyanine pigment is one in which at least one of X1 to X16 is replaced with a halogen atom. That is, the halogenated phthalocyanine pigment is a pigment having a structure in which at least one halogen atom is bonded to one phthalocyanine molecule and at most 16 halogen atoms are bonded in total per phthalocyanine molecule.
- a halogenated phthalocyanine pigment having a larger number of halogen groups is more greenish.
- the number of halogen atoms substituted in the halogenated phthalocyanine pigment is preferably 1 or more, more preferably 8 or more, more preferably 12 or more, and more preferably 14 or more in order to exhibit a green hue.
- the halogenated phthalocyanine pigment A3 may have two hydrogen atoms at the center M of the phthalocyanine skeleton, or may be a halogenated metal phthalocyanine pigment in which M is a metal atom.
- M is a metal atom
- the type of metal is not particularly limited, but manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), or aluminum ( Al) is particularly desirable.
- M may have a ligand.
- Halogenated phthalocyanine pigment A3 includes C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like.
- Halogenated phthalocyanine pigment A3 may be produced by a conventionally known method, such as FASTGEN GREEN 2YK (C.I. Pigment Green 36) manufactured by DIC, Cyanine Green 5370 (C Pigment Green 36), FASTGEN GREEN 5740 (C.I. Pigment Green 7) manufactured by DIC, Fastogen GREEN A110 (C.I. Pigment Green 58) manufactured by DIC, and the like. .
- the volume-based cumulative 50% particle diameter (D50) of Pigment A3 is not particularly limited, but the lower limit of the volume-based cumulative 50% particle diameter (D50) is preferably 30 nm or more, more preferably 40 nm or more. More preferably, it is 50 nm or more. This improves the weather resistance of the halogenated phthalocyanine pigment A3.
- the upper limit of the volume-based cumulative 50% particle diameter (D50) is preferably 150 nm or less, more preferably 140 nm or less, and even more preferably 130 nm or less. This makes it possible to more effectively suppress the precipitation of the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition, thereby improving the color tone stability.
- the volume-based cumulative 90% particle size (D90) of Pigment A3 is not particularly limited, but the lower limit of the volume-based cumulative 90% particle size (D90) is preferably 50 nm or more, more preferably 60 nm or more. , 70 nm or more. This improves the weather resistance of the halogenated phthalocyanine pigment A3.
- the upper limit of the volume-based cumulative 90% particle diameter (D90) is preferably 300 nm or less, more preferably 290 nm or less, and even more preferably 280 nm or less. This makes it possible to more effectively suppress the precipitation of the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition, thereby improving the color tone stability.
- the content of pigment A3 is not particularly limited, but the lower limit of the content of pigment A3 is preferably 0.5% by mass or more, and preferably 1.0% by mass or more, based on the total amount of the non-aqueous ink composition. More preferably, it is 1.5% by mass or more. As a result, the print density becomes sufficient, and the color reproducibility of the recorded matter can be improved.
- the upper limit of the content of Pigment A3 is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and 5.0% by mass or less in the total amount of the non-aqueous ink composition. is more preferred.
- the non-aqueous ink composition according to the present embodiment may further contain coloring materials (including pigments and dyes) other than the above-described halogenated phthalocyanine pigment A3.
- coloring materials include pigments and dyes having similar skeletons and hues (cyan, green, yellow) to the halogenated phthalocyanine pigment A3.
- C.I. color index
- a dispersing aid (pigment derivative), which will be described later, may be used together with the pigment dispersant.
- the dispersion stability of the pigment can be improved, and the storage stability of the non-aqueous ink composition can be improved.
- Organic solvent is capable of dispersing or dissolving each component contained in the non-aqueous ink composition according to this embodiment.
- the organic solvent contains organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)).
- the alkylamide solvent (b1) by containing the alkylamide solvent (b1), it becomes possible to disperse the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition for a long period of time, and the storage stability and color tone stability are improved. , and cleaning recoverability can be improved.
- the affinity with the pigment dispersant for dispersing the halogenated phthalocyanine pigment A3 is improved, and it is possible to effectively disperse it in a non-aqueous ink composition containing an alkylamide solvent. This is probably because the precipitation of the halogenated phthalocyanine pigment A3 can be suppressed.
- the inclusion of the cyclic amide solvent (b2) or the lactone solvent (b3) makes it possible to disperse the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition for a long period of time. It was found that storage stability, color tone stability, and recovery from cleaning can be improved.
- Preferred types of solvents in the alkylamide-based solvent (b1), the cyclic amide-based solvent (b2), and the lactone-based solvent (b3) are the alkylamide-based solvent (b1) in the non-aqueous ink composition of the first embodiment described above. , cyclic amide solvent (b2), and lactone solvent (b3).
- organic solvents B "containing an alkylamide solvent (b1)” or “containing a cyclic amide solvent (b2)” is preferable, and among them, "containing an alkylamide solvent (b1) ' is more preferred.
- the organic solvent B contains at least one of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3), the effect is sufficiently exhibited. You may mix two or more types from. When two or more organic solvents B are mixed, the preferred range of the total content of the organic solvents B contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
- the non-aqueous ink composition according to this embodiment may contain an organic solvent other than the organic solvent B described above.
- organic solvent other than the organic solvent B described above.
- glycol ether dialkyl in which the OH groups at both ends of the glycol are alkyl-substituted
- glycol ether monoalkyl in which one OH group of the glycol is alkyl-substituted, carbonate esters, and other solvents
- oxazolidinone-based solvents, acetate-based Solvents, amide solvents different from alkylamide solvents (b1) and cyclic amide solvents (b2), alkyl alcohols, ketones or ketoalcohols, ethers, oxyethylene or oxypropylene copolymers, diols, 4 alcohols, alkanolamines, etc. oxazolidinone-based solvents, acetate-based Solvents, amide solvents different from alkylamide solvents (b1) and cyclic
- Preferred types of other organic solvents are the same as the glycol ether dialkyl, glycol ether monoalkyl, and carbonate in the non-aqueous ink composition of the first embodiment described above.
- the preferred range of the total content of other organic solvents contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
- a pigment dispersant may be used as necessary in the non-aqueous ink composition according to the present embodiment.
- a pigment dispersant having a basic group aggregation of the halogenated phthalocyanine pigment A3 in the non-aqueous ink composition can be more effectively suppressed.
- a preferred type of pigment dispersant is the same as the pigment dispersant in the non-aqueous ink composition of the first embodiment described above.
- a pigment dispersant having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less. Aggregation of Pigment A3 in the non-aqueous ink composition can be more effectively suppressed.
- the preferred range of the content of the pigment dispersant contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
- a dispersing aid may be used as necessary in the non-aqueous ink composition according to the present embodiment.
- the non-aqueous ink composition according to the present embodiment may contain no resin, but may contain a resin.
- Preferred resin types are the same as the resins in the non-aqueous ink composition of the first embodiment described above.
- the preferred range of the content of the resin contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the first embodiment described above.
- the resin contained in the non-aqueous ink composition according to the present embodiment preferably has a resin having an intrinsic viscosity of 90 mL/g or more at 25°C in a range of 5% by mass or less in the total amount of the resin.
- the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25° C. is preferably 4.0% by mass or less, more preferably 3.5% by mass or less, more preferably 2.5% by mass, based on the total amount of the resin. % or less is even more preferable.
- a surfactant may be added to the non-aqueous ink composition according to the present embodiment.
- Preferred types of surfactants are the same as the surfactants in the non-aqueous ink composition of the second embodiment described above.
- the preferred range of the content of the surfactant contained in the non-aqueous ink composition is the same as for the non-aqueous ink composition of the second embodiment described above.
- the non-aqueous ink composition according to this embodiment may optionally contain other components.
- the types of other components contained in the non-aqueous ink composition are the same as in the non-aqueous ink composition of the first embodiment described above.
- the non-aqueous ink composition according to the present embodiment is produced by mixing an organic solvent, a pigment containing pigment A1 or A2, and other components (for example, a resin) using a paint shaker. can be done. At this time, each component may be dispersed with zirconia beads. Moreover, the obtained non-aqueous ink composition may be adjusted to a desired dissolved oxygen content and dissolved nitrogen content by performing a degassing treatment or the like, if necessary.
- a pigment containing pigment A3, at least 1) a pigment containing the halogenated phthalocyanine pigment A3, and other components (for example, a resin) are mixed using a paint shaker.
- the non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition that does not intentionally contain water. And moisture may be mixed in during the manufacturing process. It is desirable that the water content in the non-aqueous ink composition is as low as possible. Excessive water content deteriorates storage stability and dischargeability, and further increases the risk of generation of solid components and the like.
- the upper limit of the water content in the non-aqueous ink composition is preferably 5.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass in the total amount of the non-aqueous ink composition. The following are particularly preferred.
- the organic solvent in advance.
- the amount of water contained in the non-aqueous composition can be reduced.
- a method for drying the organic solvent for example, a method of spraying an inert gas (e.g., nitrogen gas) dried in an inert gas atmosphere such as nitrogen for a predetermined time, a method of distilling and refining the organic solvent, and water are selected. Examples include a method of allowing the organic solvent to permeate through a semi-permeable membrane that selectively permeates the organic solvent, and a method of selectively adsorbing water mixed in the organic solvent with a water adsorbent that adsorbs water.
- an inert gas e.g., nitrogen gas
- the recording method according to the present embodiment is a recording method in which the above non-aqueous ink composition is ejected onto the surface of a substrate by an inkjet method.
- the non-aqueous ink compositions of the first and second embodiments include pigment A1 in which the substituent in the structure is changed so that the pH is in the range of 3 or more and 9 or less, or By containing A2, it satisfies the properties required for the non-aqueous ink composition ejected by the inkjet method. It satisfies the properties required for objects.
- the non-aqueous ink composition of the third embodiment has high storage stability and color tone stability even if it contains the halogenated phthalocyanine pigment A3.
- the recorded matter obtained by using the recording method also has high color tone stability.
- a method of ejecting ink by an inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.
- a recording method using the above ink composition can also be defined as a method for producing a recorded matter.
- the non-aqueous ink composition of the first embodiment among the above non-aqueous ink compositions to produce a recorded matter, the characteristics required for a non-aqueous ink composition ejected by an inkjet method were satisfied.
- a record can be produced in the state.
- the characteristics of high storage stability and high recovery from cleaning are satisfied. Records can be produced.
- a recorded matter using the non-aqueous ink composition of the third embodiment among the above non-aqueous ink compositions a recorded matter having high color tone stability can be obtained.
- the base material (recording medium) that can be used in the recording method according to the present embodiment is not particularly limited.
- Various substrates can be used, including absorbent substrates such as fabrics, and substrates with a surface coating such as substrates having a receiving layer.
- the non-aqueous ink composition is a non-aqueous ink composition that does not contain water, it is preferable that the surface is mainly made of a resin.
- the non-aqueous ink composition contains an alkylamide-based solvent (b) that is permeable to a resin base material, bleeding of printing on a medium (recording medium) whose surface is made of a resin is reduced. and the print becomes clear.
- resins include polyvinyl chloride-based polymers, acryl, PET, polycarbonate, PE, and PP. Further, it may be used for a resin base material (so-called resin base material for lamination) that assumes lamination of a film to the recording surface of a recorded matter.
- a base material (recording medium) whose surface is made of a hard or soft polyvinyl chloride polymer is preferred.
- the substrate (recording medium) whose surface is made of a polyvinyl chloride polymer include polyvinyl chloride substrates (films or sheets).
- the recording layer (also referred to as printing layer) is a layer formed by volatilization of the solvent contained in the non-aqueous ink composition, and forms a desired image.
- the non-aqueous ink composition of the first embodiment among the above non-aqueous ink compositions, the properties required for the non-aqueous ink composition ejected by the inkjet method are satisfied.
- the non-aqueous ink composition of the second embodiment has high storage stability and high recovery from cleaning. A desired image can be formed.
- the non-aqueous ink composition of the third embodiment By ejecting the non-aqueous ink composition of the third embodiment among the above non-aqueous ink compositions, a recording layer having high color tone stability can be obtained. Moreover, since the above non-aqueous ink composition has high storage stability, it is possible to form a desired image even with a non-aqueous ink composition that has been stored for a long period of time.
- the recorded matter according to this embodiment may further include a layer having a desired function on the upper surface of the recording layer (printing layer).
- a layer having a desired function on the upper surface of the recording layer may be formed for the purpose of further imparting abrasion resistance and glossiness to the recorded matter.
- a layer having a textured surface may be formed by adding a filler or changing the film thickness for each pixel.
- a weather-resistant layer containing an ultraviolet absorber, a light stabilizer, etc., a glittering layer containing a glittering pigment, or the like may be formed.
- the ink set according to the present embodiment is an ink set comprising at least the above non-aqueous ink composition.
- the above non-aqueous ink composition is a red ink, an orange ink or a green ink
- the effect of the present invention can be obtained by combining the conventionally known yellow ink, magenta ink, cyan ink and black ink. In addition to performance, it is possible to expand color reproducibility.
- an ink set containing the above non-aqueous ink composition and a glittering ink such as white ink, metallic ink, or pearl ink, or an ink set containing clear ink containing no pigment may be used.
- Inkjet recording device A conventionally known inkjet recording apparatus that ejects the above non-aqueous ink composition by an inkjet method can be used.
- an inkjet printer such as VersaArt RE-640 manufactured by Roland DG Co., etc. can be used.
- an on-carriage type and serial printer type inkjet recording apparatus will be described. It may be an off-carriage type inkjet recording device fixed to the head, or a line printer type inkjet recording device in which the ink composition is ejected onto the recording medium (substrate) without moving the inkjet head. good.
- the inkjet recording apparatus preferably includes a heating mechanism and a fixing mechanism for fixing the substrate.
- the organic solvent contained in the non-aqueous ink composition is dried by controlling the substrate surface temperature with a heating mechanism provided in the inkjet recording apparatus and drying the non-aqueous ink composition that has landed on the substrate (recording medium). can be volatilized.
- the fixing mechanism for fixing the base material makes it possible to dry the non-aqueous ink composition while the base material (recording medium) is fixed. Uniformity can be suppressed. This makes it possible to effectively dry the non-aqueous ink composition that has landed on the substrate (recording medium).
- the heating mechanism provided in the inkjet recording apparatus may be a pre-heater, a platen heater, an after-heater, or the like, or may be a mechanism for blowing warm air onto the recorded matter. Also, a plurality of these heating mechanisms may be combined.
- the surface temperature of the substrate heated by the heating mechanism is not particularly limited as long as the organic solvent contained in the non-aqueous ink composition can be volatilized, and the lower limit of the surface temperature of the substrate is 20° C. or higher. , more preferably 30° C. or higher, and even more preferably 40° C. or higher.
- the upper limit of the surface temperature of the substrate is preferably 70° C. or lower, more preferably 60° C. or lower, and even more preferably 50° C. or lower.
- the fixing mechanism for fixing the base material may be a fixing mechanism that fixes the base material with a predetermined jig, or a fixing mechanism that sucks and adsorbs the base material using negative pressure, and is not particularly limited.
- the inkjet head that ejects the above non-aqueous ink composition may be a piezo inkjet head using a piezoelectric element or a thermal inkjet head using a heating element, and is not particularly limited.
- a container for storing the non-aqueous ink composition is connected to an inkjet ejection port for ejecting the non-aqueous ink composition, and the non-aqueous ink composition is applied.
- a circulating plastic tube may be provided, and the above non-aqueous ink composition may be supplied to the inkjet head through the plastic tube and ejected by an inkjet method.
- the inkjet recording apparatus preferably has a mechanism capable of eliminating nozzle clogging.
- the effect of the present invention can be more effectively achieved by providing a mechanism capable of eliminating nozzle clogging.
- the tube connected to the storage mechanism and the inkjet ejection port has a valve mechanism that adjusts the flow path of the non-aqueous ink composition.
- the ejection stability of the non-aqueous ink composition can be further improved by supplying the non-aqueous ink composition from the storage mechanism to the inkjet ejection port via the valve mechanism.
- the material of the plastic tube is not particularly limited, but includes polyolefin resin such as polyethylene resin, ethylene propylene diene rubber, nylon, polyurethane, PTFE, and the like. Among these, polyethylene resins and ethylene propylene diene rubbers are preferred.
- the ink jet recording apparatus can be used for each color ink such as yellow, magenta, cyan, and black, as well as for light magenta, light cyan, light black, orange, green, red, and white, as described above.
- the inkjet recording apparatus may or may not have a winding mechanism for the recording medium (base material), a drying mechanism for drying the surface of the base material, and an ink circulation mechanism.
- (First embodiment) Preparation of resin (1) Acrylic resin In 300 g of diethylene glycol diethyl ether kept at 100 ° C., 150 g of methyl methacrylate and 50 g of butyl methacrylate and a predetermined amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiation agent) was added dropwise over 1.5 hours. After completion of the dropwise addition, the mixture was allowed to react at 100° C. for 2 hours and then cooled to obtain a colorless and transparent polymer solution of methyl methacrylate. Thereafter, the solvent was sufficiently distilled off from this polymer solution to obtain a polymer of methyl methacrylate.
- polymerization initiation agent t-butyl peroxy-2-ethylhexanoate
- the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (this The mass of the polymerization initiator used is shown in the following Table 1. In Table 1, it is described as "initiator amount").
- Polyester-based resin 104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were placed in a round-bottomed flask and allowed to cool for 4 hours. The temperature was gradually raised to 240° C., and the esterification reaction was carried out while removing the distillate out of the system. After completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250° C. for initial polymerization. After that, post-polymerization was carried out at 1 mmHg or less for 1 hour to obtain a polyester resin.
- PPAXEL CD-220 manufactured by Daicel
- IPDI isophorone diisocyanate
- DEF N,N-diethylformamide
- Table 1 shows the weight average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, polyester resin, polyurethane resin), and the intrinsic viscosity at 25 ° C. is 90 mL. / g or more resin ratio.
- the weight average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography).
- the ratio of resins with an intrinsic viscosity of 90 mL / g or more is determined by connecting a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T-rEX manufactured by WYATT) to a Shimadzu SEC (GPC) system, Using tetrahydrofuran as a developing solvent, the sample was first passed through a column heated to 40°C in the Shimadzu SEC ( GPC ) system, and then cooled to 25°C. Then, the concentration C was determined by a refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP ]/C).
- Pigment A1 Synthetic products 1 to 6 of pigment A1 were synthesized under the conditions shown in Table 2. Specifically, 2 parts by mass of the perinone pigment of (a1) in Table 2 was dispersed in the solvent of (a2) in Table 2, and (a3) in Table 2 was added ((a4) in Table 2. Table After stirring for the time (a6) in Table 2 under the temperature conditions of (a5) in 2, the synthetic products 1 and 2 were washed with ethanol, and the synthetic products 3, 4 and 6 were washed with water and the synthetic products 1 to 6 of the pigment A1.
- Pigment Ap (synthetic product 5) in Table 2 is a pigment synthesized by the method described in Japanese Patent No. 3076738 and is pigment A1 represented by formula (1-1). was not dispersed in a solvent.
- the pH of synthetic products 1 to 6 of Pigment A1 was measured according to the test method of JIS K5101-17-1:2004 (described in (a7) of Table 2).
- Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous ink composition. The unit is % by mass. The particle size and dispersion time of the zirconia beads are shown in Tables 3 to 10 below.
- volume-based cumulative 90% particle size (D90) of the pigment contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
- Evaluation 2 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 8% or more and less than 10%.
- Evaluation 1 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 10% or more.
- Ejection stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, an inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.) is filled with a non-aqueous ink composition, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.) is used. )) in a bi-directional high-speed printing mode (360 x 720 dpi), solid and fine lines are printed by continuous printing at a substrate surface temperature of 40 ° C, and the presence or absence of missing dots, flight deflection, and ink splattering is visually observed.
- a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.)
- a bi-directional high-speed printing mode 360 x 720 dpi
- Evaluation Criteria Evaluation 5 Within the 24-hour test period, dot missing, flight deflection, or ink scattering occurred less than 10 times. Evaluation 4: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 10 times or more and less than 20 times. Evaluation 3: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 20 times or more and less than 30 times. Evaluation 2: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 30 times or more and less than 40 times. Evaluation 1: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 40 times or more.
- Solid filling was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, with the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.), a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) was printed bidirectionally. Printing was carried out at a substrate surface temperature of 40° C. in a high-speed printing mode (360 ⁇ 720 dpi), and filling (blank spots) of the solid printed portion was confirmed (denoted as “solid filling” in the table).
- a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
- Evaluation 5 A uniform solid image is formed
- Evaluation 4 White spots cannot be visually confirmed, but slight color unevenness can be confirmed, but the design is not impaired
- Evaluation 3 White spots cannot be visually confirmed, Color unevenness can be observed.
- Evaluation 2 White spots can be observed.
- Evaluation 1 White spots can be observed remarkably, and a decrease in density is observed.
- the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for surface drying properties. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi), and the time taken to dry at 40°C was measured (referred to as "surface dryness" in the table). . Rating Criteria Rating 5: Dries in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: It dries in 8 minutes or more.
- the non-aqueous ink compositions of Examples and Comparative Examples were evaluated for color development. Specifically, high-quality printing is performed on a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) using the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.). A solid image was printed in mode (1440 ⁇ 720 dpi). The chroma was measured based on JIS Z 8721 using X-Rite eXact (manufactured by X-Rite) under the conditions of a viewing angle of 2°, a measurement range of 4 mm ⁇ , and a D65 light source.
- a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
- the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.).
- a solid image was printed in mode (1440
- Evaluation Criteria Evaluation 5 Saturation is 100 or more.
- Evaluation 4 Saturation is 90 or more and less than 100.
- Evaluation 3 Saturation is 80 or more and less than 90.
- Evaluation 2 Saturation is 70 or more and less than 80.
- Evaluation 1 Saturation is less than 70.
- the weather resistance of prints produced using the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples was evaluated.
- the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R (manufactured by MACtac)) was printed with a solid image in a high-quality print mode (1440 ⁇ 720 dpi) and dried at 40° C. for 1 hour.
- the recorded matter thus obtained was put into a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki Co., Ltd.) and subjected to a cycle test.
- Test conditions are based on JIS K-5600-7-7, black panel temperature: 63°C, xenon lamp irradiance: 60W/m 2 , temperature inside test layer: 38°C, and humidity in segment 1 is 50%. 102 minutes in a state of maintaining at 200° C., and 18 minutes of water irradiation in segment 2, which was regarded as one cycle. With 50 cycles as one set, this cycle test was continued for 10 sets. The value of hue change ⁇ E before and after the test was evaluated, and the hue was evaluated under the following conditions.
- Evaluation 4 ⁇ E is less than 20.0 and 10.0 or more.
- Evaluation 3 ⁇ E is less than 30.0 and 20.0 or more.
- Glossiness Glossiness was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (glued poly Print a solid part on a vinyl chloride film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi) at a substrate surface temperature of 40 ° C. After drying for 5 minutes in an oven at 60 ° C., the printed matter was measured for 20° gloss.
- a recording medium glued poly Print a solid part on a vinyl chloride film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi) at a substrate surface temperature of 40 ° C. After drying for 5 minutes in an oven at 60 ° C., the printed matter was measured for 20° gloss.
- the values of L * , a * , and b * were measured under the conditions of a viewing angle of 2°, a measurement range of 4 mm ⁇ , and a D65 light source (in the table, "color tone stability (sedimentation gender)”).
- the hue change ⁇ E is determined by the following formula using the values of L *1 , a *1 , b *1 before the test and L *2 , a *2 , b *2 after the test.
- ⁇ E ((L * 1 - L * 2 ) 2 + (a * 1 - a * 2 ) 2 + (b * 1 - b * 2 ) 2 ) (1/2) Evaluation Criteria Evaluation 5: ⁇ E is less than 2.0. Evaluation 4: ⁇ E is less than 2.5 and 2.0 or more. Evaluation 3: ⁇ E is less than 3.0 and 2.5 or more. Evaluation 2: ⁇ E is less than 3.5 and 3.0 or more. Evaluation 1: ⁇ E is 3.5 or more.
- the The water-based ink composition had good storage stability as compared with Examples 1-13.
- the non-aqueous ink compositions of Examples 1-14 to 1-30 and 1-72 to 1-75 in which the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C was changed the intrinsic viscosity at 25°C Compared to the non-aqueous ink compositions of Examples in which the amount of the resin having a viscosity of 90 mL/g or more is 5% by mass or less based on the total amount of the resin, Solid filling and intermittent ejection have been improved.
- the organic solvent B (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3)) of Example 1-1 containing
- the aqueous ink composition has various properties required for a non-aqueous ink composition ejected by an inkjet method even when compared with the non-aqueous ink compositions of Examples 1-31 to 1-33 that do not contain the organic solvent B. was better.
- Example 1-34 to 1-41 in which the content of the organic solvent B was changed, Examples 1-34 to 1-40 in which the content of the organic solvent B was in the range of 1% by mass to 90% by mass
- the non-aqueous ink composition of Example 1-41 has better color development and weather resistance than the non-aqueous ink composition of Example 1-41, and various properties required for non-aqueous ink compositions ejected by the inkjet method. The characteristics were better.
- the various properties required for the non-aqueous ink composition ejected by the inkjet method are also better, and the organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( A non-aqueous ink composition containing b2) and at least one selected from the group consisting of a lactone-based solvent (b3) would exhibit the effects of the present invention particularly effectively.
- Example 1-52 to 1-55 in which the content of pigment A1 was changed, the content of pigment A1 was 0.1% by mass or more and 8.0% by mass or less based on the total amount of the non-aqueous ink composition.
- the non-aqueous ink compositions of Examples 1-52 to 1-54 had better storage stability than that of Example 1-55, which is required for non-aqueous ink compositions ejected by an inkjet method. It can be seen that various properties are better.
- Example 1-60 to 1-65 in which the type of pigment dispersant was changed, the non-aqueous ink compositions of Examples 1-61 to 1-65 using a pigment dispersant having a basic group were Even compared with the non-aqueous ink composition of Example 60, the ejection stability was improved.
- the non-aqueous ink compositions of Examples 1-62 to 1-64 having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less showed particularly improved ejection stability.
- Example 1-66 to 1-69 in which the content of the pigment dispersant was changed, the range of 5 parts by mass to 150 parts by mass with respect to 100 parts by mass of the pigment in the non-aqueous ink composition
- the ink compositions of Examples 1-66 to 1-68 had improved color development evaluation and surface drying property even when compared with the non-aqueous ink composition of Example 1-69.
- Example 1-1 the ink compositions of Examples 1-70 and 1-71, which did not contain a surfactant having a siloxane skeleton, had lower glossiness than the ink composition of Example 1-1.
- the non-aqueous ink composition of Comparative Example 1-1 which contains the pigment A1 having a pH of less than 3, has poor storage stability and solid filling. However, it does not satisfy the various characteristics that are required.
- the non-aqueous ink composition of Comparative Example 1-2 which contains the pigment A1 having a pH of more than 9, has deteriorated storage stability and ejection stability, and is suitable for non-aqueous ink compositions ejected by an inkjet method. It does not meet the various required properties.
- C.I. I. Pigment Orange 31 C.I. I. Reference Examples 1-1 and 1-2 containing Pigment 64 satisfy the properties required for non-aqueous ink compositions ejected by an inkjet method, and are easily aggregated in non-aqueous ink compositions. It was confirmed that this is a problem unique to non-aqueous ink compositions containing perinone pigments.
- the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (this The mass of the polymerization initiator used at that time is shown in Table 11 below, which is indicated as "initiator amount" in Table 11.).
- Polyester-based resin 104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were placed in a round-bottomed flask and allowed to cool for 4 hours. The temperature was gradually raised to 240° C., and the esterification reaction was carried out while removing the distillate out of the system. After completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250° C. for initial polymerization. After that, post-polymerization was carried out at 1 mmHg or less for 1 hour to obtain a polyester resin.
- PVAXEL CD-220 manufactured by Daicel
- IPDI isophorone diisocyanate
- DEF N,N-diethylformamide
- a prepolymer with a 250 parts by mass of N,N-diethylformamide (DEF) was added thereto and dissolved uniformly.
- a chain extender solution dissolved in 100 parts by mass of DEF) was added, and the mixture was further stirred at 60°C for 40 minutes.
- 3.8 parts of monoisopropanolamine (MIPA: manufactured by Daicel) dissolved in 50 parts by mass of N,N-diethylformamide (DEF) was added as a reaction terminator, and finally 250 parts of N,N-diethylformamide (DEF) was added. Parts by mass were added to obtain a polyurethane solution having a solid content of 25.0% by mass.
- Table 11 shows the weight average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, polyester resin, polyurethane resin), and the intrinsic viscosity at 25 ° C. is 90 mL. / g or more resin ratio.
- the weight average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography).
- the ratio of resins with an intrinsic viscosity of 90 mL / g or more is determined by connecting a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T-rEX manufactured by WYATT) to a Shimadzu SEC (GPC) system, Using tetrahydrofuran as a developing solvent, the sample was first passed through a column heated to 40°C in the Shimadzu SEC ( GPC ) system, and then cooled to 25°C. Then, the concentration C was determined by a refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP ]/C).
- Synthetic products 1 to 3 of pigment A2 were synthesized under the conditions shown in Table 12. Specifically, 2 parts by mass of the diketopyrrolopyrrole pigment of (a8) in Table 12 was dispersed in the solvent of (a9) in Table 12, and (a10) in Table 12 was added in parts (a11) of Table 12. After stirring for the time (a13) in Table 12 under the temperature conditions of (a12) in Table 12, the mixture was washed with water to obtain Synthetic Products 1, 2 and 3 of Pigment A2.
- the pH of synthetic products 1, 2, and 3 of pigment A2 was measured according to the test method of JIS K5101-17-1:2004 ((a14) in Table 12).
- Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous ink composition. The unit is % by mass. The particle size and dispersion time of the zirconia beads are shown in Tables 13 to 20 below.
- volume-based cumulative 90% particle size (D90) of the pigment contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
- Storage stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, the non-aqueous ink composition was stored at 60° C. for one month, and changes in viscosity and volume-based cumulative 50% particle size (D50) of the pigment before and after the test were observed. evaluated the sex. The viscosity of the ink is measured at 20°C using a falling ball viscometer (AMVn manufactured by Anton Paar). It was measured at 25° C. using a particle size analyzer (NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
- Evaluation 2 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 8% or more and less than 10%.
- Evaluation 1 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 10% or more.
- Ejection stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, an inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.) is filled with a non-aqueous ink composition, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.) is used. )) in a bi-directional high-speed printing mode (360 x 720 dpi), solid and fine lines are printed by continuous printing at a substrate surface temperature of 40 ° C, and the presence or absence of missing dots, flight deflection, and ink splattering is visually observed.
- a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.)
- a bi-directional high-speed printing mode 360 x 720 dpi
- Evaluation Criteria Evaluation 5 Within the 24-hour test period, dot missing, flight deflection, or ink scattering occurred less than 10 times. Evaluation 4: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 10 times or more and less than 20 times. Evaluation 3: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 20 times or more and less than 30 times. Evaluation 2: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 30 times or more and less than 40 times. Evaluation 1: During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 40 times or more. "
- Solid filling was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, with the inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.), a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) was printed bidirectionally. Printing was carried out at a substrate surface temperature of 40° C. in a high-speed printing mode (360 ⁇ 720 dpi), and filling (blank spots) of the solid printed portion was confirmed (denoted as “solid filling” in the table).
- a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
- Evaluation Criteria Evaluation 5 A uniform solid image is formed Evaluation 4: White spots cannot be visually confirmed, but slight color unevenness can be confirmed, but the design is not impaired Evaluation 3: White spots cannot be visually confirmed However, color unevenness can be observed. Evaluation 2: White spots can be observed. Evaluation 1: White spots can be observed remarkably, and a decrease in density is observed. "
- the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for surface drying properties. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi), and the time taken to dry at 40°C was measured (referred to as "surface dryness" in the table). . Rating Criteria Rating 5: Dries in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: It dries in 8 minutes or more.
- Evaluation Criteria Evaluation 5 No bleeding of ink was observed with a loupe. Evaluation 4: No bleeding of the ink was visually observed, and 6 pt characters were clear. Evaluation 3: Slight bleeding of the ink was visually observed, but the design was not damaged. Evaluation 2: Bleeding of the ink was visually observed, but the 6pt characters were recognizable. Evaluation 1: Remarkable bleeding of the ink was visually observed, and 6 pt characters were not visually recognized.
- the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for abrasion resistance of coating films. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high quality print mode (1440 ⁇ 720 dpi) and dried at 40°C. The printed surface of the printed matter was rubbed with a piece of test cloth under a load of 200 g for 50 reciprocations, and the abrasion resistance was visually evaluated.
- a recording medium adheresive polychlorinated
- IMAGin JT5829R manufactured by MACtac
- Evaluation Criteria Evaluation 5 The ink film was not peeled off, and no ink adhered to the test cloth.
- Evaluation 4 The ink film was not peeled off, but ink adhered to the test cloth.
- Evaluation 3 The ink film was slightly peeled off, and the ink film adhered to the test cloth.
- Evaluation 2 The ink film was slightly peeled off, and the ink film adhered to the test cloth.
- Evaluation 1 Most of the ink film was peeled off, and the ink film adhered to the test cloth.
- the weather resistance of prints produced using the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples was evaluated.
- the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with adhesive (IMAGin JT5829R (manufactured by MACtac)) was printed with a solid image in a high-quality print mode (1440 ⁇ 720 dpi) and dried at 40° C. for 1 hour.
- the recorded matter thus obtained was placed in a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki Co., Ltd.) and subjected to a cycle test.
- Test conditions are based on JIS K-5600-7-7, black panel temperature: 63°C, xenon lamp irradiance: 60W/m 2 , test layer temperature: 38°C, and segment 1 humidity is 50%. 102 minutes in a state of maintaining at 200° C., and 18 minutes of water irradiation in segment 2, which was regarded as one cycle. With 50 cycles as one set, this cycle test was continued for 10 sets. The value of hue change ⁇ E before and after the test was evaluated, and the hue was evaluated under the following conditions.
- Evaluation 3 ⁇ E is less than 30.0 and 20.0 or more.
- the The water-based ink composition had good storage stability even when compared with Examples 9 and 12.
- the resin having an intrinsic viscosity of 90 mL/g or more at 25°C in which the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C was changed, the resin having an intrinsic viscosity of 90 mL/g or more at 25°C
- the non-aqueous ink compositions of Examples in the range of 5% by mass or less based on the total amount of the resin have improved solid filling and intermittent ejection properties compared to the non-aqueous ink compositions of Examples in the range of more than 5% by mass. Was.
- organic solvent B (at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)) of Example 2-1
- organic solvent B at least one selected from the group consisting of alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)
- the aqueous ink composition has high storage stability and recovery from cleaning, and the effect of the present invention is particularly effective. It can be seen that the
- Example 2-33 to 2-40 in which the content of the organic solvent B was changed, Examples 2-33 to 2-39 in which the content of the organic solvent B was in the range of 1% by mass or more and 90% by mass or less
- the non-aqueous ink composition of Example 2-40 has higher storage stability and recovery from cleaning than the non-aqueous ink composition of Example 2-40, and it can be seen that the effects of the present invention are exhibited particularly effectively.
- the various properties required for the non-aqueous ink composition ejected by the inkjet method are also better, and the organic solvent B (alkylamide solvent (b1), cyclic amide solvent ( b2) and at least one selected from the group consisting of a lactone solvent (b3)), the effects of the present invention are particularly effective.
- Example 2-51 to 2-54 in which the content of pigment A2 was changed, the content of pigment A2 was 0.1% by mass or more and 8.0% by mass or less based on the total amount of the non-aqueous ink composition.
- the non-aqueous ink compositions of Examples 2-51 to 2-53 had better storage stability than that of Example 2-54.
- Examples 2-59 to 2-64 and 2-70 in which the type of pigment dispersant was changed Examples 2-60 to 2-64 and 2-70 in which a pigment dispersant having a basic group was used
- the non-aqueous ink composition of Example 2-60 had improved ejection stability even when compared with the non-aqueous ink composition of Example 2-60.
- the non-aqueous ink compositions of Examples 2-60 to 2-63 having an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less showed particularly improved ejection stability.
- Example 2-65 to 2-68 in which the content of the pigment dispersant was changed, the range of 5 parts by mass to 150 parts by mass with respect to 100 parts by mass of the pigment in the non-aqueous ink composition
- the ink compositions of Examples 2-65 to 2-67 had improved surface drying properties and abrasion resistance of the coating film compared to the ink composition of Example 2-68.
- Example 2-69 which did not contain a surfactant having a siloxane skeleton, had a relatively slightly reduced paint film abrasion resistance.
- C.I. I. Pigment Red 149, C.I. I. Reference Examples 2-1 and 2-2 containing Pigment Red 188 satisfy the properties required for a non-aqueous ink composition ejected by an inkjet method, and easily aggregate in the non-aqueous ink composition. is a problem unique to non-aqueous ink compositions containing diketopyrrolopyrrole pigments.
- the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 30,000 to 105,000 (this The mass of the polymerization initiator used at that time is shown in Table 1 below, which is indicated as "initiator amount" in Table 21).
- Polyester-based resin 104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were charged into a round-bottom flask, and 240 parts by mass were added over 4 hours.
- the temperature was gradually raised to °C, and the esterification reaction was carried out while removing the distillate out of the system. After completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250° C. for initial polymerization. After that, post-polymerization was carried out at 1 mmHg or less for 1 hour to obtain a polyester resin.
- PPAXEL CD-220 manufactured by Daicel
- IPDI isophorone diisocyanate
- DEF N,N-diethylformamide
- N,N-diethylformamide (DEF) was added to this and dissolving it uniformly.
- 12 parts by mass of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) was dissolved in 100 parts by mass of DEF.
- the elongation agent solution was added and stirred at 60° C. for an additional 40 minutes.
- a reaction terminator in which 3.8 parts by mass of monoisopropanolamine (MIPA: manufactured by Daicel) is dissolved in 50 parts by mass of N,N-diethylformamide (DEF) is added, and finally N,N-diethylformamide (DEF) is added.
- MIPA monoisopropanolamine
- DEF N,N-diethylformamide
- Table 21 shows the weight average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, polyester resin, polyurethane resin) and the intrinsic viscosity at 25 ° C. of 90 mL. / g or more resin ratio.
- the weight average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography).
- the ratio of the resin with an intrinsic viscosity of 90 mL / g or more is determined by connecting a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T-rEX manufactured by WYATT) to a Shimadzu SEC (GPC) system, Using tetrahydrofuran as a developing solvent, the sample was first passed through a column heated to 40°C in the Shimadzu SEC (GPC) system, and then cooled to 25°C. ⁇ SP ] was determined, the concentration C was determined by a refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP ]/C).
- Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous ink composition. The unit is % by mass. The particle size and dispersion time of the zirconia beads are shown in Tables 22 to 29 below.
- volume-based cumulative 90% particle size (D90) of the pigment contained in the non-aqueous ink composition was measured using a particle size distribution analyzer (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
- Storage stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, the non-aqueous ink composition was stored at 60° C. for one month, and changes in viscosity and volume-based cumulative 50% particle size (D50) of the pigment before and after the test were observed. evaluated the sex. The viscosity of the ink is measured at 20°C using a falling ball viscometer (AMVn manufactured by Anton Paar). It was measured at 25° C. using a particle size analyzer (NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.).
- the non-aqueous ink composition was evaluated based on which of the "viscosity” and "volume-based cumulative 50% particle diameter (D50) of the pigment” had a larger rate of change (in the table, "storage stability”).
- Evaluation Criteria Evaluation 5 The rate of change in both the viscosity and the volume-based cumulative 50% particle size (D50) of the pigment is less than 3%.
- Evaluation 4 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 3% or more and less than 5%.
- Evaluation 3 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 5% or more and less than 8%.
- Evaluation 2 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 8% or more and less than 10%.
- Evaluation 1 Either the change rate of the viscosity or the volume-based cumulative 50% particle diameter (D50) of the pigment is 10% or more.
- Ejection stability was evaluated for the non-aqueous ink compositions of Examples, Comparative Examples, and Reference Examples. Specifically, an inkjet printer (trade name: VersaArt RE-640, manufactured by Roland DG Co., Ltd.) is filled with a non-aqueous ink composition, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.) is used. )) in a bi-directional high-speed printing mode (360 x 720 dpi), solid and fine lines are printed by continuous printing at a substrate surface temperature of 40 ° C, and the presence or absence of missing dots, flight deflection, and ink splattering is visually observed.
- a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: MACtac Co., Ltd.)
- a bi-directional high-speed printing mode 360 x 720 dpi
- Evaluation 3 ⁇ E is less than 3.0 and 2.5 or more.
- the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples were evaluated for surface drying properties. Specifically, the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (adhesive polychlorinated A solid image was printed on a vinyl film (IMAGin JT5829R: manufactured by MACtac) in a high-quality print mode (1440 x 720 dpi), and the time taken to dry at 40°C was measured (referred to as "surface dryness" in the table). . Rating Criteria Rating 5: Dries in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: It dries in 8 minutes or more.
- Evaluation Criteria Evaluation 5 No bleeding of ink was observed with a loupe. Evaluation 4: No bleeding of the ink was visually observed, and 6 pt characters were clear. Evaluation 3: Slight bleeding of the ink was visually observed, but the design was not damaged. Evaluation 2: Bleeding of the ink was visually observed, but the 6pt characters were recognizable. Evaluation 1: Remarkable bleeding of the ink was visually observed, and 6 pt characters were not visually recognized.
- the weather resistance of prints produced using the non-aqueous ink compositions of Examples, Comparative Examples and Reference Examples was evaluated.
- the non-aqueous ink compositions of Examples and Comparative Examples were applied to a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R (manufactured by MACtac)) was printed with a solid image in a high-quality print mode (1440 ⁇ 720 dpi) and dried at 40° C. for 1 hour.
- the recorded matter thus obtained was put into a xenon weather meter (ATLAS Ci4000: manufactured by Toyo Seiki Co., Ltd.) and subjected to a cycle test.
- Test conditions are based on JIS K-5600-7-7, black panel temperature: 63°C, xenon lamp irradiance: 60W/m 2 , temperature inside test layer: 38°C, and humidity in segment 1 is 50%. 102 minutes in a state of maintaining at 200° C., and 18 minutes of water irradiation in segment 2, which was regarded as one cycle. With 50 cycles as one set, this cycle test was continued for 10 sets. The value of hue change ⁇ E before and after the test was evaluated, and the hue was evaluated under the following conditions.
- Evaluation 4 ⁇ E is less than 10.0 and 5.0 or more.
- Evaluation 3 ⁇ E is less than 15.0 and 10.0 or more.
- Evaluation 2 ⁇ E is less than 20.0 and 15.0 or more.
- Pigment Green 7 in the table is chlorinated copper phthalocyanine and corresponds to a halogenated phthalocyanine pigment (density: 2.0 g/cm 3 ).
- Pigment Green 36 in the table is a brominated chlorinated copper phthalocyanine and corresponds to a halogenated phthalocyanine pigment (density: 2.7 g/cm 3 ).
- Pigment Green 58 in the table is a halogenated zinc phthalocyanine and corresponds to a halogenated phthalocyanine pigment.
- C.I. I. Pigment Blue 15:4" (density: 1.6 g/cm 3 ) and "C.I. Pigment Yellow 155" (density: 1.45 g/cm 3 ) correspond to pigments that are not halogenated phthalocyanine pigments.
- the halogenated phthalocyanine pigment A3 is contained, and the organic solvent is an organic solvent B (alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)
- organic solvent B alkylamide solvent (b1), cyclic amide solvent (b2), and lactone solvent (b3)
- the non-aqueous ink compositions of the examples containing at least one selected from the group consisting of (1) have high storage stability, high color tone stability, and high recovery from cleaning, even if they contain a halogenated phthalocyanine pigment. I understand.
- the content of the organic solvent B (alkylamide solvent) was 5% by mass or more.
- the non-aqueous ink compositions of Examples 3-9 to 3-14 had better color tone stability than that of Example 3-8.
- the storage stability and color tone stability were good.
- Examples 3-28 to 3-33 in which the volume-based cumulative 50% particle diameter (D50) and the volume-based cumulative 90% particle diameter (D90) of the halogenated phthalocyanine pigment A3 were changed, D50 is 150 nm or less and D90 is 300 nm or less, Examples 3-28 to 3-31 have better storage stability and color tone stability than the non-aqueous ink composition of Example 3-33.
- the content of the pigment A3 was 0.1% by mass or more and 8.0% by mass or less.
- the non-aqueous ink compositions of Examples 3-36 to 3-36 had better storage stability and color tone stability than the non-aqueous ink composition of Example 3-37.
- the resin having an intrinsic viscosity of 90 mL/g or more at 25°C in which the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C was changed, the resin having an intrinsic viscosity of 90 mL/g or more at 25°C
- the non-aqueous ink compositions of Examples in the range of 5% by mass or less based on the total amount of the resin exhibited solid filling and ejection stability compared to the non-aqueous ink compositions of Examples in the range of more than 5% by mass. was improving.
- Example 3-55 to 3-60 and 3-66 in which the type of pigment dispersant was changed, Examples 3-56 to 3-60 and 3-66 in which a pigment dispersant having a basic group was used
- the non-aqueous ink composition of Example 3-55 had improved storage stability and ejection stability compared to the non-aqueous ink composition of Example 3-55.
- the non-aqueous ink compositions of Examples 3-57 to 3-60 and 3-66 which have an amine value in the range of 20 mgKOH/g or more and 100 mgKOH/g or less, have particularly improved storage stability and ejection stability. rice field.
- Example 3-61 to 3-64 in which the content of the pigment dispersant was changed, the range of 5 parts by mass to 150 parts by mass with respect to 100 parts by mass of the pigment in the non-aqueous ink composition
- the ink compositions of Examples 3-61 to 3-63 had improved surface drying properties compared to the ink composition of Example 3-64.
- Example 3-68 which did not contain a surfactant having a siloxane skeleton, had a relatively slightly reduced bleeding property.
- Comparative Examples 3-1 to 3-3 containing no organic solvent B (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3))
- the non-aqueous ink composition of -3 does not exhibit the effects of the present invention.
- non-aqueous ink composition of Reference Example 3-1 which did not contain the halogenated phthalocyanine pigment A3, had good storage stability and color tone stability even though it did not contain the organic solvent B.
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Abstract
Description
前記顔料は、下記式(1-1)で示される顔料A1又は下記式(1-2)で示される顔料A2の少なくとも1つを含有し、
前記顔料A1及びA2のpHは3以上9以下の範囲内である、
非水性インク組成物。
有機溶剤B:アルキルアミド系溶剤(b1)、環状アミド系溶剤(b2)、及びラクトン系溶剤(b3)からなる群より選択される少なくとも1つ
有機溶剤B:アルキルアミド系溶剤(b1)、環状アミド系溶剤(b2)、及びラクトン系溶剤(b3)からなる群より選択される少なくとも1つ
前記環状アミド系溶剤(b2)は、ε-カプロラクタム、N-メチルカプロラクタム、及びN-ビニルカプロラクタムからなる群より選択される少なくとも1つを含有する(17)に記載の非水性インク組成物。
記録方法。
本発明の1つの実施形態(例えば、第1、第2、第3実施形態の非水性インク組成物)の非水性インク組成物は、顔料と、顔料分散剤と、有機溶剤と、を含有するインクジェット法によって吐出される非水性インク組成物である。ここで、本明細書において、「非水性インク組成物」とは、水を主成分とする水性インク組成物とは異なり、水を意図的に含有させずに製造された有機溶剤を含むインク組成物であることを意味する。
≪1-1.第1実施形態の非水性インク組成物≫
本実施の形態に係る第1実施形態の非水性インク組成物は、顔料と、顔料分散剤と、有機溶剤と、を含有するインクジェット法によって吐出される非水性インク組成物である。ここで、「非水性インク組成物」とは、水を主成分とする水性インク組成物とは異なり、水を意図的に含有させずに製造された有機溶剤を含むインク組成物であることを意味する。
有機溶剤は、本実施の形態に係る非水性インク組成物に含有される各成分を分散又は溶解することができるものである。有機溶剤は、特に限定されないが、顔料A1を含有する顔料を分散させて、本発明の効果をより効果的に奏する観点から、有機溶剤B(アルキルアミド系溶剤(b1)、環状アミド系溶剤(b2)、及びラクトン系溶剤(b3)からなる群より選択される少なくとも1つ)を含有することが好ましい。
アルキルアミド系溶剤とは、アルキル基(CnH2n+1-)と-C(=O)-N-基(アミド結合)を有する化合物であって、水素若しくはアルキル基と-C(=O)-N-基から構成された化合物からなる溶剤である。アルキルアミド系溶剤は、例えば以下の構造を有するものを好ましく用いることができる。
環状アミド系溶剤(b2)とは、環状構造を有し、その環状構造に-C(=O)-N-基を有する溶剤である。環状アミド系溶剤は、例えば以下の構造を有するものを好ましく用いることができる。
ラクトン系溶剤とは、環状エステル構造を有する溶剤である。ラクトン系溶剤は、例えば以下の構造を有するものを好ましく用いることができる。
本実施の形態に係る非水性インク組成物は、上記の有機溶剤B以外の有機溶剤を含有していてもよい。具体的には、グリコールの両末端のOH基がアルキル置換されたグリコールエーテルジアルキルやグリコールの片方のOH基がアルキル置換されたグリコールエーテルモノアルキルや炭酸エステルなどが挙げられる。
(式(5)中、R8、R10は、それぞれ独立して、水素または炭素数1以上8以下の分岐しても良いアルキル基であり、R9は炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。)
本実施の形態に係る非水性インク組成物において必要に応じて分散剤を用いてもよい。分散剤としては、非水性インク組成物において用いられている任意の分散剤を用いることができる。分散剤としては、高分子分散剤を用いるとよい。こうした分散剤としては、主鎖がポリエステル系、ポリアクリル系、ポリウレタン系、ポリアミン系、ポリカプロラクトン系などからなり、側鎖としてアミノ基、カルボキシル基、スルホン基、ヒドロキシル基などの極性基を有するものである。ポリアクリル系分散剤では、例えば、Disperbyk-2000、2001、2008、2009、2010、2020、2020N、2022、2025、2050、2070、2095、2150、2151、2155、2163、2164、BYKJET-9130、9131,9132,9133,9151(ビック・ケミー社製)、EfkaPX4310、PX4320、PX4330、PA4401、4402、PA4403、4570、7411、7477、PX4700、PX4701(BASF社製)、TREPLUS D-1200、D-1410、D-1420、MD-1000(大塚化学社製)、フローレンDOPA-15BHFS、17HF、22、G-700、900、NC-500、GW-1500(共栄社化学(株)製)、などが用いられる。ポリカプロラクトン系分散剤では、例えば、アジスパーPB821、PB822、PB881(味の素ファインテクノ(株)製)、ヒノアクトKF-1000、T-6000、T-7000、T-8000、T-8000E、T-9050(川研ファインケミカル(株)製)、Solsperse20000、24000、32000、32500、32550、32600、33000、33500、34000、35200、36000、37500、39000、71000、76400、76500、86000、88000、J180、J200(ルーブリゾール社製)、TEGO Dispers652、655、685、688、690(エボニック・ジャパン社製)などが用いられる。好ましい分散剤としては、BYKJET-9130、9131,9132,9133,9151、EfkaPX4310、PX4320、PX4330、PX4700、PX4701、Solsperse20000、24000、32000、33000、33500、34000、35200、39000、71000、76500、86000、88000、J180、J200、TEGO Dispers655、685、688、690などが用いられる。これらの単独、又はそれらの混合物を用いることができる。
本実施の形態に係る非水性インク組成物において必要に応じて分散助剤を用いてもよい。分散助剤は色材(顔料)の表面に吸着し、官能基が非水性インク組成物中の有機溶剤や分散剤との親和力を高め、分散安定性を向上させる。分散助剤としては、上記に記載された顔料の誘導体が好ましく、有機顔料残基に酸性基、塩基性基、中性基などの官能基を有する公知の顔料誘導体を用いることができる。後述する第2、第3実施形態の非水性インク組成物においても同様である。
本実施の形態に係る非水性インク組成物は樹脂を含有しなくともよいが、樹脂を含有していてもよい。樹脂を含有することにより、非水性インク組成物により形成される記録層の定着性、耐水性並びに延伸性を向上させることができる。さらに、得られる記録物の光沢性を向上させることができる。後述する第2、第3実施形態の非水性インク組成物においても同様である。
本実施の形態に係る非水性インク組成物においては、ノズル部やチューブ内等の機器内での非水性インク組成物の揮発抑制、固化防止、又、固化した際の再溶解性を目的として、又、表面張力を低下させ記録媒体(基材)との濡れ性を向上させる目的で、また、インク組成物の基材上でのにじみ抑制を目的として、また、塗膜の耐擦性向上を目的として、また、記録物の更なる光沢性の向上を目的として、界面活性剤を添加してもよい。後述する第2、第3実施形態の非水性インク組成物においても同様である。
本実施の形態に係る非水性インク組成物は、酸化防止剤や紫外線吸収剤等の安定剤、エポキシ化物等、多価カルボン酸、表面調整剤、レベリング剤(アクリル系やシリコン系等)、消泡剤、pH調整剤、殺菌剤、防腐剤、防臭剤、電荷調整剤、湿潤剤等の公知の添加剤を任意成分として含んでもよい。酸化防止剤の具体例としては、例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、ヒドラジン系酸化防止剤等が挙げられる。具体的には、BHA(2,3-ブチル-4-オキシアニソール)、BHT(2,6-ジ-t-ブチル-p-クレゾール)等が例示される。また、紫外線吸収剤としてはベンゾフェノン系化合物、又はベンゾトリアゾール系化合物を用いることができる。また、エポキシ化物の具体例としては、エポキシグリセリド、エポキシ脂肪酸モノエステル、およびエポキシヘキサヒドロフタレートなどが例示され、具体的にはアデカサイザーO-130P、アデカサイザーO-180A(ADEKA社製)等が例示される。多価カルボン酸の具体例としては、クエン酸、マレイン酸などが例示される。
本実施の形態に係る第2実施形態の非水性インク組成物は、顔料と、顔料分散剤と、有機溶剤と、を含有するインクジェット法によって吐出される非水性インク組成物である。
有機溶剤は、本実施の形態に係る非水性インク組成物に含有される各成分を分散又は溶解することができるものである。有機溶剤は、特に限定されないが、顔料A2を含有する顔料を分散させて、本発明の効果をより効果的に奏する観点から、有機溶剤B(アルキルアミド系溶剤(b1)、環状アミド系溶剤(b2)、及びラクトン系溶剤(b3)からなる群より選択される少なくとも1つ)を含有することが好ましい。
本実施の形態に係る非水性インク組成物は、上記の有機溶剤B以外の有機溶剤を含有していてもよい。具体的には、グリコールの両末端のOH基がアルキル置換されたグリコールエーテルジアルキルやグリコールの片方のOH基がアルキル置換されたグリコールエーテルモノアルキルや炭酸エステルやその他の溶剤(オキサゾリジノン系溶剤、アセテート系溶剤、アルキルアミド系溶剤(b1)や環状アミド系溶剤(b2)とは異なるアミド系溶剤、アルキルアルコール類、ケトン又はケトアルコール類、エーテル類、オキシエチレン又はオキシプロピレン共重合体、ジオール類、4価アルコール類、アルカノールアミン類等)が挙げられる。その他の有機溶剤における好ましい溶剤の種類は、上述した第1実施形態の非水性インク組成物におけるグリコールエーテルジアルキルやグリコールエーテルモノアルキルや炭酸エステルと同様である。非水性インク組成物に含有されるその他の有機溶剤の合計含有量の好ましい範囲は、上述した第1実施形態の非水性インク組成物と同様である。
本実施の形態に係る非水性インク組成物において必要に応じて分散剤を用いてもよい。好ましい顔料分散剤の種類は、上述した第1実施形態の非水性インク組成物における顔料分散剤と同様である。
本実施の形態に係る非水性インク組成物において必要に応じて分散助剤を用いてもよい。
本実施の形態に係る非水性インク組成物は樹脂を含有しなくともよいが、樹脂を含有していてもよい。好ましい樹脂の種類は、上述した第1実施形態の非水性インク組成物における樹脂と同様である。非水性インク組成物に含有される樹脂の含有量や5℃における固有粘度が90mL/g以上の樹脂の好ましい範囲は、上述した第1実施形態の非水性インク組成物と同様である。
本実施の形態に係る非水性インク組成物は界面活性剤を添加してもよい。
本実施の形態に係る非水性インク組成物は、その他の成分を任意成分として含んでもよい。非水性インク組成物に含有されるその他の成分の種類は、上述した第1実施形態の非水性インク組成物と同様である。
本実施の形態に係る非水性インク組成物は、顔料と、顔料分散剤と、有機溶剤と、を含有するインクジェット法によって吐出される非水性インク組成物である。
本実施の形態に係る非水性インク組成物に含有される顔料は、ハロゲン化フタロシアニン顔料A3を含有する。ハロゲン化フタロシアニン顔料A3は、下記式のようなフタロシアニン骨格を有する化合物である。
有機溶剤は、本実施の形態に係る非水性インク組成物に含有される各成分を分散又は溶解することができるものである。有機溶剤は、有機溶剤B(アルキルアミド系溶剤(b1)、環状アミド系溶剤(b2)、及びラクトン系溶剤(b3)からなる群より選択される少なくとも1つ)を含有する。
本実施の形態に係る非水性インク組成物は、上記の有機溶剤B以外の有機溶剤を含有していてもよい。具体的には、グリコールの両末端のOH基がアルキル置換されたグリコールエーテルジアルキルやグリコールの片方のOH基がアルキル置換されたグリコールエーテルモノアルキルや炭酸エステルやその他の溶剤(オキサゾリジノン系溶剤、アセテート系溶剤、アルキルアミド系溶剤(b1)や環状アミド系溶剤(b2)とは異なるアミド系溶剤、アルキルアルコール類、ケトン又はケトアルコール類、エーテル類、オキシエチレン又はオキシプロピレン共重合体、ジオール類、4価アルコール類、アルカノールアミン類等)が挙げられる。その他の有機溶剤における好ましい溶剤の種類は、上述した第1実施形態の非水性インク組成物におけるグリコールエーテルジアルキルやグリコールエーテルモノアルキルや炭酸エステルと同様である。非水性インク組成物に含有されるその他の有機溶剤の合計含有量の好ましい範囲は、上述した第1実施形態の非水性インク組成物と同様である。
本実施の形態に係る非水性インク組成物において必要に応じて顔料分散剤を用いてもよい。特に、顔料A3を含有する本実施の形態に係る非水性インク組成物において、塩基性基を有する顔料分散剤を使用することが好ましい。また、塩基性基を有する顔料分散剤を使用することで非水性インク組成物中でのハロゲン化フタロシアニン顔料A3の凝集をより効果的に抑制することができる。好ましい顔料分散剤の種類は、上述した第1実施形態の非水性インク組成物における顔料分散剤と同様である。
本実施の形態に係る非水性インク組成物において必要に応じて分散助剤を用いてもよい。
本実施の形態に係る非水性インク組成物は樹脂を含有しなくともよいが、樹脂を含有していてもよい。好ましい樹脂の種類は、上述した第1実施形態の非水性インク組成物における樹脂と同様である。非水性インク組成物に含有される樹脂の含有量の好ましい範囲は、上述した第1実施形態の非水性インク組成物と同様である。
本実施の形態に係る非水性インク組成物は界面活性剤を添加してもよい。好ましい界面活性剤の種類は、上述した第2実施形態の非水性インク組成物における界面活性剤と同様である。非水性インク組成物に含有される界面活性剤の含有量の好ましい範囲は、上述した第2実施形態の非水性インク組成物と同様である。
本実施の形態に係る非水性インク組成物は、その他の成分を任意成分として含んでもよい。非水性インク組成物に含有されるその他の成分の種類は、上述した第1実施形態の非水性インク組成物と同様である。
本実施の形態に係る非水性インク組成物の製造方法は、有機溶剤と、顔料A1、又A2を含有する顔料と他成分(例えば樹脂等)をペイントシェイカーを用いて混合することにより製造することができる。この際、ジルコニアビーズにて各成分を分散させてもよい。また、得られた非水性インク組成物は、必要に応じて脱気処理するなどして所望の溶存酸素量や溶存窒素量に調整してもよい。
本実施の形態に係る記録方法は、上記の非水性インク組成物を、インクジェット方式にて基材の表面に吐出する記録方法である。上記の非水性インク組成物のうち第1及び第2実施形態の非水性インク組成物は、pHは3以上9以下の範囲内になるように構造中の置換基が変更された顔料A1、又はA2を含有することで、インクジェット法によって吐出される非水性インク組成物に要求される特性を満たすものであり、本実施の形態に係る記録方法においても、インクジェット法によって吐出される非水性インク組成物に要求される特性を満たすものである。上記の非水性インク組成物のうち第3実施形態の非水性インク組成物は、ハロゲン化フタロシアニン顔料A3を含んでいても保存安定性及び色調安定性が高いものであり、本実施の形態に係る記録方法を使用して得られた記録物においても色調安定性が高いものである。インクジェット法により吐出する方式は、圧電素子を用いたピエゾ方式であっても、発熱体を用いたサーマル方式であってもよく、特に限定されない。
上記のインク組成物を用いた記録方法は、記録物の製造方法と定義することもできる。上記の非水性インク組成物のうち第1実施形態の非水性インク組成物を使用して記録物を製造することにより、インクジェット法によって吐出される非水性インク組成物に要求される特性を満たした状態で記録物を製造することができる。また、上記の非水性インク組成物のうち第2実施形態の非水性インク組成物を使用して記録物を製造することにより、保存安定性が高く、クリーニング回復性が高い特性を満たした状態で記録物を製造することができる。また、上記の非水性インク組成物のうち第3実施形態の非水性インク組成物を使用して記録物を製造することにより、色調安定性が高い記録物が得られる。
上述した実施形態の記録物の製造方法により製造された記録物を構成する各層について説明する。
本実施の形態に係る記録方法に使用することのできる基材(記録媒体)としては、特に限定はされず、樹脂基材、金属、板ガラスなどの非吸収性基材であっても、紙や布帛などの吸収性基材であっても、受容層を備える基材のような表面塗工が施された基材であってもよく、種々の基材を使用することができる。
記録層(印刷層ともいう。)とは、上記の非水性インク組成物に含まれる溶媒が揮発することにより形成される層であり、所望の画像を形成する層である。上記の非水性インク組成物のうち第1実施形態の非水性インク組成物を吐出することでインクジェット法によって吐出される非水性インク組成物に要求される特性を満たすものとなる。上記の非水性インク組成物のうち第2実施形態の非水性インク組成物は保存安定性が高く、クリーニング回復性が高いものであるので、長期間保存された非水性インク組成物であっても所望の画像を形成することが可能である。上記の非水性インク組成物のうち第3実施形態の非水性インク組成物を吐出することで色調安定性が高い記録層となる。また、上記の非水性インク組成物は保存安定性が高いものであるので、長期間保存された非水性インク組成物であっても所望の画像を形成することが可能である。
本実施の形態に係る記録物は、さらに記録層(印刷層)の上表面に所望の機能を有する層を備えてもよい。例えば、記録物に耐擦性や光沢性をさらに付与する目的で、樹脂、ワックスの少なくとも1つを含有するオーバーコート層が形成されていてもよい。また、フィラーを含有させ、又は膜厚をピクセル単位で変化させること等により、表面に凹凸感(マット面)を表現された層が形成されていてもよい。また、記録物に耐候性を付与するために、紫外線吸収剤や光安定化剤等を含む耐候層や光輝性顔料を含む光輝性層等が形成されていてもよい。
本実施の形態に係るインクセットは、上記の非水性インク組成物を少なくとも備えるインクセットである。例えば、上記の非水性インク組成物がレッドインク、オレンジインク又はグリーンインクである場合には、従来公知のイエローインク、マゼンタインク、シアンインク、ブラックインクと、を組み合わせることで、本発明の効果を奏することに加えて、色再現性を拡げることが可能となる。
上記の非水性インク組成物をインクジェット法により吐出するインクジェット記録装置は、従来公知のものを使用することができる。例えば、VersaArt RE-640、ローランドDG(株)製のようなインクジェットプリンターなどを使用することができる。
1.樹脂の作製
(1)アクリル系樹脂
100℃に保たれたジエチレングリコールジエチルエーテル300g中に、メタクリル酸メチル150g及びメタクリル酸ブチル50gと所定量のt-ブチルパーオキシ-2-エチルヘキサノエート(重合開始剤)との混合物を1.5時間かけて滴下した。滴下終了後、100℃で2時間反応させた後冷却して、無色透明のメタクリル酸メチルの重合体溶液を得た。その後、この重合体溶液から溶媒を十分に留去して、メタクリル酸メチルの重合体を得た。このとき重合開始剤であるt-ブチルパーオキシ-2-エチルヘキサノエートの量を変更して、メタクリル酸メチル(アクリル系樹脂)の重合平均分子量を30000~105000になるように制御した(このとき使用した重合開始剤の質量を下記表1に記載した。表1中「開始剤量」と表記した。)。
撹拌装置を備えたオートクレーブに、窒素置換後、脱イオン水100部、メタノール40部、塩化ビニル32部、酢酸ビニル5部、グリシジルメタクリレート0.2部、ヒドロキシプロピルアクリレート3.55部、ヒドロキシプロピルメチルセルロース(懸濁剤)を0.1部、ジ-2-エチルヘキシルパーオキシジカーボネート(重合開始剤)を0.026部、ジ-3,5,5-トリメチルヘキサノールパーオキサイド(重合開始剤)を所定量仕込み、窒素ガス雰囲気下に撹拌しながら63℃に昇温し、63℃に到達直後に塩化ビニル48部を6時間で、グリシジルメタクリレート0.6部、ヒドロキシプロピルアクリレート10.65部を混合したものを5.4時間で連続圧入し、共重合反応させた。オートクレーブ内圧が0.3MPaになった時点で残圧を抜き、冷却して樹脂スラリーを取り出し、ろ過、乾燥して塩化ビニル系共重合樹脂を得た。このとき重合開始剤であるジ-3,5,5-トリメチルヘキサノールパーオキサイドの量を変更して、塩化ビニル-酢酸ビニル共重合体樹脂の重合平均分子量を40000~75000になるように制御した(このとき使用した重合開始剤の質量を下記表1に記載した。表1中「開始剤量」と表記した。)。
市販品のセルロース系樹脂(EASTMAN CHEMICAL社のCAB551-0.01、CAB553-0.4、CAP482-0.5)を用いた。
テレフタル酸104質量部、イソフタル酸104質量部、エチレングリコール79質量部、ネオペンチルグリコール89質量部、テトラブチルチタネート0.1質量部を丸底フラスコに仕込み、4時間かけて240℃まで徐々に昇温し、留出物を系外に除きながらエステル化反応を行った。エステル化反応終了後30分かけて10mmHgまで減圧、温度を250℃まで昇温し初期重合を行った。その後1mmHg以下で1時間後期重合を行い、ポリエステル系樹脂を得た。
ポリカーボネートジオール(プラクセルCD―220:ダイセル製)192.5質量部とイソホロンジイソシアネート(IPDI:エボニック製)41.6質量部、N,N-ジエチルホルムアミド(DEF)100質量部を丸底フラスコに入れ均一に混合後、T100BHJ(触媒)0.01質量部とN,N-ジエチルホルムアミド(DEF)0.09質量部の混合液を入れ75℃で3時間反応させて末端にイソシアネート基をもつプレポリマーを得た。これにN,N-ジエチルホルムアミド(DEF)を250質量部投入し均一に溶解後、3アミノメチル3,5,5トリメチルシクロヘキシルアミン(IPD:エボニック製)12質量部をDEF100質量部に溶解した鎖伸長剤溶液を添加し60℃でさらに40分撹拌した。その後モノイソプロパノールアミン(MIPA:ダイセル製)3.8質量部をN,N-ジエチルホルムアミド(DEF)50質量部に溶解した反応停止剤を添加し、最後にN,N-ジエチルホルムアミド(DEF)を250質量部添加して固形分25.0質量%のポリウレタン溶液を得た。
表2に記載の条件により顔料A1の合成品1~6を合成した。具体的には表2の(a1)のペリノン系顔料2質量部を表2の(a2)の溶媒に分散させて、表2の(a3)を(表2の(a4)部添加した。表2の(a5)の温度条件で表2の(a6)時間撹拌後、合成品1、2についてはエタノール、水洗し、合成品3、4、6は水洗して顔料A1の合成品1~6を得た。表2中顔料Ap(合成品5)とは特許第3076738に記載の方法で合成された顔料であって式(1-1)で示される顔料A1である。なお、合成品5については溶媒に分散させる処理を行わなかった。
それぞれの有機溶剤、樹脂、分散剤、顔料(色材)下記表の割合になるように各成分のように実施例及び比較例の非水性インク組成物を作製した。具体的には、ペイントシェイカーを用いてジルコニアビーズにて各成分を分散させて非水性インク組成物を調製した。単位は質量%である。なお、下記表3~10にジルコニアビーズの粒径、分散時間を記載する。
(保存安定性)
実施例、比較例および参考例の非水性インク組成物について保存安定性を評価した。具体的には、非水性インク組成物を60℃で1ヶ月間保存し、試験前後の粘度及び顔料の体積基準累積50%粒子径(D50)の変化を観察し、下記の基準で、保存安定性を評価した。なお、インクの粘度は、落球式粘度計(アントンパール社製AMVn)を用いて、20℃の条件下で測定され、顔料の体積基準累積50%粒子径(D50)は、粒子径分布測定装置(マイクロトラックベル(株)製粒度分析計NANOTRACWAVE)を用いて25℃の条件下で測定した。なお、下記の評価は「粘度」及び「体積基準累積50%粒子径(D50)」のうち、変化率が大きかった方をその非水性インク組成物の評価とした(表中、「保存安定性」と表記)。
評価基準
評価5:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれも3%未満である。
評価4:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが3%以上5%未満である。
評価3:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが5%以上8%未満である。
評価2:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが8%以上10%未満である。
評価1:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが10%以上である。
実施例、比較例および参考例の非水性インク組成物について吐出安定性を評価した。具体的には、インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)に非水性インク組成物を充填して、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に双方向の高速印刷モード(360x720dpi)で、基材表面温度40℃にて連続印刷でベタ及び細線を印刷し、ドット抜け、飛行曲がり、インクの飛び散りの有無を目視により観察し、発生回数を計測した(表中、「吐出安定性」と表記)。
評価基準
評価5:細線が正しく再現できている。
評価4:細線がおおむね正しく再現できている。
評価3:わずかに細線に曲がりがみられる。
評価2:着弾位置がずれており、曲がりが見られる。
評価1:着弾位置のずれが酷く、細線を再現できない。
実施例、比較例および参考例の非水性インク組成物について間欠吐出性を評価した。具体的には、インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に双方向の高速印刷モード(360x720dpi)で、基材表面温度40℃にて長期間に亘り、常温下で、上記記録媒体に断続的な印刷を実施し、ドット抜け、飛行曲がり及びインクの飛び散りの有無を観察し、発生回数を計数し評価した(表中、「間欠吐出性」と表記)。
評価基準
評価5:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が10回未満であった。
評価4:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が10回以上20回未満であった。
評価3:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が20回以上30回未満であった。
評価2:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が30回以上40回未満であった。
評価1:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が40回以上であった。
実施例、比較例および参考例の非水性インク組成物についてベタ埋まりを評価した。具体的には、上記インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に双方向の高速印刷モード(360x720dpi)で、基材表面温度40℃にて印刷を実施し、ベタ印字を行った部分の埋まり(白抜け)を確認した(表中、「ベタ埋まり」と表記)。
評価5:均一なベタが形成できている
評価4:目視で白抜けは確認できないが、わずかに色ムラが確認できるが意匠性は損なわれていない
評価3:目視で白抜けは確認できないが、色ムラが確認できる
評価2:白抜けが確認できる
評価1:顕著に白抜けが確認でき、濃度感の低下がみられる。
実施例、比較例および参考例の非水性インク組成物について表面乾燥性を評価した。具体的には、実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像の印刷を行い、40℃で乾燥するまでの時間を計測した(表中、「表面乾燥性」と表記)。
評価基準
評価5:2分未満で乾燥する。
評価4:2分以上4分未満で乾燥する。
評価3:4分以上6分未満で乾燥する。
評価2:6分以上8分未満で乾燥する。
評価1:8分以上で乾燥する。
実施例、比較例および参考例の非水性インク組成物について滲み性を評価した。具体的には、上記インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)で、基材表面温度50℃で各色のベタ部中にベタ部と異なる色の6ptの文字がある画像を印刷し、得られた印字物を60℃のオーブンで5分間乾燥後、当該印字物の滲みを目視、ルーペ(x10)で観察した。
評価基準
評価5:ルーペでインクの滲みが観察されなかった。
評価4:目視でインクの滲みが観察されず、6ptの文字が鮮明である。
評価3:目視でインクの滲みがわずかに観察されたが、意匠性は損なわれない。
評価2:目視でインクの滲みが観察されたが、6ptの文字は識別可能である。
評価1:目視でインクの滲みが顕著に観察され、6ptの文字は視認できなかった。
実施例及び比較例の非水性インク組成物について発色性を評価した。具体的には、上記インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像を印字した。彩度は、JIS Z 8721に基づき、X-Rite eXact(エックスライト社製)を用い、視野角2°、測定範囲 4mmφ、D65光源の条件で測定を行うことにより求めた。(表中、「発色性」と表記)。
評価基準
評価5:彩度が100以上である。
評価4:彩度が90以上、100未満である。
評価3:彩度が80以上、90未満である。
評価2:彩度が70以上、80未満である。
評価1:彩度が70未満である。
実施例、比較例および参考例の非水性インク組成物を使用して作製された印字物の耐候性を評価した。実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像の印刷を行い、40℃で1時間乾燥させた。
得られた記録物をキセノンウェザーメーター(ATLAS Ci4000:東洋精機製)内に投入し、サイクル試験を行った。試験条件はJIS K―5600-7-7に基づき、ブラックパネル温度:63℃、キセノンランプの放射照度:60W/m2、試験層内温度:38℃、に保ち、セグメント1では湿度を50%に保った状態で102分間、セグメント2では水照射を18分間行い、これを1サイクルとした。50サイクルを1セットとし、このサイクル試験を継続して10セット行った。 試験前後の色相変化ΔEの値を評価した、色相は以下の条件で評価した。X-Rite eXact(エックスライト社製)を用い、視野角2°、測定範囲 4mmφ、D65光源の条件でL*、a*、b*の値を測定した(表中、「耐候性」と表記)。
色相変化ΔEは、試験前L*1、a*1、b*1、試験後L*2、a*2、b*2の値を使用し、以下の式で求められる
ΔE=((L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2)(1/2)
評価基準
評価5:ΔEが10.0未満である。
評価4:ΔEが20.0未満、10.0以上である。
評価3:ΔEが30.0未満、20.0以上である。
評価2:ΔEが40.0未満、30.0以上である。
評価1:ΔEが50.0以上である。
実施例、比較例および参考例の非水性インク組成物について光沢性を評価した。具体的には、実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)で、基材表面温度40℃でベタ部の印刷を行い、60℃オーブンで5分乾燥させた後、当該印字物の20°光沢度を測定した。光沢度はハンディタイプの光沢度計PhopointIQ-S(コニカミノルタ社製)で測定した(表中、「光沢性」と表記)。
評価基準
評価5:20°光沢が70以上
評価4:20°光沢が65以上70未満
評価3:20°光沢が55以上65未満
評価2:20°光沢が50以上55未満
評価1:20°光沢が50未満
実施例、比較例および参考例の非水性インク組成物の沈降性の評価を行った。具体的には、非水性インク組成物30gを室温で1ヶ月間保存し、試験全後のインクの上澄み1gを取り、バーコーター#8で記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に展色し40℃オーブンで乾燥させた。試験前後の色相変化ΔEの値を評価した、色相は以下の条件で評価した。X-Rite eXact(エックスライト社製)を用い、視野角2°、測定範囲 4mmφ、D65光源の条件でL*、a*、b*の値を測定した(表中、「色調安定性(沈降性)」と表記」)。
色相変化ΔEは、試験前L*1、a*1、b*1、試験後L*2、a*2、b*2の値を使用し、以下の式で求められる。
ΔE=((L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2)(1/2)
評価基準
評価5:ΔEが2.0未満である。
評価4:ΔEが2.5未満、2.0以上である。
評価3:ΔEが3.0未満、2.5以上である。
評価2:ΔEが3.5未満、3.0以上である。
評価1:ΔEが3.5以上である。
1.樹脂の作製
(1)アクリル系樹脂
100℃に保たれたジエチレングリコールジエチルエーテル300g中に、メタクリル酸メチル150g及びメタクリル酸ブチル50gと所定量のt-ブチルパーオキシ-2-エチルヘキサノエート(重合開始剤)との混合物を1.5時間かけて滴下した。滴下終了後、100℃で2時間反応させた後冷却して、無色透明のメタクリル酸メチルの重合体溶液を得た。その後、この重合体溶液から溶媒を十分に留去して、メタクリル酸メチルの重合体を得た。このとき重合開始剤であるt-ブチルパーオキシ-2-エチルヘキサノエートの量を変更して、メタクリル酸メチル(アクリル系樹脂)の重合平均分子量を30000~105000になるように制御した(このとき使用した重合開始剤の質量を下記表11に記載した。表11中「開始剤量」と表記した。)。
撹拌装置を備えたオートクレーブに、窒素置換後、脱イオン水100部、メタノール40部、塩化ビニル32部、酢酸ビニル5部、グリシジルメタクリレート0.2部、ヒドロキシプロピルアクリレート3.55部、ヒドロキシプロピルメチルセルロース(懸濁剤)を0.1部、ジ-2-エチルヘキシルパーオキシジカーボネート(重合開始剤)を0.026部、ジ-3,5,5-トリメチルヘキサノールパーオキサイド(重合開始剤)を所定量仕込み、窒素ガス雰囲気下に撹拌しながら63℃に昇温し、63℃に到達直後に塩化ビニル48部を6時間で、グリシジルメタクリレート0.6部、ヒドロキシプロピルアクリレート10.65部を混合したものを5.4時間で連続圧入し、共重合反応させた。オートクレーブ内圧が0.3MPaになった時点で残圧を抜き、冷却して樹脂スラリーを取り出し、ろ過、乾燥して塩化ビニル系共重合樹脂を得た。このとき重合開始剤であるジ-3,5,5-トリメチルヘキサノールパーオキサイドの量を変更して、塩化ビニル-酢酸ビニル共重合体樹脂の重合平均分子量を40000~75000になるように制御した(このとき使用した重合開始剤の質量を下記表11に記載した。表11中「開始剤量」と表記した。)。
市販品のセルロース系樹脂(EASTMAN CHEMICAL社のCAB551-0.01、CAB553-0.4)を用いた。
テレフタル酸104質量部、イソフタル酸104質量部、エチレングリコール79質量部、ネオペンチルグリコール89質量部、テトラブチルチタネート0.1質量部を丸底フラスコに仕込み、4時間かけて240℃まで徐々に昇温し、留出物を系外に除きながらエステル化反応を行った。エステル化反応終了後30分かけて10mmHgまで減圧、温度を250℃まで昇温し初期重合を行った。その後1mmHg以下で1時間後期重合を行い、ポリエステル樹脂を得た。
ポリカーボネートジオール(プラクセルCD―220:ダイセル製)192.5質量部とイソホロンジイソシアネート(IPDI:エボニック製)41.6質量部、N,N-ジエチルホルムアミド(DEF)100質量部を丸底フラスコに入れ均一に混合後、T100BHJ(触媒)0.01部とN,N-ジエチルホルムアミド(DEF)0.09部の混合液を入れ75℃で3時間反応させて末端にイソシアネート基をもつプレポリマーを得た。これにN,N-ジエチルホルムアミド(DEF)を250質量部投入し均一に溶解後、3アミノメチル3,5,5トリメチルシクロヘキシルアミン(IPD:エボニック製)12質量部をN,N-ジエチルホルムアミド(DEF)100質量部に溶解した鎖伸長剤溶液を添加し60℃でさらに40分撹拌した。その後モノイソプロパノールアミン(MIPA:ダイセル製)3.8部をN,N-ジエチルホルムアミド(DEF)50質量部に溶解した反応停止剤を添加し、最後にN,N-ジエチルホルムアミド(DEF)を250質量部添加して固形分25.0質量%のポリウレタン溶液を得た。
表12に記載の条件により顔料A2の合成品1~3を合成した。具体的には表12の(a8)のジケトピロロピロール顔料2質量部を表12の(a9)の溶媒に分散させて、表12の(a10)を表12の(a11)部添加した。表12の(a12)の温度条件で表12の(a13)時間撹拌後、水洗して顔料A2の合成品1、2、3を得た。
それぞれの有機溶剤、樹脂、分散剤、顔料(色材)下記表の割合になるように各成分のように実施例及び比較例の非水性インク組成物を作製した。具体的には、ペイントシェイカーを用いてジルコニアビーズにて各成分を分散させて非水性インク組成物を調製した。単位は質量%である。なお、下記表13~20にジルコニアビーズの粒径、分散時間を記載する。
(保存安定性)
実施例、比較例および参考例の非水性インク組成物について保存安定性を評価した。具体的には、非水性インク組成物を60℃で1ヶ月間保存し、試験前後の粘度及び顔料の体積基準累積50%粒子径(D50)の変化を観察し、下記の基準で、保存安定性を評価した。なお、インクの粘度は、落球式粘度計(アントンパール社製AMVn)を用いて、20℃の条件下で測定され、顔料の体積基準累積50%粒子径(D50)は、粒子径分布測定装置(マイクロトラックベル(株)製粒度分析計NANOTRACWAVE)を用いて25℃の条件下で測定した。なお、下記の評価は「粘度」及び「体積基準累積50%粒子径(D50)」のうち、変化率が大きかった方をその非水性インク組成物の評価とした(表中、「保存安定性」と表記)。
評価基準
評価5:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれも3%未満である。
評価4:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが3%以上5%未満である。
評価3:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが5%以上8%未満である。
評価2:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが8%以上10%未満である。
評価1:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが10%以上である。
実施例、比較例および参考例の非水性インク組成物について吐出安定性を評価した。具体的には、インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)に非水性インク組成物を充填して、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に双方向の高速印刷モード(360x720dpi)で、基材表面温度40℃にて連続印刷でベタ及び細線を印刷し、ドット抜け、飛行曲がり、インクの飛び散りの有無を目視により観察し、発生回数を計測した(表中、「吐出安定性」と表記)。
評価基準
評価5:細線が正しく再現できている。
評価4:細線がおおむね正しく再現できている。
評価3:わずかに細線に曲がりがみられる。
評価2:着弾位置がずれており、曲がりが見られる。
評価1:着弾位置のずれが酷く、細線を再現できない。
実施例、比較例および参考例の非水性インク組成物について間欠吐出性を評価した。具体的には、インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に双方向の高速印刷モード(360x720dpi)で、基材表面温度40℃にて長期間に亘り、常温下で、上記記録媒体に断続的な印刷を実施し、ドット抜け、飛行曲がり及びインクの飛び散りの有無を観察し、発生回数を計数し評価した(表中、「間欠吐出性」と表記)。
評価基準
評価5:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が10回未満であった。
評価4:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が10回以上20回未満であった。
評価3:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が20回以上30回未満であった。
評価2:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が30回以上40回未満であった。
評価1:24時間の試験期間内で、ドット抜け、飛行曲がり又はインクの飛び散りの発生が40回以上であった。"
実施例、比較例および参考例の非水性インク組成物についてベタ埋まりを評価した。具体的には、上記インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に双方向の高速印刷モード(360x720dpi)で、基材表面温度40℃にて印刷を実施し、ベタ印字を行った部分の埋まり(白抜け)を確認した(表中、「ベタ埋まり」と表記)。
評価基準
評価5:均一なベタが形成できている
評価4:目視で白抜けは確認できないが、わずかに色ムラが確認できるが意匠性は損なわれていない
評価3:目視で白抜けは確認できないが、色ムラが確認できる
評価2:白抜けが確認できる
評価1:顕著に白抜けが確認でき、濃度感の低下がみられる。"
実施例、比較例および参考例の非水性インク組成物について表面乾燥性を評価した。具体的には、実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像の印刷を行い、40℃で乾燥するまでの時間を計測した(表中、「表面乾燥性」と表記)。
評価基準
評価5:2分未満で乾燥する。
評価4:2分以上4分未満で乾燥する。
評価3:4分以上6分未満で乾燥する。
評価2:6分以上8分未満で乾燥する。
評価1:8分以上で乾燥する。
実施例、比較例および参考例の非水性インク組成物について滲み性を評価した。具体的には、上記インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)、基材表面温度50℃で各色のベタ部中にベタ部と異なる色の6ptの文字がある画像を印刷し、得られた印字物を60℃のオーブンで5分間乾燥後、当該印字物の滲みを目視、ルーペ(x10)で観察した。
評価基準
評価5:ルーペでインクの滲みが観察されなかった。
評価4:目視でインクの滲みが観察されず、6ptの文字が鮮明である。
評価3:目視でインクの滲みがわずかに観察されたが、意匠性は損なわれない。
評価2:目視でインクの滲みが観察されたが、6ptの文字は識別可能である。
評価1:目視でインクの滲みが顕著に観察され、6ptの文字は視認できなかった。
実施例、比較例および参考例の非水性インク組成物について塗膜耐擦性を評価した。具体的には、実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像の印刷を行い、40℃で乾燥させた。印刷物の印刷面を試験用布片にて荷重200g、50往復で擦り、目視で耐擦過性を評価した。(表中、「塗膜耐擦性」と表記。)
評価基準
評価5:インク膜が剥がれず、試験用布片にもインクの付着がなかった。
評価4:インク膜が剥がれなかったが、試験用布片にはインクの付着があった。
評価3:インク膜がわずかに剥がれ、試験用布片にインク膜が付着した。
評価2:インク膜がやや剥がれ、試験用布片にインク膜が付着した。
評価1:インク膜の殆どが剥がれ、試験用布片にインク膜が付着した。
実施例、比較例および参考例の非水性インク組成物について、ヘッドでのノズル詰まりが発生した際に、プリンターのクリーニング動作によりノズル詰まりの解消が行えるかを評価した。具体的には、クリーニングシステムを備えた上記インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いて、実施例及び比較例のインク組成物を充填して印刷高品質印刷モード(1440x720dpi)で1.80m2のベタ画像の印刷を行い、室温25℃にて1週間放置し、その後ノズルチェックパターンを印刷し、抜けが無くなるまでクリーニングを行った(表中、「クリーニング回復性」と表記)。
評価基準
評価5:抜けがない
評価4:ノーマルクリーニング1回でノズル詰まりを解消する。
評価3:ノーマルクリーニング2~3回でノズル詰まりを解消する。
評価2:ノーマルクリーニング4~5回でノズル詰まりを解消する。
評価1:ノーマルクリーニング6回でもノズル詰まりを解消しない。
実施例、比較例および参考例の非水性インク組成物を使用して作製された印字物の耐候性を評価した。実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像の印刷を行い、40℃で1時間乾燥させた。
得られた記録物をキセノンウェザーメーター(ATLAS Ci4000:東洋精機製)内に投入し、サイクル試験を行った。試験条件はJIS K―5600-7-7に基づき、ブラックパネル温度:63℃、キセノンランプの放射照度:60W/m2、試験層内温度:38℃、に保ち、セグメント1では湿度を50%に保った状態で102分間、セグメント2では水照射を18分間行い、これを1サイクルとした。50サイクルを1セットとし、このサイクル試験を継続して10セット行った。
試験前後の色相変化ΔEの値を評価した、色相は以下の条件で評価した。X-Rite eXact(エックスライト社製)を用い、視野角2°、測定範囲 4mmφ、D65光源の条件でL*、a*、b*の値を測定した(表中、「耐候性」と表記)。
色相変化ΔEは、試験前L*1、a*1、b*1、試験後L*2、a*2、b*2の値を使用し、以下の式で求められる
ΔE=((L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2)(1/2)
評価基準
評価5:ΔEが10.0未満である。
評価4:ΔEが20.0未満、10.0以上である。
評価3:ΔEが30.0未満、20.0以上である。
評価2:ΔEが40.0未満、30.0以上である。
評価1:ΔEが50.0以上である。
1.樹脂の作製
(1)アクリル系樹脂
100℃に保たれたジエチレングリコールジエチルエーテル300g中に、メタクリル酸メチル150g及びメタクリル酸ブチル50gと所定量のt-ブチルパーオキシ-2-エチルヘキサノエート(重合開始剤)との混合物を1.5時間かけて滴下した。滴下終了後、100℃で2時間反応させた後冷却して、無色透明のメタクリル酸メチルの重合体溶液を得た。その後、この重合体溶液から溶媒を十分に留去して、メタクリル酸メチルの重合体を得た。このとき重合開始剤であるt-ブチルパーオキシ-2-エチルヘキサノエートの量を変更して、メタクリル酸メチル(アクリル系樹脂)の重合平均分子量を30000~105000になるように制御した(このとき使用した重合開始剤の質量を下記表1に記載した。表21中「開始剤量」と表記した。)。
撹拌装置を備えたオートクレーブに、窒素置換後、脱イオン水100部、メタノール40部、塩化ビニル32部、酢酸ビニル5部、グリシジルメタクリレート0.2部、ヒドロキシプロピルアクリレート3.55部、ヒドロキシプロピルメチルセルロース(懸濁剤)を0.1部、ジ-2-エチルヘキシルパーオキシジカーボネート(重合開始剤)を0.026部、ジ-3,5,5-トリメチルヘキサノールパーオキサイド(重合開始剤)を所定量仕込み、窒素ガス雰囲気下に撹拌しながら63℃に昇温し、63℃に到達直後に塩化ビニル48部を6時間で、グリシジルメタクリレート0.6部、ヒドロキシプロピルアクリレート10.65部を混合したものを5.4時間で連続圧入し、共重合反応させた。オートクレーブ内圧が0.3MPaになった時点で残圧を抜き、冷却して樹脂スラリーを取り出し、ろ過、乾燥して塩化ビニル系共重合樹脂を得た。このとき重合開始剤であるジ-3,5,5-トリメチルヘキサノールパーオキサイドの量を変更して、塩化ビニル-酢酸ビニル共重合体樹脂の重合平均分子量を40000~75000になるように制御した(このとき使用した重合開始剤の質量を下記表21に記載した。表21中「開始剤量」と表記した。)。
市販品のセルロース系樹脂(EASTMAN CHEMICAL社のCAB551-0.01、CAB553-0.4)を用いた。
テレフタル酸104質量部、イソフタル酸104質量部、エチレングリコール79部、ネオペンチルグリコール89質量部、テトラブチルチタネート0.1質量部を丸底フラスコに仕込み、4時間かけて240℃まで徐々に昇温し、留出物を系外に除きながらエステル化反応を行った。エステル化反応終了後30分かけて10mmHgまで減圧、温度を250℃まで昇温し初期重合を行った。その後1mmHg以下で1時間後期重合を行い、ポリエステル樹脂を得た。
ポリカーボネートジオール(プラクセルCD―220:ダイセル製)192.5質量部とイソホロンジイソシアネート(IPDI:エボニック製)41.6質量部、N,N-ジエチルホルムアミド(DEF)100質量部を丸底フラスコに入れ均一に混合後、T100BHJ(触媒)0.01質量部とN,N-ジエチルホルムアミド(DEF)0.09質量部の混合液を入れ75℃で3時間反応させて末端にイソシアネート基をもつプレポリマーを得た。これにN,N-ジエチルホルムアミド(DEF)を250質量部投入し均一に溶解後、3アミノメチル3,5,5トリメチルシクロヘキシルアミン(IPD:エボニック製)12質量部をDEF100質量部に溶解した鎖伸長剤溶液を添加し60℃でさらに40分撹拌した。その後モノイソプロパノールアミン(MIPA:ダイセル製)3.8質量部をN,N-ジエチルホルムアミド(DEF)50質量部に溶解した反応停止剤を添加し、最後にN,N-ジエチルホルムアミド(DEF)を250質量部添加して固形分25.0質量%のポリウレタン溶液を得た。
それぞれの有機溶剤、樹脂、分散剤、顔料(色材)下記表の割合になるように各成分のように実施例及び比較例の非水性インク組成物を作製した。具体的には、ペイントシェイカーを用いてジルコニアビーズにて各成分を分散させて非水性インク組成物を調製した。単位は質量%である。なお、下記表22~29にジルコニアビーズの粒径、分散時間を記載する。
(保存安定性)
実施例、比較例および参考例の非水性インク組成物について保存安定性を評価した。具体的には、非水性インク組成物を60℃で1ヶ月間保存し、試験前後の粘度及び顔料の体積基準累積50%粒子径(D50)の変化を観察し、下記の基準で、保存安定性を評価した。なお、インクの粘度は、落球式粘度計(アントンパール社製AMVn)を用いて、20℃の条件下で測定され、顔料の体積基準累積50%粒子径(D50)は、粒子径分布測定装置(マイクロトラックベル(株)製粒度分析計NANOTRACWAVE)を用いて25℃の条件下で測定した。なお、下記の評価は「粘度」及び「顔料の体積基準累積50%粒子径(D50)」のうち、変化率が大きかった方をその非水性インク組成物の評価とした(表中、「保存安定性」と表記)。
評価基準
評価5:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれも3%未満である。
評価4:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが3%以上5%未満である。
評価3:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが5%以上8%未満である。
評価2:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが8%以上10%未満である。
評価1:粘度及び顔料の体積基準累積50%粒子径(D50)の変化率がいずれかが10%以上である。
実施例、比較例および参考例の非水性インク組成物について吐出安定性を評価した。具体的には、インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)に非水性インク組成物を充填して、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に双方向の高速印刷モード(360x720dpi)で、基材表面温度40℃にて連続印刷でベタ及び細線を印刷し、ドット抜け、飛行曲がり、インクの飛び散りの有無を目視により観察し、発生回数を計測した(表中、「吐出安定性」と表記)。
評価基準
評価5:細線が正しく再現できている。
評価4:細線がおおむね正しく再現できている。
評価3:わずかに細線に曲がりがみられる。
評価2:着弾位置がずれており、曲がりが見られる。
評価1:着弾位置のずれが酷く、細線を再現できない。
実施例、比較例および参考例の非水性インク組成物について、ヘッドでのノズル詰まりが発生した際に、プリンターのクリーニング動作によりノズル詰まりの解消が行えるかを評価した。
具体的には、クリーニングシステムを備えた上記インクジェットプリンター((商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いて、実施例及び比較例のインク組成物を充填して高品質印刷モード(1440x720dpi)で1.80m2のベタ画像を印刷後、室温25℃にて1週間放置し、その後ノズルチェックパターンを印刷し、抜けが無くなるまでクリーニングを行った(表中、「クリーニング回復性」と表記)。
評価基準
評価5:抜けがない
評価4:クリーニング1回でノズル詰まりを解消する。
評価3:クリーニング2~3回でノズル詰まりを解消する。
評価2:クリーニング4~5回でノズル詰まりを解消する。
評価1:クリーニング6回でもノズル詰まりを解消しない。
実施例、比較例および参考例の非水性インク組成物の沈降性の評価を行った。具体的には、非水性インク組成物30gを室温で1ヶ月間保存し、試験前後のインクの上澄み1gを取り、バーコーター#8で記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に展色し40℃オーブンで乾燥させた。試験前後の色相変化ΔEの値を評価した、色相は以下の条件で評価した。X-Rite eXact(エックスライト社製)を用い、視野角2°、測定範囲 4mmφ、D65光源の条件でL*、a*、b*の値を測定した(表中、「色調安定性(沈降性)」と表記」)。
色相変化ΔEは、試験前L*1、a*1、b*1、試験後L*2、a*2、b*2の値を使用し、以下の式で求められる
ΔE=((L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2)(1/2)
評価基準
評価5:ΔEが2.0未満である。
評価4:ΔEが2.5未満、2.0以上である。
評価3:ΔEが3.0未満、2.5以上である。
評価2:ΔEが3.5未満、3.0以上である。
評価1:ΔEが3.5以上である。
実施例、比較例および参考例の非水性インク組成物について表面乾燥性を評価した。具体的には、実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像の印刷を行い、40℃で乾燥するまでの時間を計測した(表中、「表面乾燥性」と表記)。
評価基準
評価5:2分未満で乾燥する。
評価4:2分以上4分未満で乾燥する。
評価3:4分以上6分未満で乾燥する。
評価2:6分以上8分未満で乾燥する。
評価1:8分以上で乾燥する。
実施例、比較例および参考例の非水性インク組成物について滲み性を評価した。具体的には、上記インクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)にて、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)、基材表面温度50℃で各色のベタ部中にベタ部と異なる色の6ptの文字がある画像を印刷し、得られた印字物を60℃のオーブンで5分間乾燥後、当該印字物の滲みを目視、ルーペ(x10)で観察した。
評価基準
評価5:ルーペでインクの滲みが観察されなかった。
評価4:目視でインクの滲みが観察されず、6ptの文字が鮮明である。
評価3:目視でインクの滲みがわずかに観察されたが、意匠性は損なわれない。
評価2:目視でインクの滲みが観察されたが、6ptの文字は識別可能である。
評価1:目視でインクの滲みが顕著に観察され、6ptの文字は視認できなかった。
実施例、比較例および参考例の非水性インク組成物を使用して作製された印字物の耐候性を評価した。実施例及び比較例の非水性インク組成物をインクジェットプリンター(商品名 VersaArt RE-640、ローランドDG(株)製を使用)を用いたインクジェット方式にて記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製))に高品質印刷モード(1440x720dpi)でベタ画像の印刷を行い、40℃で1時間乾燥させた。
得られた記録物をキセノンウェザーメーター(ATLAS Ci4000:東洋精機製)内に投入し、サイクル試験を行った。試験条件はJIS K―5600-7-7に基づき、ブラックパネル温度:63℃、キセノンランプの放射照度:60W/m2、試験層内温度:38℃、に保ち、セグメント1では湿度を50%に保った状態で102分間、セグメント2では水照射を18分間行い、これを1サイクルとした。50サイクルを1セットとし、このサイクル試験を継続して10セット行った。
試験前後の色相変化ΔEの値を評価した、色相は以下の条件で評価した。X-Rite eXact(エックスライト社製)を用い、視野角2°、測定範囲 4mmφ、D65光源の条件でL*、a*、b*の値を測定した。
色相変化ΔEは、試験前L*1、a*1、b*1、試験後L*2、a*2、b*2の値を使用し、以下の式で求められる
ΔE=((L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2)(1/2)
評価基準
評価5:ΔEが5.0未満である。
評価4:ΔEが10.0未満、5.0以上である。
評価3:ΔEが15.0未満、10.0以上である。
評価2:ΔEが20.0未満、15.0以上である。
評価1:ΔEが20.0以上である。
上記で製造した実施例3-1の非水性インク組成物を使用して水分量の違いによる評価を行った。具体的には、上記で製造した実施例3-1の非水性インク組成物に下記表に示した量(非水性インク組成物100質量部に対する質量部)の水(イオン交換水)を添加し、水添加後の非水性インク組成物について上記と同様に評価を行った。なお、表中の「水分含有量」とは、カールフィッシャー水分計901(メトロームジャパン社製)を用いて求めた値である。
Claims (34)
- 顔料と、顔料分散剤と、有機溶剤と、を含有するインクジェット法によって吐出される非水性インク組成物であって、
前記顔料は、下記式(1-1)で示される顔料A1又は下記式(1-2)で示される顔料A2の少なくとも1つを含有し、
前記顔料A1及びA2のpHは3以上9以下の範囲内である、
非水性インク組成物。
- 前記顔料A1及びA2の体積基準累積90%粒子径(D90)は500nm以下である、
請求項1に記載の非水性インク組成物。 - 前記顔料A1及びA2の含有量は、前記非水性インク組成物全量中0.1質量%以上8.0質量%以下である、
請求項1又は2に記載の非水性インク組成物。 - 前記有機溶剤は、下記有機溶剤Bを含有する、
請求項1から3のいずれかに記載の非水性インク組成物。
有機溶剤B:アルキルアミド系溶剤(b1)、環状アミド系溶剤(b2)、及びラクトン系溶剤(b3)からなる群より選択される少なくとも1つ - 顔料と、顔料分散剤と、有機溶剤と、を含有するインクジェット法によって吐出される非水性インク組成物であって、
前記顔料は、ハロゲン化フタロシアニン顔料A3を含有し、
前記有機溶剤は、下記有機溶剤Bを含有する、
非水性インク組成物。
有機溶剤B:アルキルアミド系溶剤(b1)、環状アミド系溶剤(b2)、及びラクトン系溶剤(b3)からなる群より選択される少なくとも1つ - 前記顔料A3の体積基準累積50%粒子径(D50)は、30nm以上150nm以下である、
請求項5に記載の非水性インク組成物。 - 前記顔料A3の体積基準累積90%粒子径(D90)は、50nm以上300nm以下である、
請求項5又は6に記載の非水性インク組成物。 - 前記顔料A3の含有量は、前記非水性インク組成物全量中0.1質量%以上8.0質量%以下である、
請求項5から7のいずれかに記載の非水性インク組成物。 - 前記顔料A3は、塩素化フタロシアニン顔料、臭素化フタロシアニン顔料、及び塩素臭素化フタロシアニン顔料からなる群より選択される少なくとも1つである、
請求項5から8のいずれかに記載の非水性インク組成物。 - 前記顔料A3は、ハロゲン化銅フタロシアニン顔料、及びハロゲン化亜鉛フタロシアニン顔料からなる群より選択される少なくとも1つである、
請求項5から9のいずれかに記載の非水性インク組成物。 - 前記有機溶剤は、グリコールエーテル系溶剤を含有する、
請求項5から10のいずれかに記載の非水性インク組成物。 - 水分の含有量は、非水性インク組成物全量中1.0質量%以下の範囲である、
請求項5から11のいずれかに記載の非水性インク組成物。 - 前記有機溶剤Bは、アルキルアミド系溶剤(b1)を含有する、
請求項4から12のいずれかに記載の非水性インク組成物。 - 前記アルキルアミド系溶剤(b1)は、N,N-ジエチルホルムアミド、N,N-ジエチルプロパンアミド、及びN,N-ジエチルアセトアミドからなる群より選択される少なくとも1つを含有する
請求項14に記載の非水性インク組成物。 - 前記有機溶剤は、環状アミド系溶剤(b2)を含有する、
請求項4から12のいずれかに記載の非水性インク組成物。 - 前記環状アミド系溶剤(b2)は、ε-カプロラクタム、N-メチルカプロラクタム、及びN-ビニルカプロラクタムからなる群より選択される少なくとも1つを含有する
請求項17に記載の非水性インク組成物。 - 前記有機溶剤は、ラクトン系溶剤(b3)を含有する、
請求項4から12のいずれかに記載の非水性インク組成物。 - 前記ラクトン系溶剤(b3)は、γ-ブチロラクトン、γ-バレロラクトン、及びε-カプロラクトンからなる群より選択される少なくとも1つを含有する
請求項20に記載の非水性インク組成物。 - 前記有機溶剤Bの含有量は、前記非水性インク組成物全量中1質量%以上90質量%以下の範囲である、
請求項4から21のいずれかに記載の非水性インク組成物。 - 前記顔料分散剤は塩基性基を有する、
請求項1から22のいずれかに記載の非水性インク組成物。 - 前記顔料分散剤のアミン価が20mgKOH/g以上100mgKOH/g以下の範囲である、
請求項1から23のいずれかに記載の非水性インク組成物。 - 前記顔料分散剤の含有量は、前記非水性インク組成物中の顔料100質量部に対して5質量部以上150質量部以下の範囲である、
請求項1から24のいずれかに記載の非水性インク組成物。 - さらに樹脂を含有し、
前記樹脂は、25℃における固有粘度が90mL/g以上の樹脂が樹脂全量中5質量%以下の範囲である、
請求項1から25のいずれかに記載の非水性インク組成物。 - 前記樹脂は、アクリル系樹脂、塩化ビニル系樹脂、セルロース系樹脂、ポリエステル系樹脂、およびポリウレタン系樹脂からなる群より選択される少なくとも1種以上を含有する、
請求項26に記載の非水性インク組成物。 - さらに界面活性剤を含有し、
前記界面活性剤は、シロキサン骨格を有する界面活性剤を含有する、
請求項1から27のいずれかに記載の非水性インク組成物。 - 非水性インク組成物を貯蔵する貯蔵機構と、インクジェット吐出口と、前記非水性インク組成物を流通させるチューブと、を備え、前記チューブは、前記貯蔵機構と前記インクジェット吐出口とに接続され、且つ前記非水性インク組成物の流路を調整する弁機構を備えるインクジェット記録装置に用いられる
請求項1から28のいずれかに記載の非水性インク組成物。 - 請求項1から29のいずれかに記載の非水性インク組成物を、インクジェット方式にて基材の表面に吐出する
記録方法。 - 請求項1から29のいずれかに記載の非水性インク組成物を、インクジェット方式にて基材の表面に吐出する
記録物の製造方法。 - 請求項1から29のいずれかに記載の非水性インク組成物を少なくとも備えるインクセット。
- 請求項1から29のいずれかに記載の非水性インク組成物の印刷層が基材の表面に形成された
記録物。 - 請求項1から29のいずれかに記載の非水性インク組成物をインクジェット法により吐出するインクジェット記録装置であって、
前記非水性インク組成物を貯蔵する貯蔵機構と、
インクジェット吐出口と、
前記非水性インク組成物を流通させるチューブと、
を備え、
前記チューブは、前記貯蔵機構と前記インクジェット吐出口とに接続され、且つ前記非水性インク組成物の流路を調整する弁機構を備える、
インクジェット記録装置。
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JP2993392B2 (ja) | 1995-04-14 | 1999-12-20 | 東洋インキ製造株式会社 | 表面処理顔料およびその製造方法 |
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JP2013177597A (ja) * | 2013-04-05 | 2013-09-09 | Dnp Fine Chemicals Co Ltd | 油性インクセット |
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JPWO2022211030A1 (ja) | 2022-10-06 |
EP4316854A1 (en) | 2024-02-07 |
JP7106779B1 (ja) | 2022-07-26 |
JP7125567B1 (ja) | 2022-08-24 |
JP2022159236A (ja) | 2022-10-17 |
JP7085080B1 (ja) | 2022-06-15 |
JP2022159266A (ja) | 2022-10-17 |
JP7106780B1 (ja) | 2022-07-26 |
US20240174876A1 (en) | 2024-05-30 |
JP2022159193A (ja) | 2022-10-17 |
JP2022159237A (ja) | 2022-10-17 |
JP2022159264A (ja) | 2022-10-17 |
JP7141561B1 (ja) | 2022-09-22 |
JP2022159265A (ja) | 2022-10-17 |
JP7141562B1 (ja) | 2022-09-22 |
TW202248372A (zh) | 2022-12-16 |
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