WO2014050751A1 - 画像形成方法 - Google Patents
画像形成方法 Download PDFInfo
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- WO2014050751A1 WO2014050751A1 PCT/JP2013/075528 JP2013075528W WO2014050751A1 WO 2014050751 A1 WO2014050751 A1 WO 2014050751A1 JP 2013075528 W JP2013075528 W JP 2013075528W WO 2014050751 A1 WO2014050751 A1 WO 2014050751A1
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- treatment liquid
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- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001955 polymer synthesis method Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- VSFOXJWBPGONDR-UHFFFAOYSA-M potassium;3-prop-2-enoyloxypropane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)CCCOC(=O)C=C VSFOXJWBPGONDR-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- BUOKUWQCVSZNCF-UHFFFAOYSA-N selenadiazole Chemical group C1=C[se]N=N1 BUOKUWQCVSZNCF-UHFFFAOYSA-N 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
- B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
Definitions
- the present invention relates to an image forming method.
- the abrasion resistance after drawing becomes important. That is, when the abrasion resistance of the image is low, the roll paper after drawing is stacked in a short time after drawing, and when the papers are in contact with each other and rubbed, the image is blurred, which is a product You may lose value.
- a failure occurs such that the character is blurred when the character image is drawn, or the character can not be read when the hollow character is drawn, and the bar code
- QR code registered trademark
- a failure may occur such that the image can not be read normally.
- Such a phenomenon is particularly likely to occur particularly in paper in which the ink is easily held on the paper surface, for example, ink jet-dedicated paper having no porous receptive layer.
- an ink used for the ink jet method a water-based ink attracts attention from the point of considering the environment.
- an aqueous ink containing an adduct of ethylene oxide or propylene oxide of glycerin is disclosed from the viewpoints of the ejection stability of the ink and the printing quality such as little bleeding on plain paper (see, for example, Patent Document 1) ).
- the composition contains a colorant, resin particles, a water-soluble organic solvent, and water.
- An ink set is known that includes an ink composition to be mixed, a coagulant that aggregates components in the ink composition, and a treatment liquid that includes a water-soluble polymer that does not cause aggregation of components in the ink composition (for example, , Patent Document 2).
- An object of the present invention is to provide an image forming method for forming a high resolution image while having excellent abrasion resistance (sometimes referred to as abrasion resistance), and to achieve such an object. I assume.
- An image forming method for achieving the problems to be solved by the present invention is as follows. ⁇ 1> A treatment liquid applying step of applying a treatment liquid containing an organic acidic compound represented by the following general formula (I), a water-soluble polymer compound, and water onto a recording medium, and a treatment liquid of the recording medium It is an image forming method including an ink applying step of applying an ink composition containing a pigment, a pyrrolidone derivative, a compound represented by the following general formula (II), and water on the applying surface.
- n represents an integer of 2 or more
- m represents an integer of 3 or more.
- AO represents at least one of ethyleneoxy and propyleneoxy.
- the ⁇ 3> ink applying step is the image forming method according to ⁇ 1> or ⁇ 2>, wherein the recording medium is transported at a transport speed of 50 m / min or more.
- ⁇ 4> The image forming method according to any one of ⁇ 1> to ⁇ 3>, wherein the pyrrolidone derivative is at least one of 2-pyrrolidone and N-methyl-2-pyrrolidone.
- ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the content of the pyrrolidone derivative in the ink composition is 3.0% by mass to 20.0% by mass with respect to the total mass of the ink composition.
- the content of the organic acidic compound in the treatment liquid is 0.5 mass% to 20.0 mass% with respect to the total mass of the treatment liquid It is an image formation method of a statement.
- ⁇ 7> The image forming method according to any one of ⁇ 1> to ⁇ 6>, wherein AO in the general formula (II) is propyleneoxy.
- R a1 represents a hydrogen atom or a methyl group.
- L a1 represents a single bond, -COO-, or -CON (R a3 )-.
- R a3 represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- L a2 represents a single bond, or a divalent C 1-30 linking group which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- a a represents an ionic group.
- R b1 represents a hydrogen atom or a methyl group.
- L b1 represents a single bond, -COO-, or -CON (R b3 )-.
- R b3 represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- R b2 represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- R b2 is a hydrogen atom
- L b1 is a single bond.
- R b2 is a linear C 1-12 aliphatic hydrocarbon group, a C 3-12 aliphatic hydrocarbon group having a branched structure, or a C 3-12 aliphatic having a ring structure
- the image forming method according to ⁇ 8> which is a hydrocarbon group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms.
- R a1 is a hydrogen atom
- L a1 is -COO- or -CONH-
- L a2 is an alkylene group having 1 to 12 carbon atoms
- a a is a sulfonic acid group or a salt thereof
- R b1 is a hydrogen atom or a methyl group
- L b1 is -COO-
- R b2 is a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a C 3 to 12 fatty acid having a branched structure Hydrocarbon group, an aliphatic hydrocarbon group having 3 to 12 carbon atoms having a ring structure, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms ⁇ 8> or ⁇ 9>
- an image forming method in which an image having high abrasion resistance and high resolution is formed.
- FIGS. 1A and 1B are examples of Japanese kanji images drawn by the image forming method of the present invention.
- FIGS. 2 (a) and 2 (b) are other embodiments of the image of Japanese kanji drawn by the image forming method of the present invention.
- the image forming method of the present invention comprises a treatment liquid application step of applying a treatment liquid containing the organic acidic compound represented by the general formula (I), a water-soluble polymer compound, and water onto a recording medium, and the treatment liquid.
- An ink applying step of applying an ink composition containing a pigment, a pyrrolidone derivative, a compound represented by the general formula (II), and water is provided on the applied recording medium surface.
- the image forming method of the present invention may further be provided with other steps such as heat fixation of the formed image, as necessary.
- the ink composition is also simply referred to as an ink.
- the organic acidic compound represented by the general formula (I) is also referred to as a specific organic acidic compound, and the compound represented by the general formula (II) is also referred to as a specific glycerin compound.
- the problem called the strike through which the ink composition soaks into the recording medium and slips off to the back side of the recording medium is suppressed.
- the ink composition does not pass through the recording medium and stays inside the recording medium close to the ink application surface of the recording medium, the bleeding of the ink composition can be sufficiently suppressed. It was not. If bleeding of the ink composition occurs even in the recording medium, the image tends to be blurred and the resolution of the image reduced when the image is drawn with the ink composition.
- the ink composition is applied onto the recording medium by applying the treatment liquid containing the specific organic acid compound, the water-soluble polymer compound, and water before applying the ink composition to the recording medium.
- An object hardly penetrates into the recording medium and can stay on the surface of the recording medium. Therefore, the bleeding of the ink composition can be prevented, and the resolution of the image can be increased. Further, since the ink composition does not penetrate into the recording medium, the image density is likely to be increased.
- the ink composition when the ink composition is not impregnated into the recording medium and is allowed to remain on the surface of the recording medium, a dried product of the ink composition (that is, an image) remains on the surface of the recording medium. It becomes easy to receive.
- a pyrrolidone derivative and a specific glycerin-based compound it is possible to maintain an image strength which hardly causes an image defect such as a scratch. Therefore, the formed image is also excellent in abrasion resistance.
- the treatment liquid applying step the treatment liquid containing the organic acidic compound represented by the general formula (I), the water-soluble polymer compound, and water is applied onto the recording medium. That is, in the image forming method of the present invention, before applying the ink composition, a treatment liquid for aggregating components (such as pigment) in the ink composition is applied on the recording medium, The ink composition is applied and imaged in contact with the processing liquid applied above. As a result, image formation can be speeded up (for example, image formation while conveying the recording medium at a conveyance speed of 50 m / min or more), and an image with high image density and resolution can be obtained even when high speed recording is performed.
- a treatment liquid for aggregating components such as pigment
- the application of the processing liquid to the recording medium may be performed by immersing the recording medium in the processing liquid, a bar coater, an extrusion die coater, an air doctor coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater. It can carry out by various methods, such as a known application using an ink, application by an inkjet method, and the like.
- the treatment liquid it is preferable to heat and dry the treatment liquid on the recording medium after the treatment liquid is applied on the recording medium and before the ink composition is applied.
- ink colorability such as bleeding prevention is improved, and a visible image with good color density and hue can be recorded.
- the heating and drying can be performed by a known heating means such as a heater, an air blowing means utilizing air blowing such as a drier, or a combination of these.
- a heating method for example, a method of applying heat with a heater or the like from the opposite side to the application surface of the recording medium, a method of applying warm air or hot air to the application surface of the recording medium, an infrared heater A heating method etc. are mentioned, You may heat combining these plurality.
- the recording medium is not particularly limited, and general printing paper mainly made of cellulose, which is used for general offset printing and the like, can be used.
- coated paper As a recording medium, so-called coated paper may be used.
- a coating layer also referred to as a coating layer
- an inorganic pigment and the like is provided on the surface of a high-quality paper or neutral paper, which is generally not surface-treated. It is a recording medium.
- Coated paper tends to have gloss unevenness in the image area, but when the treatment liquid contains a phosphoric acid or a phosphoric acid compound, generation of gloss unevenness in the image area can be effectively suppressed.
- art paper, coated paper, lightweight coated paper or finely coated paper is preferred.
- the inorganic pigment contained in the coating layer is not particularly limited, but from the viewpoint of more remarkably exhibiting the effect of suppressing the gloss unevenness by containing the phosphoric acid or the phosphoric acid compound in the treatment liquid, silica, kalion, clay , Calcined clay, zinc oxide, tin oxide, magnesium sulfate, aluminum oxide, aluminum hydroxide, pseudoboehmite, calcium carbonate, satin white, aluminum silicate, smectite, zeolite, magnesium silicate, magnesium carbonate, magnesium oxide, and diatomaceous earth It is preferably at least one, more preferably calcium carbonate, silica and potassium. In particular, when calcium carbonate is contained in the coating layer, the effect of suppressing the gloss unevenness by the phosphoric acid or the phosphoric acid compound is particularly remarkable.
- Fine paper (A) such as “New NPI high quality” made by Co., Ltd.
- fine coated paper such as "OK Everlight Coat” made by Oji Paper Co., Ltd. and “Aurora S” made by Nippon Paper Industries Co., Ltd.
- Oji Lightweight coated paper (A3) such as “OK coat L” manufactured by Paper Co., Ltd. and “Aurora L” manufactured by Nippon Paper Co., Ltd. “OK Top Coat +” manufactured by Oji Paper Co., Ltd.
- Coated paper such as “Aurora coat” (A2, B2), “OK Kinto +” manufactured by Oji Paper Co., Ltd., and art paper (A1) such as “Tokishi Art” manufactured by Mitsubishi Paper Co., Ltd. Can be mentioned. It is also possible to use various types of photo paper for inkjet recording.
- the absorption coefficient Ka for water is preferably 0.05 to 0.5 and mL / m 2.
- the recording medium is ms 1/2 , more preferably 0.1 to 0.4 mL / m 2 ⁇ ms 1/2 , and still more preferably 0.2 to 0.3 mL / m 2 ⁇ ms It is a 1/2 recording medium.
- the absorption coefficient Ka for water is the same as that described in JAPAN TAPPI Paper and Pulp Test Method No. 51: 2000 (issued by the Japan Institute of Paper and Pulp Technology).
- the absorption coefficient Ka is an automatic scanning liquid absorption meter It is calculated from the difference between the transfer amount of water with a contact time of 100 ms and a contact time of 900 ms using KM500Win (manufactured by Kumagaya Riki Co., Ltd.).
- the treatment liquid contains a specific organic acid compound, a water-soluble polymer compound, and water.
- the treatment liquid may contain other components as needed, such as silicone oil.
- the treatment liquid is a liquid in which components (such as pigments) in the ink composition are aggregated by the specific organic acid compound.
- the treatment liquid contains at least one kind of the organic acidic compound (specific organic acidic compound) represented by the general formula (I).
- the organic acidic compound represented by the following general formula (I) has a high ability to aggregate the ink composition (pigment etc.), and the movement of the ink droplet applied on the recording medium is effectively suppressed. As a result, the roughness of the image resulting from the movement of the ink droplet is effectively suppressed.
- n represents an integer of 2 or more
- m represents an integer of 3 or more.
- n is preferably an integer of 3 to 5. Image roughness is further suppressed as n is 3 or more. When n is 5 or less, the abrasion resistance of the image (physical strength of the image, hereinafter the same) is further improved.
- m is preferably an integer of 3 to 5. When m is 3 or more, the movement of the ink droplet is further suppressed. When m is 5 or less, the abrasion resistance of the image is further improved.
- Specific examples of the specific organic acid compound include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and the like.
- the content of the specific organic acidic compound in the treatment liquid is not particularly limited, but is preferably 0.5% by mass to 20% by mass, and more preferably 0.5% by mass to 15% by mass, with respect to the total mass of the treatment liquid 0.5 to 10% by mass is more preferable.
- the content of the organic acidic compound represented by the general formula (I) in the processing liquid is 0.5% by mass or more, the roughness of the image can be further suppressed, and when the content is 20% by mass or less, the image resistance Rubbing properties are further improved.
- the treatment liquid may further contain another organic acid compound other than the specific organic acid compound, and, for example, a monovalent saturated fatty acid represented by the general formula (I) in which 1 is 1, a general formula (I) In which m is 2 and bivalent saturated fatty acids and monovalent or polyvalent unsaturated fatty acids are exemplified.
- the other organic acidic compound is preferably a compound containing two carboxy groups in one molecule. Examples of the compound containing two carboxy groups in one molecule include tartaric acid, phthalic acid, 4-methylphthalic acid, DL-malic acid, malonic acid, glutaric acid, dimethylmalonic acid and maleic acid. Among them, DL-malic acid, malonic acid, glutaric acid, dimethylmalonic acid and maleic acid are preferable.
- the total organic acid compound (the total of the specific organic acid compound and the other organic acid compound) in the treatment liquid is 5.0% by mass to 40. It is preferable that it is 0 mass%.
- the content of the specific organic acidic compound is preferably 10% by mass to 50% by mass with respect to the total mass of all the organic acidic compounds. In the case of drawing on coated paper, when the content of the specific organic acid compound in all organic acid compounds is 5% by mass or more, the roughness of the image can be further suppressed, and when the content is 50% by mass or less Sex is further improved.
- the content of the total organic acid compound in the treatment liquid is the entire content of the treatment liquid from the viewpoint of suppressing the cohesion of the ink and image roughness.
- the content is preferably 5.0% by mass to 40.0% by mass, and more preferably 10.0% by mass to 30.0% by mass.
- the treatment liquid in the present invention contains at least one water-soluble polymer compound.
- the aggregation speed at the time of aggregating the components in the ink composition with the organic acidic compound can be suppressed to a certain extent, and the ink droplets applied to the recording medium can be expanded to the target size. Thereby, it is possible to suppress the roughness of the image caused by the insufficient spread of the ink.
- water-soluble means that it can be dissolved in water at a certain concentration or more, and it may be any one that can be dissolved (desirably uniformly) in an aqueous treatment liquid.
- the solubility in water at 25 ° C. is preferably 5% by mass or more, and more preferably 10% by mass or more.
- the treatment liquid contains a water-soluble polymer compound
- bubbles tend to be generated in the treatment liquid, and coating unevenness of the treatment liquid due to the bubbles tends to easily occur. Therefore, in the present invention, by including the silicone oil in the treatment liquid containing the water-soluble polymer compound, it is possible to suppress the unevenness in the application of the treatment liquid due to the bubbles in the treatment liquid while suppressing the roughness of the image.
- the water-soluble polymer compound is not particularly limited, and known water-soluble polymer compounds such as polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, polyethylene glycol and the like can be used.
- water-soluble polymer compound a specific polymer compound described later is also suitable.
- the weight average molecular weight of the water-soluble polymer compound is not particularly limited, but can be, for example, 10000 to 100,000, preferably 20,000 to 80,000, and more preferably 30,000 to 80,000.
- the content of the water-soluble polymer compound in the treatment liquid in the present invention is not particularly limited, but it is preferably 0.1% by mass to 10% by mass with respect to the total amount of the treatment liquid
- the content is more preferably 4% by mass, still more preferably 0.1% by mass to 2% by mass, and particularly preferably 0.1% by mass to 1% by mass. If the content of the water-soluble polymer compound in the treatment liquid is 0.1% by mass or more, the spread of ink droplets can be further promoted, and the content of the water-soluble polymer compound in the treatment liquid is 10% by mass or less If there is, the thickening of the treatment liquid can be further suppressed. In addition, when the content of the water-soluble polymer compound in the treatment liquid is 10% by mass or less, the application unevenness of the treatment liquid due to the bubbles in the treatment liquid can be further suppressed.
- a polymer compound containing a hydrophilic structural unit having an ionic group (preferably, an anionic group) (hereinafter, also referred to as “specific polymer compound”) is preferable.
- specific polymer compound a polymer compound containing a hydrophilic structural unit having an ionic group (preferably, an anionic group)
- the reason why the specific polymer compound can promote the spread of the ink droplets applied to the recording medium and the image roughness is further suppressed is presumed as follows.
- the specific polymer compound maintains affinity with a solvent (for example, water) in the treatment liquid by the action of the ionic group in the side chain moiety.
- the polymer compound in the treatment liquid applied onto the recording medium, the polymer compound is mainly near the surface of the treatment liquid (the side away from the recording medium) by the action of the main chain portion and the side chain portion excluding the ionic group.
- the specific polymer compound existing near the surface of the treatment liquid prevents the penetration of the treatment liquid into the ink composition to some extent, and as a result, It is considered that the aggregation speed of the ink composition by the organic acidic compound is suppressed to a certain extent, and the spreading of the ink droplet is promoted.
- the specific polymer compound is likely to be present near the surface of the treatment liquid, thereby exhibiting a high effect of suppressing the image roughness.
- the specific polymer compound was used as the water-soluble polymer compound, bubbles were more likely to be generated in the treatment liquid, and application unevenness of the treatment liquid due to the bubbles was more likely to occur. . Therefore, when the specific polymer compound is used as the water-soluble polymer compound, the above-mentioned effect of suppressing the application unevenness of the treatment liquid with the silicone oil is more significantly exhibited.
- Examples of the ionic group in the specific polymer compound include a carboxy group, a sulfonic acid group, a phosphoric acid group, a boronic acid group, an amino group, an ammonium group, and salts thereof.
- a carboxy group, a sulfonic acid group, a phosphoric acid group, or a salt thereof more preferably a carboxy group, a sulfonic acid group, or a salt thereof, and still more preferably a sulfonic acid group or a salt thereof It is salt.
- the content of the structural unit having an ionic group (preferably an anionic group) in the water-soluble polymer compound can be, for example, 10 to 100% by mass in the total mass of the water-soluble polymer compound, and The content is preferably 90% by mass, more preferably 10 to 70% by mass, still more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass.
- the specific polymer compound more preferably contains a hydrophilic structural unit having an ionic group (preferably an anionic group, particularly preferably a sulfonic acid group) and a hydrophobic structural unit.
- a hydrophilic structural unit having an ionic group preferably an anionic group, particularly preferably a sulfonic acid group
- a hydrophobic structural unit By including the hydrophobic structural unit, the specific polymer compound is more easily present on the surface of the treatment liquid, so the spread of ink droplets applied to the recording medium is further promoted and the image roughness is further suppressed.
- the specific polymer compound contains a hydrophilic structural unit having an ionic group (preferably an anionic group, particularly preferably a sulfonic acid group) and a hydrophobic structural unit
- the specific polymer compound is treated Since it is likely to be present near the surface of the liquid, a better effect of suppressing roughness can be obtained.
- bubbles are more likely to be generated in the treatment liquid, and application unevenness of the treatment liquid due to the bubbles is further likely to occur. Therefore, when a specific polymer compound containing a hydrophilic structural unit having an ionic group (preferably an anionic group, particularly preferably a sulfonic acid group) and a hydrophobic structural unit is used as the specific polymer compound.
- the effect of the coating nonuniformity suppression by silicone oil is exhibited more notably.
- the content of the hydrophobic structural unit in the specific polymer compound can be, for example, 10 to 90% by mass, preferably 30 to 90% by mass, based on the total mass of the specific polymer compound, preferably 50 to 90
- the content is more preferably in the range of 60% to 80% by mass.
- a hydrophilic structural unit having an ionic group preferably an anionic group, particularly preferably a sulfonic acid group
- a structural unit represented by the following general formula (A) is preferable, and it is hydrophobic
- the structural unit is preferably a structural unit represented by the following general formula (B).
- R a1 represents a hydrogen atom or a methyl group.
- L a1 represents a single bond, -COO-, or -CON (R a3 )-.
- R a3 represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- L a2 represents a single bond, or a divalent C 1-30 linking group which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- a a represents an ionic group.
- L a1 is preferably -COO- or CON (R a3 )-, more preferably -COO- or CONH-, and particularly preferably -CONH-.
- the monovalent C 1 -C 30 monovalent group which may contain at least one of an ether bond, a thioether bond, and an ester bond in R a3 is a C 1-30 monovalent hydrocarbon group, or And a monovalent group having 1 to 30 carbon atoms which is formed by linking at least one of an ether bond, a thioether bond, and an ester bond and at least one of a hydrocarbon group.
- Examples of the hydrocarbon group in R a3 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group composed of a combination thereof.
- the aliphatic hydrocarbon group is not limited to a linear hydrocarbon group, and may have at least one of a ring structure (alicyclic structure) and a branched structure.
- the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the group consisting of a combination thereof may be unsubstituted or substituted by a substituent. Examples of the substituent include an alkoxy group, a hydroxy group, a halogen atom and the like.
- alkyl group, an alkenyl group, an alkynyl group is mentioned as a specific example of the aliphatic hydrocarbon group in this invention. These may have a branched structure or may have a cyclic structure. Moreover, these may be substituted by the substituent.
- alkyl group a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned as an unsubstituted alkyl group.
- substituted alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like.
- aromatic hydrocarbon group ie, aryl group
- aromatic hydrocarbon group ie, aryl group
- the condensed aromatic ring compound having 8 or more carbon atoms is an aromatic ring in which two or more benzene rings are fused, and / or an alicyclic hydrocarbon in which at least one aromatic ring is fused to an aromatic ring And an aromatic compound having 8 or more carbon atoms.
- Specific examples of the condensed aromatic ring compound having 8 or more carbon atoms include naphthalene, anthracene, fluorene, phenanthrene, acenaphthene and the like.
- an aralkyl group and an alkylaryl group are mentioned. These may have a branched structure or may have an alicyclic structure. Moreover, these may be substituted by the substituent.
- a monovalent group formed by linking at least one of an ether bond, a thioether bond, and an ester bond and at least one of a hydrocarbon group includes an alkoxy group, an alkylthio group, Alkylcarbonyloxy group, alkyloxycarbonyl group, aryloxy group, arylthio group, arylcarbonyloxy group, aryloxycarbonyl group, alkyloxyaryl group, aryloxyalkyl group, alkylthioaryl group, arylthioalkyl group, alkylcarbonyloxyaryl Groups, arylcarbonyloxyalkyl groups, alkyloxycarbonylaryl groups, aryloxycarbonylalkyl groups, and the like.
- the carbon number of the aliphatic hydrocarbon group is preferably 1 to 12, more preferably 1 to 8, still more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1.
- the carbon number of the aromatic hydrocarbon group for R a3 is preferably 6 to 16, more preferably 6 to 14, still more preferably 6 to 10, and particularly preferably 6.
- the carbon number of the hydrocarbon group consisting of a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group in R a3 is preferably 7 to 28, more preferably 7 to 15, still more preferably 7 to 12, Is particularly preferred.
- R a3 preferably, at least one of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an ether bond, a thioether bond, and an ester bond and at least one hydrocarbon group are linked to each other It is a monovalent group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a hydrogen atom.
- the divalent C 1-30 linking group which may contain at least one of an ether bond, a thioether bond, and an ester bond is a C 1-30 divalent hydrocarbon group, Or a divalent group having 1 to 30 carbon atoms which is constituted by linking at least one of an ether bond, a thioether bond, and an ester bond and at least one of a hydrocarbon group.
- the hydrocarbon group in L a2 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group composed of a combination thereof.
- aliphatic hydrocarbon group in L a2 examples include an alkylene group, an alkenylene group, and an alkynylene group which may have a branched structure or an alicyclic structure.
- an arylene alkylene which may have a branched structure or may have an alicyclic structure And alkylene arylene groups.
- Examples of the “divalent group formed by linking at least one of an ether bond, a thioether bond, and an ester bond with at least one of a hydrocarbon group” in L a2 include the aforementioned “ether bond, thioether bond, And a divalent group in which one hydrogen atom has been removed from the group exemplified by “a monovalent group constituted by linking at least one type of ester bond and at least one type of hydrocarbon group”.
- the carbon number of the aliphatic hydrocarbon group is preferably 1 to 12, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 3 to 4 carbon atoms.
- the carbon number of the aromatic hydrocarbon group in L a2 is preferably 6 to 16, more preferably 6 to 14, more preferably 6 to 10, and particularly preferably 6.
- the carbon number of the hydrocarbon group composed of a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group is preferably 7 to 28, more preferably 7 to 15, and more preferably 7 to 12, Is particularly preferred.
- L a2 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or at least one of an ether bond, a thioether bond or an ester bond and at least one of a hydrocarbon group
- the group is preferably a group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, still more preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
- an alkylene group having 1 to 12 carbon atoms particularly preferably an alkylene group having 1 to 12 carbon atoms.
- the ionic group represented by A a cationic groups include anionic groups, among them the anionic group is preferable.
- the cationic group represents a group capable of being dissociated into a cation or a group dissociating into a cation
- the anionic group represents a group capable of being dissociated into an anion or a group dissociating into an anion .
- Specific examples of A a include a carboxy group, a sulfonic acid group, a phosphoric acid group, a boronic acid group, an amino group, an ammonium group, and salts thereof.
- a carboxy group, a sulfonic acid group, a phosphoric acid group, or a salt thereof more preferably a carboxy group, a sulfonic acid group, or a salt thereof, from the viewpoint of appropriate acidity.
- a sulfonic acid group or a salt thereof is preferred.
- the structural unit represented by the general formula (A) is a structural unit derived from a monomer having an ionic group (that is, a structural unit formed by polymerization of a monomer having an ionic group) It may be a structural unit formed by introducing an ionic group after formation of the base polymer).
- the structural unit in terms of production efficiency and stability, it is preferable that the structural unit is derived from a monomer having an ionic group.
- the monomer having an ionic group a commonly used monomer can be used without particular limitation.
- Examples of the monomer having an anionic group as the ionic group include monomers having a carboxy group. Specifically, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, 2 And-methacryloyloxymethylsuccinic acid and the like.
- Examples of the monomer having a sulfonic acid group include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate and bis- (3-sulfopropyl) -itaconate. .
- a monomer having a phosphoric acid group for example, vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2 Acryloyloxyethyl phosphate and the like.
- the monomer which has an anionic group can be used individually by 1 type or in mixture of 2 or more types.
- monomers having a cationic group as the ionic group monomers described in "Polymer Handbook 4th Edition John Wiley & Sons" etc. may be mentioned, and these may each be used alone or in combination. The above can be mixed and used.
- the content of the structural unit represented by the general formula (A) can be, for example, 10 to 100% by mass, preferably 10 to 90% by mass in the total mass of the specific polymer compound, and 10
- the content is more preferably 70 to 70% by mass, further preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass.
- R a1 is a hydrogen atom
- L a1 is -COO- or -CONH-
- L a2 is An alkylene group having 1 to 12 carbon atoms
- a a is a sulfonic acid group or a salt thereof is preferable
- L a1 is -CONH-
- L a2 is an alkylene group having 3 to 4 carbon atoms
- a combination in which a is a sulfonic acid group or a salt thereof is more preferable
- L a2 is an alkylene group having 4 carbon atoms and A a is a sulfonic acid group or a salt thereof is particularly preferable.
- the carboxy group, the sulfonic acid group, and the phosphoric acid group may be in the form of a salt.
- R b1 represents a hydrogen atom or a methyl group.
- L b1 represents a single bond, -COO-, or -CON (R b3 )-.
- R b3 represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- R b2 represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond.
- R b2 is a hydrogen atom
- L b1 is a single bond.
- L b1 is preferably -COO- or -CON (R b3 )-, more preferably -COO- or CONH-, particularly preferably -COO-.
- the monovalent group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond is a monovalent hydrocarbon group having 1 to 30 carbon atoms, or And a monovalent group having 1 to 30 carbon atoms which is formed by linking at least one of an ether bond, a thioether bond, and an ester bond and at least one of a hydrocarbon group.
- examples of the hydrocarbon group include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups consisting of a combination thereof.
- examples of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the group consisting of a combination thereof are as described above.
- the carbon number of the aliphatic hydrocarbon group is preferably 1 to 12, more preferably 1 to 8, still more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1.
- the carbon number of the aromatic hydrocarbon group is preferably 6 to 16, more preferably 6 to 14, still more preferably 6 to 10, and particularly preferably 6.
- the number of carbon atoms of the hydrocarbon group consisting of a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group in R b3 is preferably 7 to 28, more preferably 7 to 15, and still more preferably 7 to 12, Is particularly preferred.
- R b3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or at least one of an ether bond, a thioether bond or an ester bond and at least one of a hydrocarbon group It is a monovalent group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a hydrogen atom.
- a monovalent hydrocarbon group having 1 to 30 carbon atoms which may contain at least one of an ether bond, a thioether bond, and an ester bond
- a monovalent hydrocarbon group having 1 to 30 carbon atoms can be mentioned Or a monovalent group having 1 to 30 carbon atoms which is configured by linking at least one of an ether bond, a thioether bond, and an ester bond and at least one of a hydrocarbon group.
- examples of the hydrocarbon group include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups consisting of a combination thereof.
- examples of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the group consisting of a combination thereof are as described above.
- the carbon number of the aliphatic hydrocarbon group is preferably 1 to 12, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4 when the ring structure and branched structure are not included. preferable.
- the carbon number of the aliphatic hydrocarbon group is preferably 3 to 12, more preferably 6 to 12, and particularly preferably 6 to 10, in the case where it contains a ring structure.
- the carbon number of the aliphatic hydrocarbon group is preferably 3 to 12, more preferably 6 to 12, and particularly preferably 6 to 10, in the case where it contains a branched structure.
- the carbon number of the aromatic hydrocarbon group is preferably 6 to 16, more preferably 6 to 14, still more preferably 6 to 10, and particularly preferably 6.
- the carbon number of a group consisting of a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group is preferably 7 to 28, more preferably 7 to 15, still more preferably 7 to 12, and particularly preferably 7 to 9 preferable.
- an aliphatic hydrocarbon group that is, a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having an alicyclic structure
- an aliphatic hydrocarbon group and an aromatic hydrocarbon group A monovalent group (preferably an aralkyl group); a monovalent group formed by linking at least one of an ether bond, a thioether bond or an ester bond and at least one of an aliphatic hydrocarbon group (preferably An aryloxy group); a monovalent group (preferably an aryloxyalkyl group) constituted by linking at least one of an ether bond, a thioether bond or an ester bond, an aliphatic hydrocarbon group and an aromatic hydrocarbon group; It is.
- R b2 represents an aliphatic hydrocarbon group (ie, a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a ring structure); an aliphatic hydrocarbon group and an aromatic hydrocarbon group A group consisting of a combination thereof (preferably an aralkyl group); a monovalent group formed by linking an aliphatic hydrocarbon group and an aromatic hydrocarbon group by at least one of an ether bond, a thioether bond or an ester bond ( Preferably an aryloxyalkyl group);
- a group (preferably an aralkyl group) consisting of a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group as R b2 ; an aliphatic hydrocarbon group by at least one of an ether bond, a thioether bond or an ester bond And an aromatic hydrocarbon group connected to form a monovalent group (preferably an aryloxyalkyl group).
- R b2 a group (preferably an aralkyl group) consisting of a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group is particularly preferable.
- a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a carbon number of 3 to 6 carbon atoms having a branched structure 12 aliphatic hydrocarbon groups, aliphatic hydrocarbon groups having 3 to 12 carbon atoms having a ring structure, aralkyl groups having 7 to 12 carbon atoms, or aryloxyalkyl groups having 7 to 12 carbon atoms are preferable, and branched structures Aliphatic hydrocarbon group having 3 to 12 carbon atoms, aliphatic hydrocarbon group having 3 to 12 carbon atoms having a ring structure, aralkyl group having 7 to 12 carbon atoms, or aryloxyalkyl group having 7 to 12 carbon atoms More preferably, an aralkyl group having 7 to 12 carbon atoms or an aryloxyalkyl group having 7 to 12 carbon atoms is more preferable, and an aralkyl group having 7 to 12 carbon atoms or an aryloxyalkyl group having 7 to 12 carbon
- R b1 is a hydrogen atom or a methyl group
- L b1 is -COO-
- R b2 is a straight-chain aliphatic having 1 to 12 carbon atoms
- a combination of 12 aryloxyalkyl groups is preferred, and R b1 is a methyl group, R b2 is a branched C 3-12 aliphatic hydrocarbon group having a branched structure, and a C 3-12 carbon ring having a ring structure
- the structural unit represented by the general formula (B) is preferably a structural unit derived from the following monomers. That is, specific examples of the monomer constituting the structural unit represented by the general formula (B) include styrene, ⁇ -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate and n-propyl (meth) acrylate , Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, octyl (meth) acrylate, tert-octyl (meth) acrylate, stearyl (meth
- the specific polymer compound In order for the specific polymer compound to be present in the vicinity of the surface of the treatment liquid applied onto the recording medium, it is considered preferable that the flowability be low at the time of heat drying of the treatment liquid. Therefore, as the specific polymer compound, one having a high glass transition temperature which generally correlates with the softening temperature of the polymer compound is preferable. From that point of view, as a monomer for forming the structural unit represented by formula (B), methacrylate is more preferable than acrylate.
- the total content thereof is, for example, 10 to 90% by mass in the total mass of the specific polymer compound. It is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and particularly preferably 60 to 80% by mass.
- the specific polymer compound contains at least one of the structural units represented by the general formula (B) in addition to the structural unit represented by the general formula (A).
- the structural unit represented by the general formula (A) and the general formula (B) from the viewpoint that it is easy to control the property and the property existing near the surface of the treatment liquid by adjusting the composition ratio of the structural unit It is particularly preferable to include three or more structural units selected from the group consisting of structural units represented by
- the specific polymer compound in the present invention may optionally contain other structural units other than the structural unit represented by General Formula (A) and the structural unit represented by General Formula (B).
- structural units for example, among structural units derived from known vinyl monomers, structural units other than structural units represented by General Formula (A) and structural units represented by General Formula (B) are used be able to.
- the weight average molecular weight of the specific polymer compound is not particularly limited, but can be, for example, 10000 to 100,000, preferably 20,000 to 80,000, and more preferably 30,000 to 80,000.
- the content of the specific polymer compound in the treatment liquid in the present invention is not particularly limited, but preferably 0.1 mass% to 10 mass% with respect to the total amount of the treatment liquid, 0.1 mass% to 4 More preferably, it is 0.1% by mass to 2% by mass, and particularly preferably 0.1% by mass to 1% by mass. If the content of the specific polymer compound in the treatment liquid is 0.1% by mass or more, the spreading of the ink droplet can be further promoted, and if the content of the specific polymer compound in the treatment liquid is 10% by mass or less The thickening of the treatment liquid can be further suppressed. In addition, when the content of the specific polymer compound in the treatment liquid is 10% by mass or less, the coating unevenness of the treatment liquid caused by the bubbles in the treatment liquid can be further suppressed.
- the specific polymer compound may be a monomer (preferably a monomer) for forming a structural unit represented by at least the general formula (A) by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization and emulsion polymerization.
- the monomer component containing the monomer for forming the structural unit represented by General formula (B) can be synthesize
- the polymerization reaction can be carried out by known operations such as batch system, semi-continuous system, continuous system and the like.
- a solution polymerization method using a polymerization initiator (for example, a radical polymerization initiator) is particularly preferable.
- the solvent used in the solution polymerization method is, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, It may be a single solvent or a mixture of two or more of various organic solvents such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol and 1-butanol, or may be a mixed solvent with water.
- the polymerization temperature can be set in relation to the molecular weight of the polymer to be produced, the type of initiator and the like, and is usually about 0 ° C. to 100 ° C., but polymerization is preferably performed in the range of 50 to 100 ° C.
- the reaction time is preferably about 1 to 30 hours.
- the obtained polymer may be subjected to purification such as reprecipitation.
- a, b, c and d indicate the content ratio (mass%) of each structural unit. The sum of a, b, c and d is 100.
- a combination in which a is 0 to 73, b is 0 to 90, c is 10 to 90, and d is 0 to 90 is preferable.
- Specific combinations of a / b / c / d in the exemplified compounds A-1 to A-29 are 5/5/90/0, 33/33/34/0, 17/50/33/0, 50.
- the treatment liquid in the present invention contains water.
- the content of water is not particularly limited, but is preferably in the range of 10% by mass to 99% by mass, more preferably 50% by mass to 90% by mass, and still more preferably 60% by mass to 80% by mass.
- the treatment liquid preferably contains at least one silicone oil.
- a silicone oil it is possible to suppress the application unevenness of the treatment liquid caused by the bubbles in the treatment liquid.
- an antifoaming agent may be used to suppress bubbles in a liquid, but the use of a silicone oil suppresses application unevenness of the treatment liquid more than when using an antifoaming agent other than silicone oil. Easy to do.
- silicone oil there is no particular restriction as silicone oil, and silicone oil (the concept of silicone oil includes modified silicone oil such as hydrophilic silicone oil is also included in the concept of silicone oil) which is used as an active ingredient of known silicone antifoaming agent is appropriately selected It can be used.
- the silicone oil is not particularly limited, and examples thereof include organopolysiloxanes such as dimethylpolysiloxane and modified organopolysiloxanes such as polyoxyalkylene modified organopolysiloxanes. These may be used alone or in combination of two or more.
- the silicone oil for example, the silicone oil described in Japanese Patent Publication No. 07-090128 or the silicone oil described in Japanese Patent No. 3976113 can be used.
- a silicone oil having a viscosity of 100 to 100,000 mm 2 / s at 25 ° C. is preferable from the viewpoint of antifoaming property.
- the form in which the silicone oil is dispersed in the treatment liquid from the viewpoint of further suppressing the generation of the foam in the treatment liquid and suppressing the coating unevenness caused by the foam.
- the form in which the silicone oil is dispersed in the treatment liquid by the surfactant that is, the form in which the silicone oil is emulsified and dispersed in the treatment liquid
- a specific method for forming a form in which silicone oil is dispersed in a treatment liquid with a surfactant a method using an emulsion-type silicone antifoaming agent described later in the preparation of the treatment liquid is suitable.
- the surfactant for dispersing the silicone oil can be appropriately selected from surfactants which can emulsify and disperse the silicone oil in the treatment liquid containing water.
- a nonionic surfactant is suitable as a surfactant for dispersing the silicone oil.
- a surfactant exemplified as a surface tension regulator to be described later can be used as the surfactant for dispersing the silicone oil.
- the silicone antifoaming agent is an antifoaming agent containing silicone oil as an active ingredient.
- silicone antifoamer each form of an oil type silicone antifoamer, a compound type silicone antifoamer, an emulsion type silicone antifoamer, a self-emulsification silicone antifoamer etc. is mentioned, for example.
- the oil type silicone antifoaming agent refers to silicone oil (including modified silicone oil such as hydrophilic silicone oil) itself.
- Hydrophilic silicone oils are also referred to as "hydrophilic oil type silicone antifoam agents" and the like.
- the compound-type silicone antifoaming agent is a form in which particles such as silica and alumina are dispersed in an oil-type silicone antifoaming agent to improve antifoaming properties.
- the emulsion type silicone antifoaming agent is a form in which the compound type silicone antifoaming agent is made into an O / W type emulsion by an emulsifier (surfactant) to increase the dispersibility in water.
- the self-emulsifying silicone antifoaming agent contains silicone oil and silica, and is in the form of easily becoming an O / W type emulsion when diluted in water.
- silicone antifoaming agent a compound silicone antifoaming agent, an emulsion silicone antifoaming agent, and a self-emulsifying silicone antifoaming agent, which contain silica particles excellent in antifoaming properties, are preferable.
- the emulsion type silicone antifoaming agent is preferable in that the effect of suppressing the application unevenness is particularly remarkable.
- a commercial item can be used for a silicone antifoamer.
- Commercially available products include KS-508, KS-531, KS-537, KS-604, KM-72, KM-72F, KM-90, KM-98 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SF- 8427, SF-8428, SH-3749, SH-8400, FZ-2101, FZ-2104, FZ-2118, FZ-2203, FZ-2207 (manufactured by Toray Dow Corning Co., Ltd.), BYK-345, BYK-346, BYK-348 (all, made by Big Chemie Japan KK), TSA-739, TSA-7341, TSA-732, TSA-732A, TSA-772, TSA-730, TSA-770, TSA-775 , YMA6509, TSA-737, TSA-737F, YSA-6406, TSA-780 (or more, momentary performance Nsu Materials Japan made
- the content of silicone oil in the treatment liquid is not particularly limited, but from the viewpoint of further suppressing the decrease in surface tension of the treatment liquid due to the addition of silicone oil and further suppressing the roughness of the image, relative to the total amount of treatment liquid. 1500 ppm or less is preferable, 1000 ppm or less is more preferable, and 500 ppm or less is particularly preferable.
- the content of the silicone oil is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, and particularly preferably 10.0% by mass or less, based on the total amount of the water-soluble polymer compound.
- the lower limit of the content of the silicone oil in the treatment liquid is not particularly limited, but from the viewpoint of further suppressing the application unevenness of the treatment liquid, the lower limit of the content of the silicone oil in the treatment liquid is the total amount of the treatment liquid. On the other hand, 5 ppm is preferable, 10 ppm is more preferable, and 50 ppm is particularly preferable.
- the lower limit of the silicone oil content in the treatment liquid is preferably 0.1% by mass, more preferably 0.2% by mass, and particularly preferably 1.0% by mass with respect to the total amount of the water-soluble polymer compound. . In the present invention, "ppm" is based on mass.
- the treatment liquid in the present invention may contain at least one of phosphoric acid and a phosphoric acid compound as an inorganic acid. Thereby, the gloss unevenness of the image is suppressed. It is considered that the gloss unevenness of the image is caused by the reaction of the component (for example, calcium carbonate) in the recording medium and the organic acidic compound in the processing liquid.
- a phosphoric acid compound for example, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, or salts thereof can be used.
- the content of the total organic acidic compound relative to the total of the total organic acidic compound and the phosphoric acid and the phosphoric acid compound is not particularly limited, but is preferably 60% by mass to 90% by mass.
- the content of the total organic acidic compound is 60% by mass or more based on the total of the organic acidic compound and the phosphoric acid and the phosphoric acid compound, the image roughness is further suppressed.
- the content of the total organic acidic compound is 90% by mass or less based on the total of the organic acidic compound and the phosphoric acid and the phosphoric acid compound, the gloss unevenness of the image is further suppressed and the abrasion resistance of the image is further improved.
- the treatment liquid in the present invention preferably contains at least one selected from organic solvents.
- the organic solvent is preferably an organic solvent which is dissolved in 5 g or more of water at 100 ° C. at 20 ° C. (hereinafter, also referred to as “water-soluble organic solvent”).
- water-soluble organic solvent the same one as the water-soluble organic solvent contained in the ink described later can be used.
- polyalkylene glycol or a derivative thereof is preferable from the viewpoint of curl suppression, and diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, dipropylene glycol, tripropylene glycol monoalkyl ether, polyoxypropylene glyceryl ether, poly More preferably, it is at least one selected from oxyethylene polyoxypropylene glycol.
- the content of the organic solvent in the treatment liquid is not particularly limited, but is preferably 1 to 30% by mass, and more preferably 5 to 15% by mass with respect to the whole treatment liquid, from the viewpoint of curl suppression. More preferable.
- the treatment liquid in the present invention may contain at least one selected from nitrogen-containing heterocyclic compounds and organic mercapto compounds. This improves the abrasion resistance of the image and the transportability of the recording medium. Among them, it is preferable to contain a nitrogen-containing heterocyclic compound.
- the structure of the nitrogen-containing heterocyclic compound is preferably a nitrogen-containing 5-membered ring structure or a 6-membered ring structure, and more preferably a nitrogen-containing 5-membered ring structure.
- nitrogen-containing 5-membered ring structures or nitrogen-containing 6-membered ring structures preferred is a 5- or 6-membered heterocyclic ring structure containing at least one of carbon, nitrogen, oxygen, sulfur and selenium atoms.
- the hetero ring may be fused with a carbon aromatic ring or a heteroaromatic ring.
- hetero ring examples include tetrazole ring, triazole ring, imidazole ring, thiadiazole ring, oxadiazole ring, selenadiazole ring, oxazole ring, thiazole ring, benzoxazole ring, benzthiazole ring, benzimidazole ring, pyrimidine ring, tria
- examples include zaneden ring, tetraazaindene ring, pentaazaindene ring and the like.
- These rings may have a substituent, and the substituent is a nitro group, a halogen atom (eg, chlorine atom, bromine atom), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (eg, methyl) , Ethyl, propyl, t-butyl and cyanoethyl groups, aryl groups (eg, phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl and naphthyl groups), alkenyl groups (for example, For example, allyl group), aralkyl group (for example, each group of benzyl, 4-methylbenzyl, phenethyl), sulfonyl group (for example, each group of methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl
- preferable nitrogen-containing heterocyclic compounds include the following. That is, imidazole, benzoimidazole, benzoindazole, benzotriazole, tetrazole, benzoxazole, benzothiazole, pyridine, quinoline, pyrimidine, piperidine, piperazine, quinoxaline, morpholine and the like can be mentioned, and these are alkyl groups, carboxy groups, sulfo groups , And the like.
- Preferred nitrogen-containing 6-membered ring compounds are compounds having a triazine ring, pyrimidine ring, pyridine ring, pyrroline ring, piperidine ring, pyridazine ring, and pyrazine ring, and among them, compounds having a triazine ring or a pyrimidine ring are preferable.
- nitrogen-containing six-membered ring compounds may have a substituent, and the substituent in that case is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms; An alkoxy group of ⁇ 6, more preferably an alkoxy group having 1 to 3 carbon atoms; a hydroxyl group; a carboxy group; a mercapto group; an alkoxyalkyl group having 1 to 6 carbon atoms, more preferably an alkoxyalkyl group having 1 to 3 carbon atoms; And a hydroxyalkyl group of 1 to 6 carbon atoms, more preferably a hydroxyalkyl group of 1 to 3 carbon atoms.
- preferable nitrogen-containing 6-membered ring compounds include triazine, methyl triazine, dimethyl triazine, hydroxyethyl triazine ring, pyrimidine, 4-methyl pyrimidine, pyridine and pyrroline.
- organic mercapto compound examples include alkyl mercapto compounds, aryl mercapto compounds, and heterocyclic mercapto compounds.
- alkyl mercapto compound examples include cysteine and thiomalic acid
- aryl mercapto compound examples include thiosalicylic acid.
- heterocyclic mercapto compound examples include 2-phenyl-1-mercaptotetrazole and 2-mercaptobenzimidazole.
- 2-mercaptobenzothiazole 2-mercaptobenzoxazole, 2-mercaptopyrimidine, 2,4-dimercaptopyrimidine, 2-mercaptopyridine and the like, and these include substituents such as alkyl group, carboxy group, sulfo group and the like You may have
- benzotriazole 5-methylbenzotriazole, 5-aminobenzotriazole, 5-chlorobenzotriazole, tetrazole, 5-aminotetrazole, 5-methyltetrazole, 5-phenyltetrazole Particular preference is given to benzotriazole being most preferred.
- the nitrogen-containing heterocyclic compound and the organic mercapto compound can be used alone or in combination of two or more.
- the content (total content) of the nitrogen-containing heterocyclic compound and the organic mercapto compound in the treatment liquid is not particularly limited, but is preferably 0.1 to 5.0% by mass with respect to the total amount of the treatment liquid. More preferably, it is 0.1 to 3.0% by mass.
- the treatment liquid in the present invention may contain at least one surfactant.
- Surfactants can be used as surface tension modifiers.
- surface tension modifiers nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants and the like can be mentioned. Among them, from the viewpoint of the aggregation speed of the ink composition, nonionic surfactants or anionic surfactants are preferable.
- the surfactant include fatty acid salts, alkyl sulfuric acid ester salts, alkyl benzene sulfonic acid salts, alkyl naphthalene sulfonic acid salts, dialkyl sulfosuccinic acid salts, alkyl phosphoric acid ester salts, naphthalene sulfonic acid formalin condensates, polyoxy acids
- Anionic surfactants such as ethylene alkyl sulfate ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, Nonionic surfactants such as glycerin fatty acid ester and oxyethylene oxypropylene block copolymer are preferred.
- SURFYNOLS Air Products & Chemical Ls
- SURFYNOLS Air Products & Chemical Ls
- amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable.
- JP-A-59-157636, pp. (37) to (38), Research Disclosure No. 5 The surfactants listed as in 308119 (1989) can also be used.
- fluorine-based (fluorinated alkyl-based) surfactants, silicone-based surfactants, and the like described in JP-A-2003-322926, JP-A-2004-325707, and JP-A-2004-309806 can also be used.
- the surface tension of a process liquid can be adjusted and the surface tension of a process liquid will be 40 mN / m or more. It is preferable that it is such content.
- the content is preferably 40 to 60 mN / m, more preferably 42 to 50 mN / m, from the viewpoint of suppressing the occurrence of curling in the recording medium.
- the content is more preferably 42 to 47 mN / m.
- the surface tension of the treatment liquid is measured at 25 ° C. by a plate method using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
- the treatment liquid in the present invention may contain other aggregating components in addition to the above-mentioned organic acidic compound as long as the effects of the present invention are not impaired.
- polyvalent metal salts alkaline earth metals of the second group of the periodic table (for example, magnesium, calcium), transition metals of the third group of the periodic table (for example, lanthanum), cations from the thirteenth group of the periodic table Mention may be made of (for example aluminum), salts of lanthanides (for example neodymium) and polyallylamine, polyallylamine derivatives.
- carboxylates (formic acid, acetic acid, benzoates and the like), nitrates, chlorides and thiocyanates are suitable.
- calcium or magnesium salts of carboxylic acids (formic acid, acetic acid, benzoate and the like), calcium or magnesium salts of nitric acid, calcium chloride, magnesium chloride, and calcium or magnesium salts of thiocyanic acid are preferable.
- the content of the polyvalent metal salt in the treatment liquid can be, for example, 1 to 10% by mass.
- the treatment liquid in the present invention can further contain other additives.
- additives for example, anti-fading agent, emulsion stabilizer, penetration accelerator, UV absorber, preservative, mildew agent, pH adjuster, viscosity modifier, dispersion stabilizer, rust inhibitor, chelating agent And other known additives.
- the treatment liquid in the present invention contains substantially no colorant such as a pigment, and specifically, the content of the colorant relative to the total amount of the treatment liquid is less than 1% by mass (more preferably 0.5% by mass or less). And more preferably 0.1% by mass or less).
- the treatment liquid in the present invention preferably has a pH (25 ° C. ⁇ 1 ° C.) of 3.5 or less from the viewpoint of the aggregation rate of the ink composition, and more preferably 0.5 to 2.5. More preferably, it is 0.5 to 2.0.
- the viscosity of the treatment liquid is preferably in the range of 1 to 30 mPa ⁇ s, more preferably in the range of 1 to 20 mPa ⁇ s, and still more preferably in the range of 2 to 15 mPa ⁇ s, from the viewpoint of the aggregation speed of the ink composition.
- the range of 2 to 10 mPa ⁇ s is particularly preferred.
- the viscosity is measured under the conditions of 25 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
- an ink composition containing a pigment, a pyrrolidone derivative, a specific glycerin compound and water is applied to the processing liquid application surface of the recording medium which has passed through the processing liquid application process.
- the infiltration of the ink composition into the recording medium is suppressed by applying the treatment liquid to the recording medium before the image formation by the ink composition, and the bleeding is prevented. Furthermore, by forming an image using an ink composition containing at least a pyrrolidone derivative and a specific glycerin compound in the ink composition, the image bearing on the surface of the recording medium is provided with abrasion resistance. As a result, the image on the surface of the recording medium is unlikely to be lost even under external load.
- the image obtained by the image forming method of the present invention has excellent scratch resistance, it is also possible to form a large number of images at high speed by setting the conveyance speed of the recording medium to 80 m / min or more.
- the conveyance speed of the recording medium is high, the ink composition which has dropped can rapidly penetrate into the recording medium, or when the image can not maintain a certain level of strength for a short time, the recording media rub each other and the image quality is easily deteriorated. . This phenomenon is particularly likely to occur at a transport speed of 80 m / min or more.
- the transport speed is preferably faster, more preferably 100 m / min or more, and still more preferably 150 m / min or more.
- the upper limit of the transport speed is not particularly limited, but is preferably 350 m / min from the viewpoint of the need to stably transport the recording medium.
- the application of the ink composition to the treatment liquid application surface of the recording medium can use the same method as the application of the treatment liquid to the recording medium.
- the formation of an image using an inkjet method can be performed by discharging an ink composition to a desired recording medium by supplying energy.
- the method described in paragraphs [0093] to [0105] of JP-A-2003-306623 can be applied.
- the ink jet method is not particularly limited, and the ink may be formed using a known method, for example, a charge control method in which the ink is ejected using electrostatic attraction, or a piezoelectric element which generates mechanical strain by application of a voltage.
- Piezo ink jet system to discharge acoustic ink jet system to change electric signal to acoustic beam and irradiate ink to discharge ink by using radiation pressure, and heat ink to form bubble, and use thermal generated pressure
- It may be any of inkjet (bubble jet (registered trademark)) method and the like.
- the ink jet method includes a method of ejecting many low density inks with a small volume called photo ink, a method of improving the image quality using a plurality of inks having substantially the same hue and different densities, and a colorless and transparent ink. The method used is included.
- a piezo inkjet method is suitable.
- the continuous discharge performance and the discharge stability of the ink are further improved.
- the distortion form of the piezoelectric element may be any of a deflection mode, a longitudinal mode, and a shear mode.
- the structure of the piezoelectric element and the structure of the piezoelectric head can adopt known techniques without particular limitation.
- the inkjet method applicable to the present invention may be a shuttle method in which recording is performed while scanning the head in the width direction of the recording medium using a short serial head, but it corresponds to the entire area of one side of the recording medium It is preferable that a line system using a line head in which the recording elements are arranged is applied.
- a line method an image is recorded on the entire surface of the recording medium by scanning the recording medium in a direction (hereinafter, may be referred to as a sub-scanning direction) orthogonal to the arrangement direction of the recording elements (main scanning direction). be able to.
- the ink applying step in the present invention may be a step of applying the ink composition to the recording medium transported in the sub scanning direction at a transport speed of 50 m / min or more by the inkjet method.
- the amount of droplets of the ink composition ejected from the head is preferably 0.5 pl (picoliter) to 6 pl, more preferably 1 pl to 5 pl, and still more preferably 2 pl to 4 pl from the viewpoint of obtaining a high definition image. .
- the ink composition used in the ink application step contains a pigment, a pyrrolidone derivative, a specific glycerin compound, and water.
- the ink composition may further contain other components such as resin particles, if necessary.
- the ink composition in the present invention contains at least one kind of pigment.
- the pigment can be appropriately selected depending on the purpose, and may be either an organic pigment or an inorganic pigment.
- the organic pigment include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, aniline black and the like. Among these, azo pigments, polycyclic pigments and the like are more preferable.
- an azo pigment an azo lake, an insoluble azo pigment, a condensation azo pigment, a chelate azo pigment etc. are mentioned, for example.
- polycyclic pigments examples include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, and the like.
- dye chelates include basic dye chelates and acid dye chelates.
- the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chromium yellow, carbon black and the like. Among these, carbon black is particularly preferable. In addition, as carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, a thermal method, is mentioned, for example. Among these pigments, water dispersible pigments are preferred.
- the following pigments (1) to (4) can be mentioned as specific examples of the water-dispersible pigment.
- An encapsulated pigment that is, a polymer dispersion obtained by incorporating a pigment in polymer fine particles, more specifically, coating the pigment with a hydrophilic water-insoluble resin and hydrophilizing the resin layer on the pigment surface
- self-dispersing pigment that is, having at least one hydrophilic group on the surface, and at least one of water dispersibility and water solubility in the absence of a dispersant
- resin-dispersed pigment that is, a weight-average molecular weight of 50,000 or less Pigment dispersed with water-soluble polymer compound (4)
- Surfactant dispersed pigment ie, pigment dispersed with surfactant
- the resin of the encapsulated pigment is preferably, but not limited to, a polymer compound having self-dispersing ability or dissolving ability in a mixed solvent of water and a water-soluble organic solvent, and having an anionic group (acidic).
- the number average molecular weight of the resin is preferably in the range of 1,000 to 100,000, and particularly preferably in the range of 3,000 to 50,000.
- this resin is preferably a resin which is dissolved in an organic solvent to be a solution.
- the resin can exhibit the function as a coating film on a pigment or as a coating when used as an ink.
- the resin is preferably used in the form of a salt of an alkali metal or an organic amine.
- the resin of the encapsulated pigment include thermoplastic, thermosetting or modified acrylics, epoxys, polyurethanes, polyethers, polyamides, unsaturated polyesters, phenols, silicones, or fluorines.
- Resins polyvinyl resins such as vinyl chloride, vinyl acetate, polyvinyl alcohol, or polyvinyl butyral; polyester resins such as alkyd resin and phthalic acid resin; melamine resin, melamine formaldehyde resin, amino alkyd cocondensation resin, urea resin, urea And amino-based materials such as resins; or materials having anionic groups such as copolymers or mixtures thereof.
- an anionic acrylic resin is, for example, an acrylic monomer having an anionic group (hereinafter, referred to as “anionic group-containing acrylic monomer”) and, if necessary, an anionic group-containing acrylic monomer. It is obtained by polymerizing other polymerizable monomers in a solvent.
- anionic group-containing acrylic monomer include acrylic monomers having one or more anionic groups selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphonic group, among which an acrylic monomer having a carboxy group is particularly preferred. Particularly preferred.
- acrylic monomer having a carboxy group examples include acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like. Among these, acrylic acid or methacrylic acid is preferable.
- the encapsulated pigment can be produced by conventional physical and chemical methods. For example, as described in JP-A-9-151342, JP-A-10-140065, JP-A-11-209672, JP-A-11-172180, JP-A-10-25440, or JP-A-11-43636. It can be manufactured by a method. Specific examples thereof include phase inversion emulsification methods and acid precipitation methods described in JP-A-9-151342 and JP-A-10-140065, and among them, phase inversion emulsification is preferable in terms of dispersion stability. preferable. The phase inversion emulsification method will be described later.
- a self-dispersible pigment is one of the preferred examples.
- the self-dispersion pigment refers to a large number of hydrophilic functional groups and / or salts thereof (hereinafter referred to as "dispersion-imparting groups") either directly on the pigment surface or indirectly via an alkyl group, an alkyl ether group, an aryl group or the like.
- These pigments are pigments that can be dispersed in an aqueous medium without the use of dispersants for pigment dispersion.
- "dispersion in an aqueous medium without using a dispersing agent” means that the pigment can be dispersed in an aqueous medium without using a dispersing agent for dispersing the pigment.
- An ink containing a self-dispersion pigment as a coloring agent usually does not need to contain a dispersant to be dispersed in order to disperse the pigment, so there is almost no foaming due to a decrease in the defoaming property caused by the dispersant, and the ejection stability It is easy to prepare an ink excellent in
- the imparting group is bonded by subjecting the pigment to physical treatment or chemical treatment to bind (graft) an active species having a dispersing property or a dispersing property to the pigment surface.
- a vacuum plasma process etc. can be illustrated, for example.
- a wet oxidation method in which the pigment surface is oxidized with an oxidizing agent in water a method in which a carboxy group is bonded via a phenyl group by bonding p-aminobenzoic acid to the pigment surface, Etc. can be illustrated.
- a self-dispersible pigment surface-treated by oxidation treatment with hypohalous acid and / or hypohalite or ozone oxidation can be mentioned as a preferred example.
- a commercially available product may be used as the self-dispersion pigment, and specifically, Microjet CW-1 (trade name; manufactured by Orient Chemical Industries, Ltd.), CAB-O-JET 200, CAB-O-JET 300 (trade name) And Cabot Co., Ltd.).
- the pigment is preferably an encapsulated pigment in which a water-insoluble resin is used among pigment dispersants and at least a part of the surface of the pigment is coated with a water-insoluble resin, for example, a polymer emulsion in which the pigment is contained in water-insoluble resin particles. More specifically, a water-dispersible pigment is preferred, which is capable of covering at least a part of the pigment with a water-insoluble resin, forming a resin layer on the surface of the pigment and dispersing it in water. It is preferable to use such a water-insoluble resin-coated encapsulated pigment from the viewpoint of pigment cohesion and to form a high resolution image when recording at high speed.
- the phase inversion emulsification method is basically a self-dispersion (phase inversion emulsification) method in which a mixed melt of a resin having a self-dispersing ability or a dissolving ability and a pigment is dispersed in water.
- the mixed melt may contain a polymer compound and a curing agent.
- the mixed melt refers to a state including not being dissolved, mixed, or dissolved and mixed, or any of these two states.
- the “phase inversion emulsification method” the method described in JP-A-10-140065 can be mentioned.
- the descriptions in JP-A-9-151342 and JP-A-10-140065 can be referred to.
- Pigment dispersant The pigment dispersant can achieve easy dispersion when the pigment is dispersed, and dispersion stabilization after the dispersion.
- a pigment dispersant a nonionic compound, an anionic compound, a cationic compound, an amphoteric compound, etc. are mentioned.
- copolymers of monomers having an ⁇ , ⁇ -ethylenically unsaturated group can be mentioned.
- Examples of monomers having an ⁇ , ⁇ -ethylenically unsaturated group include ethylene, propylene, butene, pentene, hexene, vinyl acetate, allyl acetate, acrylic acid, methacrylic acid, crotonic acid, crotonic acid ester, itaconic acid, itaconic acid Acid monoester, maleic acid, maleic acid monoester, maleic acid diester, fumaric acid, fumaric acid monoester, vinyl sulfonic acid, styrene sulfonic acid, sulfonated vinyl naphthalene, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, bismethacryloxy Styrene derivatives such as ethyl phosphate, methacryloxyethyl phenyl acid phosphate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, styrene, ⁇ -methylstyrene
- a copolymer obtained by copolymerizing one or more monomers having an ⁇ , ⁇ -ethylenically unsaturated group can be used as the polymer dispersant.
- the pigment dispersant preferably has a weight average molecular weight of 2,000 to 60,000.
- the addition amount of the pigment dispersant to the pigment is preferably in the range of 10% to 100% of the pigment on a mass basis, more preferably 20% to 70% of the pigment, and still more preferably 40% to 50% of the pigment It is.
- the pigment in the present invention is preferably a resin-coated pigment in which at least a part of the pigment surface is coated with a crosslinked polymer obtained by crosslinking a water-soluble resin with a crosslinking agent.
- the water soluble resin acts as a dispersant to disperse the pigment.
- the pigment is coated with a cross-linked polymer to provide excellent stability (stability against pH fluctuation, stability against temperature fluctuation) when made into an ink composition using a pigment dispersion or a pigment dispersion. can do.
- water-soluble resin examples include polyvinyls, polyurethanes, polyesters, etc. Among them, polyvinyls are preferable.
- the water-soluble resin has a group that causes a crosslinking reaction in the molecule by the crosslinking agent.
- a group is not particularly limited, and examples thereof include a carboxy group or a salt thereof, an isocyanate group, an epoxy group and the like.
- the water-soluble resin that can be used in the present invention is preferably a copolymer obtained using a carboxy group-containing monomer as a copolymerization component.
- carboxy group-containing monomers include methacrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid, etc. Among them, methacrylic acid and ⁇ -carboxy are preferable from the viewpoint of crosslinkability and dispersion stability. Ethyl acrylate is preferred.
- an optionally selected hydrophilic monomer or hydrophobic monomer may be used as a copolymerization component.
- the hydrophilic monomer may be ionic or nonionic.
- the hydrophobic monomer is not particularly limited, but an alkyl methacrylate having 1 to 20 carbon atoms or an alkyl acrylate having 1 to 20 carbon atoms is preferable.
- the water soluble resin may be either a random polymer or a block or graft polymer.
- the acid value of the water-soluble resin (the number of mg of KOH required to neutralize 1 g of the water-soluble resin) is preferably 135 mg KOH / g to 250 mg KOH / g from the viewpoint of pigment dispersibility and dispersion stability More preferably, it is 135 mg KOH / g to 200 mg KOH / g, and particularly preferably 135 mg KOH / g to 180 mg KOH / g.
- the synthesis method of the polymer as the water-soluble resin is not particularly limited, random polymerization of vinyl monomers is preferable in view of dispersion stability.
- the crosslinking agent a compound having two or more sites that cause a crosslinking reaction can be used.
- a bifunctional or more epoxy compound is preferable in terms of excellent reactivity with a carboxy group.
- the difunctional or higher epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl Ether, polypropylene glycol diglycidyl ether and the like are mentioned, and polyethylene glycol diglycidyl ether and diethylene glycol diglycidyl ether are preferable.
- the molar ratio of the crosslinking site of the crosslinking agent to the crosslinking site of the water-soluble resin is preferably 1: 1.1 to 1:10 from the viewpoint of the crosslinking reaction rate and the stability of the dispersion after crosslinking, and 1: 1 1 to 1: 5 are more preferred, and 1: 1.1 to 1: 3 are most preferred.
- the amount of the water-soluble resin to the pigment is preferably 10% by mass to 250% by mass, more preferably 10% by mass to 200% by mass, still more preferably 20% by mass to 150% by mass, and 30% by mass to 100% by mass Particularly preferred.
- a resin-coated pigment coated with a crosslinked polymer in which the pigment surface is crosslinked with a water-soluble resin with a crosslinking agent can be obtained through the step of dispersing the pigment using a water-soluble resin and then crosslinking with a crosslinking agent.
- a method to be performed through the following steps (1) to (3) is shown.
- the pigments may be used singly or in combination of two or more selected from each group or each group.
- the content of the pigment in the ink composition is preferably 0.1% by mass to 15% by mass with respect to the total mass of the ink from the viewpoint of color density, granularity, ink stability, and ejection reliability. An amount of 0.5% by mass to 12% by mass is more preferable, and an amount of 1% by mass to 10% by mass is particularly preferable.
- the ink composition in the present invention contains at least one pyrrolidone derivative.
- a pyrrolidone derivative in the composition containing the specific glycerin compound described later, the scratch resistance of the image is improved while preventing the ink strike-through phenomenon, and the image is scratched when processing many sheets at high speed. An abrasion failure such as sticking is prevented.
- the pyrrolidone derivative in the present invention can be used without limitation as long as it is a compound having a 5-membered ring containing a lactam structure.
- the lactam structure is a structure containing -CO-NR- in part of the ring, and R in the structure represents a monovalent group.
- Examples of monovalent groups include hydrogen atoms, alkyl groups, aryl groups and alkenyl groups. Among them, a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable.
- the alkyl group, the aryl group and the alkenyl group may or may not have a substituent, but preferably do not have a substituent.
- R in CO—NR— is an alkyl group
- the carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
- the alkyl group may be linear, branched or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, octyl group, nonyl group And decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
- examples of the substituent include an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxyl group, a carboxy group, a halogen atom (fluorine atom, chlorine atom, iodine Atoms etc.).
- R in CO—NR— is an aryl group
- the carbon number of the aryl group is preferably 6 to 20, more preferably 6 to 14, and particularly preferably 6 to 10.
- Specific examples of the aryl group include phenyl group, naphthyl group and anthryl group.
- examples of the substituent include an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxy group, a halogen atom (fluorine atom, chlorine atom, iodine Atoms etc.).
- R in CO—NR— is an alkenyl group
- the carbon number of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.
- the alkenyl group may have a linear structure, a branched structure or a cyclic structure.
- alkenyl group examples include ethenyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2 -Butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1- Heptenyl group, 1-octenyl group and the like can be mentioned.
- examples of the substituent include an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxyl group, a carboxy group, a halogen atom (fluorine atom, chlorine atom, iodine Atoms etc.).
- the pyrrolidone derivative is preferably a compound represented by general formula (P-1).
- R 1 represents a hydrogen atom, an alkyl group, an aryl group or an alkenyl group.
- the alkyl group, the aryl group and the alkenyl group represented by R 1 have the same meaning as the alkyl group, the aryl group and the alkenyl group represented by R in the above-mentioned “structure containing —CO—NR—”, respectively
- the preferable aspect of is also the same.
- R 2 in General Formula (P-1) represents a hydrogen atom or an alkyl group.
- the alkyl group represented by R 2 preferably has 1 to 10 carbon atoms, and may have any of a linear structure, a branched structure, and a cyclic structure.
- R 2 in the general formula (P-1) is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.
- R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- An embodiment is preferred, and an embodiment in which R 1 and R 2 are both hydrogen atoms is particularly preferred.
- pyrrolidone derivatives in the present invention for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 5-methyl- Examples thereof include 2-pyrrolidone, N-phenyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone and the like.
- 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone are preferable, and 2-pyrrolidone and N-methyl-2-pyrrolidone are more preferable from the viewpoint of improving the abrasion resistance of the image.
- 2-pyrrolidone is particularly preferred.
- the content of the pyrrolidone derivative in the present invention in the ink composition is preferably 3.0% by mass to 20.0% by mass, and more preferably 5% by mass to 16% by mass, with respect to the total mass of the ink composition. It is more preferably 6% by mass to 15% by mass.
- the content of the pyrrolidone derivative is 3.0% by mass or more, the abrasion resistance of the image can be further improved.
- the content of the pyrrolidone derivative is 20.0% by mass or less, it is advantageous for maintaining the stability of the ink composition.
- the content ratio (p / s; mass ratio) of the pyrrolidone derivative (p) to the specific glycerin compound (s) described later is preferably 0.075 or more and 4.0 or less.
- the content ratio p / s is 0.075 or more, the abrasion resistance of the image can be further improved.
- the content ratio p / s is 4.0 or less, the effect of preventing the penetration phenomenon caused by the penetration of the ink composition applied to the recording medium to the back surface side is high, and it is advantageous for suppressing the curling.
- the content ratio p / s is more preferably in the range of 0.09 or more and 3.5 or less, and particularly preferably in the range of 0.11 or more and 3.2 or less.
- the ink composition in the present invention contains at least one of the compounds represented by the general formula (II) (specific glycerin compounds).
- the specific glycerin compound is an alkylene oxide adduct of glycerin represented by the general formula (II).
- l + m + n 3-15.
- l + m + n 3-15.
- l + m + n 3-15.
- l + m + n 3-15.
- l + m + n 3-15.
- AO in the general formula (II) represents ethyleneoxy (sometimes abbreviated as EO) and / or propyleneoxy (sometimes abbreviated as PO), and among these, a propyleneoxy group is preferable.
- EO ethyleneoxy
- PO propyleneoxy
- Each AO of (AO) l , (AO) m and (AO) n may be the same or different.
- the alkylene oxide adduct of glycerin may be a commercially available product commercially available.
- polyoxypropylated glycerin ether of polypropylene glycol and glycerin
- Sannix GP-250 average molecular weight 250
- GP-400 average molecular weight 400
- GP-600 average molecular weight 600
- Sanyo Chemical Industries, Ltd. Leocon GP-250 (average molecular weight 250), GP-300 (average molecular weight 300, GP-400 (average molecular weight 400), GP-700 (average molecular weight 700) Lion Corp.
- polypropylene triol glycol triol type average molecular weight 300, average molecular weight 700 [or more, Wako Pure Chemical Industries, Ltd.] and the like.
- SP value is a value represented by the square root of molecular cohesive energy, and R.O. F. Fedors, Polymer Engineering Science, 14, p. 147 to 154 (1974).
- the SP value is preferably in the range of 27.5 or less.
- the ink composition may further contain another water-soluble organic solvent other than the specific glycerin compound.
- the SP value of 70% by mass or more of the total amount of the specific glycerin compound and the other water-soluble organic solvent contained in the ink composition is preferably 27.5 or less.
- the content of the specific glycerin compound is preferably 5.0 to 40.0% by mass, and more preferably 7.0 to 35.0% by mass, based on the total mass of the ink composition. And particularly preferably 8.0 to 30.0% by mass.
- the content of the specific glycerin compound is 5.0% by mass or more, the permeability of the ink composition to the recording medium is alleviated, and the ink is further prevented from passing through.
- water-soluble organic solvents described in paragraph Nos. [0036] to [0039] of JP-A No. 2009-190379 can be mentioned, and it may be appropriately selected from these.
- the ink composition in the present invention preferably further contains at least one of resin particles.
- the resin particles are contained, the abrasion resistance of the image can be further improved by performing heat treatment after image formation.
- the resin particles are preferably self-dispersible resin particles having a hydrophilic structural unit (repeating unit derived from hydrophilic monomer) and a hydrophobic structural unit (repeating unit derived from hydrophobic monomer), and the hydrophilic structural unit It is more preferable to contain self-dispersible resin particles having a glass transition temperature (Tg) of 80 ° C. or higher, and a hydrophobic structural unit, from the viewpoint of further improving the abrasion resistance.
- Tg glass transition temperature
- a Tg of 80 ° C. or higher indicates that it is hydrophobic.
- the Tg of the resin particles is more preferably 100 ° C. to 300 ° C., still more preferably 130 ° C. to 250 ° C., and particularly preferably 160 ° C. to 200 ° C.
- the glass transition temperature of the resin particles is 300 ° C. or less, the abrasion resistance of the recorded image is more effectively improved.
- Tg is a value measured under a normal measurement condition using a differential scanning calorimeter (DSC) EXSTAR 6220 (manufactured by SII Nano Technology Co., Ltd.). However, when the measurement is difficult due to decomposition of the resin, etc., the calculated Tg calculated by the following formula is applied.
- the value of the homopolymer glass transition temperature (Tg i ) of each monomer is the value of Polymer Handbook (3rd Edition) (J. Brandrup, E. H. Immergut (Wiley-Interscience, 1989)).
- acrylic resin acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin, benzoguanamine resin And latexes such as phenol resin, silicone resin, epoxy resin, urethane resin, paraffin resin, and fluorine resin.
- acrylic resin acrylic-styrene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin are mentioned as preferable examples.
- the weight average molecular weight of the resin particles is preferably 10,000 or more and 200,000 or less, and more preferably 100,000 or more and 200,000 or less.
- the average particle diameter of the resin particles is preferably in the range of 10 nm to 1 ⁇ m, more preferably 10 to 200 nm, still more preferably 20 to 100 nm, and particularly preferably 20 to 50 nm.
- the resin particles can be used in a dispersed state such as latex.
- the amount of the resin particles in the ink composition is 0.5 in terms of solid content with respect to the total mass of the ink composition from the viewpoint of fixability, abrasion resistance, and viscosity of the ink composition. -20% by mass is preferable, 3-20% by mass is more preferable, and 5-15% by mass is more preferable.
- the ink composition in the present invention contains water, but the amount of water is not particularly limited. Among them, the amount of water is preferably 10% by mass or more and 99% by mass or less, and more preferably 20% by mass or more and 80% by mass with respect to the total mass of the ink composition from the viewpoint of securing stability and ejection reliability. % Or less, more preferably 30% by mass or more and 70% by mass or less, and particularly preferably 40% by mass or more and 60% by mass or less.
- the water is one which is obtained by removing as much as possible ionic impurities such as pure water or ultrapure water such as ion exchange water, ultrafiltered water, reverse osmosis water, and distilled water.
- ionic impurities such as pure water or ultrapure water such as ion exchange water, ultrafiltered water, reverse osmosis water, and distilled water.
- water sterilized by ultraviolet irradiation, hydrogen peroxide addition or the like in the case where the pigment dispersion and the ink composition using the same are stored for a long period of time, since generation of mold and bacteria is prevented. .
- the ink composition in the present invention may further contain, as other components, additives such as a penetration solvent, a moisturizing agent, an antiseptic, a mildew proofing agent, a pH adjuster, a chelating agent, and the like.
- additives such as a penetration solvent, a moisturizing agent, an antiseptic, a mildew proofing agent, a pH adjuster, a chelating agent, and the like.
- additives such as a penetration solvent, a moisturizing agent, an antiseptic, a mildew proofing agent, a pH adjuster, a chelating agent, and the like.
- the image forming method of the present invention may be provided with a drying step of drying the ink applied in the ink application step.
- a drying step of drying the ink applied in the ink application step By drying, the liquid medium contained in the ink composition deposited on the recording medium, specifically, water, pyrrolidone derivative, and other water-soluble organic solvents evaporate and scatter, and a colored resin film is formed. Ru.
- a high quality image with few image defects such as scratches and peeling can be formed at high speed on the recording medium.
- the heating and drying can be performed by a known heating means such as a heater, an air blowing means utilizing air blowing such as a dryer, or a combination thereof.
- a heating method for example, a method of applying heat with a heater or the like from the ink application surface of the recording medium and the opposite side thereof (specifically, for example, warm air is applied to the ink application surface, and the opposite of the ink application surface
- the surface may be heated by a heater drum), a method of applying hot air or hot air to the ink application surface of the recording medium, a heating method using an infrared heater, and the like.
- the recording medium may be heated so that the temperature of the recording medium is 40 to 80 ° C. by blowing air, or may be brought into contact with a drying drum of 50 to 110 ° C. and dried so that the temperature of the recording medium is 40 to 80 ° C. .
- these may be used in combination and dried.
- the image forming method of the present invention may be provided with a cooling step of cooling the recording medium after being once heated and dried in the drying step.
- the cooling method may be any method as long as the temperature of the recording medium can be actively lowered. Examples of the cooling method include a method of causing the recording medium to pass through the cooling zone, a method of applying cold air to the recording medium, and a method of bringing the recording medium into contact with the cooled object.
- the image forming method of the present invention may further include a heating and fixing step of heating and fixing the ink composition on the recording medium after the ink application step, if necessary.
- the heat fixing step the image formed by the application of the ink composition is heated and fixed on a recording medium (heat fixing process).
- heat fixing process the image on the recording medium is fixed, and the scratch resistance of the image can be further improved.
- the heating is preferably performed, for example, at a temperature equal to or higher than the minimum film forming temperature (MFT) of resin particles in the image.
- MFT minimum film forming temperature
- the particles are filmed to enhance the image.
- the pressure at the time of pressure is preferably in the range of 0.1 to 3.0 MPa in terms of surface smoothing.
- the heating method is not particularly limited, but a non-contact drying method such as a method of heating with a heating element such as a nichrome wire heater, a method of supplying warm air or hot air, a method of heating with a halogen lamp, an infrared lamp, etc. It can mention suitably.
- the method of heating and pressing is not particularly limited.
- a method of pressing a heat plate against the image forming surface of a recording medium, a pair of heating and pressing rollers, a pair of heating and pressing belts, or a recording medium By using a heating and pressing device provided with a heating and pressing belt arranged on the image recording surface side and a holding roller arranged on the opposite side, the heating and fixing is carried out by bringing them into contact, such as passing a pair of rollers.
- the method to carry out is mentioned suitably.
- the treatment liquid described above and the ink composition described above may be combined to form an ink set. That is, the ink set of the present invention is represented by a treatment liquid containing an organic acidic compound represented by the general formula (I), a water-soluble polymer compound, and water, a pigment, a pyrrolidone derivative, and the general formula (II) And an ink composition containing water.
- an image having excellent scratch resistance and high resolution can be obtained.
- the details and preferred embodiments of the treatment liquid and the ink composition possessed by the ink set are the same as the details and the preferred embodiments of the treatment liquid and the ink composition used in the image forming method of the present invention.
- the weight average molecular weight was measured by gel permeation chromatography (GPC). Unless otherwise noted, GPC uses HLC-8020GPC (manufactured by Tosoh Corp.), and three columns of TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corp., 4.6 mm ID ⁇ 15 cm) as columns. THF (tetrahydrofuran) was used as an eluent. The conditions were a sample concentration of 0.45% by mass, a flow rate of 0.35 ml / min, a sample injection amount of 10 ⁇ l, a measurement temperature of 40 ° C., and an IR detector. In addition, the calibration curve can be obtained from Tosoh Corp.
- Example 1 Preparation of Water-Soluble Polymer Compound (Water-Soluble Polymer)]
- the water-soluble polymer compound (water-soluble polymer 1) used as a component in the treatment liquid was prepared as follows.
- the water soluble polymer 1 was synthesized as follows. In a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet, 30.0 g of isopropyl alcohol was charged, and the temperature was raised to 65 ° C. under a nitrogen atmosphere.
- MMA methyl methacrylate
- EA ethyl acrylate
- AMPS acrylamido-2-methylpropane sulfonic acid
- isopropyl alcohol (30 g)
- water 15 g
- V-601 polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.
- the weight average molecular weight (Mw) of the obtained water-soluble polymer 1 is 45000 (calculated by polystyrene conversion by gel permeation chromatography (GPC), and columns used are TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)) Met.
- Polymeric dispersant P-1 was synthesized as shown below according to the following scheme.
- methyl ethyl ketone 88 g is added to a 1000 ml three-necked flask equipped with a stirrer and a condenser, and heated to 72 ° C. under a nitrogen atmosphere, and then 50 g of methyl ethyl ketone, 0.85 g of dimethyl 2,2'-azobisisobutyrate and 60 g of benzyl methacrylate A solution of 10 g of methacrylic acid and 30 g of methyl methacrylate was dropped over 3 hours.
- the reaction was further carried out for 1 hour, and a solution of 0.42 g of dimethyl 2,2'-azobisisobutyrate dissolved in 2 g of methyl ethyl ketone was added thereto, and the temperature was raised to 78 ° C and heated for 4 hours.
- the resulting reaction solution was reprecipitated twice in a large excess of hexane, and the precipitated resin was dried to obtain 96 g of a polymer dispersant P-1.
- the numeral of each constituent unit of the polymer dispersant P-1 represents a mass ratio.
- the composition of the obtained resin was confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 44,600. Furthermore, it was 65.2 mgKOH / g when the acid value was calculated
- the dispersion obtained at 8000 rpm was further centrifuged for 30 minutes using a high-speed centrifugal cooler 7550 (manufactured by Kubota Mfg. Co., Ltd.) using a 50 mL centrifuge tube, and the supernatant other than the precipitate was recovered. Thereafter, the pigment concentration was determined from the absorbance spectrum, and a dispersion (cyan dispersion liquid C) of resin-coated pigment particles (pigment coated with a polymer dispersant) having a pigment concentration of 10.2% by mass was obtained. The average particle diameter of the obtained cyan dispersion liquid C was 105 nm.
- the preparation of the cyan dispersion is the same as the preparation of the cyan dispersion except that pigment red 122, which is a magenta pigment, is used instead of pigment blue 15: 3 (phthalocyanine blue A220, manufactured by Dainichiseika Co., Ltd.). Then, a dispersion (magenta dispersion M) of resin-coated pigment particles (pigment coated with polymer dispersant) was prepared. The average particle diameter of the obtained magenta dispersion M was 85 nm.
- the preparation of the cyan dispersion was the same as the preparation of the cyan dispersion except that pigment yellow 74, which is a yellow pigment, was used instead of pigment blue 15: 3 (phthalocyanine blue A220, manufactured by Dainichiseika Co., Ltd.).
- a dispersion (yellow dispersion Y) of resin-coated pigment particles (pigment coated with polymer dispersant) was prepared. The average particle size of the obtained yellow dispersion Y was 82 nm.
- black dispersion In the preparation of the cyan dispersion, in place of pigment blue 15: 3 (phthalocyanine blue A220, manufactured by Dainichi Seisei Co., Ltd.), cyan dispersion except using carbon black which is a black pigment (Nipex 160-IQ manufactured by Degussa) is used.
- a dispersion (black dispersion K) of resin-coated pigment particles (pigment coated with polymer dispersant) was prepared in the same manner as in the preparation of the solution.
- the average particle diameter of the obtained black dispersion liquid K was 130 nm.
- the composition of the ink shown in Table 1 below is obtained using each of the obtained pigment dispersions (cyan dispersion C, magenta dispersion M, yellow dispersion Y, black dispersion K) and self-dispersible resin particles B-01.
- the components were mixed as described above to prepare ink compositions (magenta ink composition M1, black ink composition K1, cyan ink composition C1, and yellow ink composition Y1).
- Each of the prepared ink compositions is filtered with a plastic disposable syringe using a PVDF 5 ⁇ m filter (Millex SV, 25 mm in diameter) to complete an ink (magenta ink M1, black ink K1, cyan ink C1, yellow ink Y1) did.
- each ink composition in sample 102 to sample 117 is the "alkylene oxide adduct of glycerin" and "2-pyrrolidone” shown in Table 1, the "specific glycerin compound” in Table 2, and The composition is changed to the type and amount shown in “pyrrolidone derivative or other solvent”.
- “water, 65%” shown in Table 1 was the remaining amount to be 100% in total according to the change amounts of “specific glycerin compound” and “pyrrolidone derivative or other solvent”.
- the composition of each processing solution in the samples 102 to 110 and the samples 113 to 117 is the composition of the processing solution of the sample 101, in which the kind and amount of the organic acidic compound are changed as shown in Table 2.
- AO in the "type” column in the “specific glycerin compound” column represents “AO” in the general formula (II), and "l + m + n” is the sum of l, m and n in the general formula (II) Means a number.
- the treatment liquid was coated on the surface of the recording medium using a coating bar so as to have a coating amount of 1.0 g / m 2 .
- Rubbing resistance An amount (ink UTF-8: character represented by E584AA), parallel (UTF-8: character represented by E4B8A6), in an amount such that the ink coating amount is 6 g / m 2 ,
- Normal characters Japanese kanji shown in FIG. 1 (a)
- inferiority UTF-8: character represented by E58AA3
- exclusive character represented by UTF-8: E584AA
- parallel UTF -8: An image consisting of hollow characters (Japanese kanji shown in FIG.
- Example 2 In the preparation of the ink set of sample 101 in Example 1, except that the treatment liquid was prepared without using the silicone oil in the treatment liquid of sample 101, the ink of sample 201 was prepared in the same manner as the preparation of the ink set of sample 101. A set was made.
- the abrasion resistance and the resolution were evaluated in the same manner as in Example 1, the same improvement in the abrasion resistance and the resolution as in the case of the sample 101 of Example 1 was recognized even in the case of the sample 201.
- coating unevenness which is considered to be caused by the bubbles of the treatment liquid was generated, and the sample 101 was superior from the viewpoint of stable resolution. From this, the treatment liquid contains the silicone oil, so that the coating unevenness can be made less likely to occur, and by forming an image using the treatment liquid containing the silicone oil, the image with stable resolution can be obtained. It turned out that it can be obtained.
- Example 3 The preparation of the ink set of sample 101 in Example 1 is the same as the preparation of the ink set of sample 101 except that the organic acidic compound in the treatment liquid of sample 101 is changed to the organic acidic compound shown in Table 3. Ink sets of samples 301 to 303 were prepared.
- the abrasion resistance and resolution of Samples 301 to 303 were evaluated in the same manner as in Sample 101 of Example 1.
- the abrasion resistance and resolution of Samples 301 to 303 were the same as those of Sample 101 in Example 1.
- Example 4 A sample was prepared in the same manner as the preparation of the ink set of sample 101 except that 2-pyrrolidone in the composition of sample 101 was changed to the pyrrolidone derivative shown in Table 4 in the preparation of the ink set of sample 101 in Example 1. An ink set of 401 to 405 was prepared.
- the abrasion resistance and the resolution of Samples 401 to 405 were evaluated in the same manner as in the case of Sample 101 in Example 1.
- the abrasion resistance and the resolution similar to those in Sample 101 of Example 1 were observed in Samples 401 to 405 as well.
- Example 5 The preparation of the ink set of sample 101 in Example 1 was repeated except that water-soluble polymer 1 in the composition of sample 101 was changed to water-soluble polymers 2 to 9 shown in Table 5; An ink set was produced.
- the water-soluble polymer 2 is “MMA / AMPS”
- the water-soluble polymer 3 is “MMA / SPA (K)”
- the water-soluble polymer 4 is “MMA”.
- / BMA / AMPS water-soluble polymer 5 as "MMA / TBMA / AMPS”
- water-soluble polymer 6 as "MMA / IBOMA / AMPS”
- water-soluble polymer 7 as "MMA / CHMA / AMPS”
- water-soluble polymer 8 is described as "MMA / BzMA / AMPS” and the water-soluble polymer 9 as "MMA / PEMA / AMPS”, respectively.
- SPA (K) represents sulfopropyl acrylate potassium salt
- TBMA represents tert-butyl methacrylate
- IBOMA represents isobornyl methacrylate
- CHMA represents cyclohexyl methacrylate
- BzMA represents benzyl methacrylate
- PEMA stands for 2-phenoxyethyl methacrylate.
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Abstract
Description
<1> 下記一般式(I)で表される有機酸性化合物と、水溶性高分子化合物と、水とを含有する処理液を記録媒体上に付与する処理液付与工程、及び記録媒体の処理液付与面に、顔料と、ピロリドン誘導体と、下記一般式(II)で表される化合物と、水とを含有するインク組成物を付与するインク付与工程を有する画像形成方法である。
一般式(A)中、La1は、単結合、-COO-、又は-CON(Ra3)-を表す。Ra3は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
一般式(A)中、La2は、単結合、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の2価の連結基を表す。
一般式(A)中、Aaはイオン性基を表す。
一般式(B)中、Lb1は、単結合、-COO-、又は-CON(Rb3)-を表す。Rb3は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
一般式(B)中、Rb2は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
但し、Rb2が水素原子であるときは、Lb1は単結合である。
<<画像形成方法>>
本発明の画像形成方法は、一般式(I)で表される有機酸性化合物、水溶性高分子化合物、及び水を含有する処理液を記録媒体上に付与する処理液付与工程と、処理液を付与した側の記録媒体面上に、顔料、ピロリドン誘導体、一般式(II)で表される化合物、及び水を含有するインク組成物を付与するインク付与工程とを有する。
本発明の画像形成方法は、必要に応じて、更に、形成された画像を加熱定着する等の他の工程が設けられていてもよい。
以下、インク組成物を、単にインクとも称する。一般式(I)で表される有機酸性化合物を特定有機酸性化合物とも称し、一般式(II)で表される化合物を特定グリセリン系化合物とも称する。
記録媒体において、インク組成物の滲みが少しでも生じてしまうと、インク組成物で画像を点描写したとき、画像がぼやけ、画像の解像度が低下してしまう傾向にある。
しかし、インク組成物を、ピロリドン誘導体と特定グリセリン系化合物とを用いて構成することで、傷等の画像欠陥が生じにくい画像強度を保つことができる。従って、形成される画像は、耐擦性にも優れる。
以下、本発明の画像形成方法を構成する処理液付与工程、インク付与工程、及び、必要に応じて設けることができる他の工程について詳述する。
処理液付与工程では、一般式(I)で表される有機酸性化合物、水溶性高分子化合物、及び水を含有する処理液を記録媒体上に付与する。
すなわち、本発明の画像形成方法では、記録媒体上に、インク組成物を付与する前に、予めインク組成物中の成分(顔料など)を凝集させるための処理液を付与しておき、記録媒体上に付与された処理液に接触するようにインク組成物を付与して画像化する。
これにより、画像形成を高速化(例えば、50m/min以上の搬送速度で記録媒体を搬送しながら画像形成)することができ、高速記録しても、画像濃度および解像度の高い画像が得られる。
加熱方法としては、例えば、記録媒体の処理液の付与面と反対側からヒーター等で熱を与える方法や、記録媒体の処理液の付与面に温風又は熱風をあてる方法、赤外線ヒーターを用いた加熱法などが挙げられ、これらの複数を組み合わせて加熱してもよい。
本発明の画像形成方法では、上述のとおり、記録媒体上に画像が形成される。
記録媒体には、特に制限はないが、一般のオフセット印刷などに用いられる、セルロースを主体とする一般印刷用紙を用いることができる。
塗工紙は、支持体となるセルロースを主体とした一般に表面処理されていない上質紙や中性紙等の表面に、無機顔料などを含有するコート層(塗工層ともいう。)を設けた記録媒体である。塗工紙は画像部の光沢ムラが発生しやすい傾向があるが、処理液にリン酸又はリン酸化合物を含む場合には、画像部の光沢ムラの発生を効果的に抑制することができる。具体的には、アート紙、コート紙、軽量コート紙、又は微塗工紙が好ましい。
処理液は、特定有機酸性化合物、水溶性高分子化合物、及び水を含有する。処理液は、シリコーンオイル等、必要に応じその他の成分を含有してもよい。
処理液は、特定有機酸性化合物により、インク組成物中の成分(顔料等)を凝集させる液である。顔料を含有するインク組成物に加え、処理液を用いることで、インクジェット記録を高速化でき、高速記録しても濃度、解像度の高い描画性(例えば細線や微細部分の再現性)に優れた画像が得られる。
処理液は一般式(I)で表される有機酸性化合物(特定有機酸性化合物)の少なくとも1種を含む。
下記一般式(I)で表される有機酸性化合物は、インク組成物(顔料等)を凝集させる能力が高く、記録媒体上に付与されたインク滴の移動が効果的に抑制される。その結果、インク滴の移動に起因する、画像のざらつきが効果的に抑制される。
また、一般式(I)において、mは、3~5の整数であることが好ましい。mが3以上であると、インク滴の移動が更に抑制される。mが5以下であると、画像の耐擦性が更に向上する。
処理液が、特定有機酸性化合物以外の他の有機酸性化合物を含む場合、他の有機酸性化合物は、一分子内に2つのカルボキシ基を含む化合物であることが好ましい。
一分子内に2つのカルボキシ基を含む化合物としては、酒石酸、フタル酸、4-メチルフタル酸、DL-リンゴ酸、マロン酸、グルタル酸、ジメチルマロン酸、マレイン酸が挙げられる。中でも、DL-リンゴ酸、マロン酸、グルタル酸、ジメチルマロン酸、マレイン酸が好ましい。
本発明における処理液は、水溶性高分子化合物を少なくとも1種含む。
これにより、インク組成物中の成分を有機酸性化合物により凝集させる際の凝集速度をある程度抑え、記録媒体に付与されたインク滴を、目的とする大きさに広げることができる。これにより、インクの広がり不足に起因する画像のざらつきを抑制できる。
ここで、「水溶性」とは、水に一定濃度以上溶解できることをいい、水性の処理液中に(望ましくは均一に)溶解し得るものであればよい。具体的には、25℃の水に対する溶解度が5質量%以上であることが好ましく、10質量以上であることがより好ましい。
そこで本発明では、水溶性高分子化合物を含む処理液にシリコーンオイルを含有させることで、画像のざらつきを抑制しながら、処理液中の泡に起因する処理液の塗布ムラを抑制できる。
また、水溶性高分子化合物としては、後述する特定高分子化合物も好適である。
処理液中における水溶性高分子化合物の含有量が0.1質量%以上であれば、インク滴の広がりをより促進でき、処理液中における水溶性高分子化合物の含有量が10質量%以下であれば、処理液の増粘をより抑制できる。また、処理液中における水溶性高分子化合物の含有量が10質量%以下であれば、処理液中の泡に起因する処理液の塗布ムラをより抑制できる。
処理液に含まれる水溶性高分子化合物としては、イオン性基(好ましくはアニオン性基)を有する親水性の構造単位を含む高分子化合物(以下、「特定高分子化合物」ともいう)が好ましい。これにより、記録媒体に付与されたインク滴の広がりをより促進することができ、画像のざらつきが更に抑制される。
特定高分子化合物は、側鎖部分のイオン性基の作用により処理液中の溶媒(例えば水)との親和性を保持する。一方、記録媒体上に付与された処理液において、高分子化合物は、主に主鎖部分とイオン性基を除いた側鎖部分との作用により、処理液の表面付近(記録媒体から離れた側の付近)に存在すると考えられる。この状態で記録媒体上の処理液にインク組成物が付与されると、処理液の表面付近に存在する特定高分子化合物によって処理液のインク組成物中への浸透がある程度妨げられ、その結果、有機酸性化合物によるインク組成物の凝集速度がある程度抑えられ、インク滴の広がりが促進されるものと考えられる。
しかし、その反面、水溶性高分子化合物として特定高分子化合物を用いた場合、処理液中に、より泡が生じやすくなり、泡に起因する処理液の塗布ムラがより発生し易いことがわかった。
従って、水溶性高分子化合物として、特定高分子化合物を用いた場合には、前述のシリコーンオイルによる処理液の塗布ムラ抑制の効果がより顕著に奏される。
水溶性高分子化合物中におけるイオン性基(好ましくはアニオン性基)を有する構造単位の含有量としては、水溶性高分子化合物の全質量中、例えば10~100質量%とすることができ、10~90質量%であることが好ましく、10~70質量%であることがより好ましく、10~50質量%であることがさらに好ましく、20~40質量%であることが特に好ましい。
疎水性の構造単位を含むことにより、特定高分子化合物が処理液表面に更に存在しやすくなるため、記録媒体に付与されたインク滴の広がりがより促進され、画像のざらつきが更に抑制される。
しかし、その反面、処理液中に更に泡が生じやすくなり、泡に起因する処理液の塗布ムラが更に発生し易くなる。
従って、特定高分子化合物として、イオン性基(好ましくはアニオン性基、特に好ましくはスルホン酸基)を有する親水性の構造単位と疎水性の構造単位とを含む特定高分子化合物を用いた場合には、シリコーンオイルによる塗布ムラ抑制の効果がより顕著に奏される。
まず、特定高分子化合物における親水性の構造単位の好ましい例である、一般式(A)で表される構造単位について説明する。
一般式(A)中、La1は、単結合、-COO-、又は-CON(Ra3)-を表す。Ra3は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
一般式(A)中、La2は、単結合、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の2価の連結基を表す。
一般式(A)中、Aaはイオン性基を表す。
La1として、好ましくは-COO-又はCON(Ra3)-であり、より好ましくは-COO-又はCONH-であり、特に好ましくは-CONH-である。
Ra3における炭化水素基としては、脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせからなる基等が挙げられる。
本発明において、脂肪族炭化水素基は直鎖の炭化水素基には限定されず、環構造(脂環構造)及び分岐構造の少なくとも一方を有していてもよい。
また、本発明において、脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせからなる基は無置換であっても置換基により置換されていてもよい。置換基としては、アルコキシ基、ヒドロキシ基、ハロゲン原子、等が挙げられる。
炭素数8以上の縮環型芳香環化合物とは、2個以上のベンゼン環が縮環した芳香環、及び/又は、少なくとも1種の芳香環と、芳香環に縮環した脂環式炭化水素とから構成される、炭素数8以上の芳香族化合物である。
炭素数8以上の縮環型芳香環化合物の具体例としては、ナフタレン、アントラセン、フルオレン、フェナントレン、アセナフテンなどが挙げられる。
Ra3において、芳香族炭化水素基の炭素数は、6~16が好ましく、6~14がより好ましく、6~10がさらに好ましく、6が特に好ましい。
Ra3において、脂肪族炭化水素基及び芳香族炭化水素基の組み合わせからなる炭化水素基の炭素数は、7~28が好ましく、7~15がより好ましく、7~12がさらに好ましく、7~9が特に好ましい。
La2における炭化水素基としては、脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせからなる基等が挙げられる。
La2における脂肪族炭化水素基と芳香族炭化水素基(アリーレン基)との組み合わせからなる基としては、分岐構造を有していてもよく、脂環構造を有していてもよい、アリーレンアルキレン基、アルキレンアリーレン基が挙げられる。
La2における「エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種と炭化水素基の少なくとも1種とが連結されて構成される2価の基」としては、前述の「エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種と炭化水素基の少なくとも1種とが連結されて構成される1価の基」で例示された基から水素原子1個を除いた2価の基が挙げられる。
La2において、芳香族炭化水素基の炭素数は、6~16が好ましく、6~14がさらに好ましく、6~10がより好ましく、6が特に好ましい。
La2において、脂肪族炭化水素基及び芳香族炭化水素基の組み合わせからなる炭化水素基の炭素数は、7~28が好ましく、7~15がさらに好ましく、7~12がより好ましく、7~9が特に好ましい。
ここで、カチオン性基とは、カチオンに解離可能な基、もしくはカチオンに解離している基を表し、アニオン性基とは、アニオンに解離可能な基、もしくはアニオンに解離している基を表す。
Aaとして、具体的には、カルボキシ基、スルホン酸基、リン酸基、ボロン酸基、アミノ基、アンモニウム基、又はこれらの塩等が挙げられる。中でも、適度な酸性という点から、好ましくは、カルボキシ基、スルホン酸基、リン酸基、又はこれらの塩であり、より好ましくは、カルボキシ基、スルホン酸基、又はこれらの塩であり、更に好ましくは、スルホン酸基又はその塩である。
イオン性基を有するモノマーとしては、通常用いられるモノマーを特に制限なく用いることができる。
またスルホン酸基を有するモノマーとしては、例えば、スチレンスルホン酸、2-アクリルアミド-2-メチルプロパンスルホン酸、3-スルホプロピル(メタ)アクリレート、ビス-(3-スルホプロピル)-イタコネート等が挙げられる。
またリン酸基を有するモノマーとしては、例えば、ビニルホスホン酸、ビニルホスフェート、ビス(メタクリロキシエチル)ホスフェート、ジフェニル-2-アクリロイロキシエチルホスフェート、ジフェニル-2-メタクリロイロキシエチルホスフェート、ジブチル-2-アクリロイロキシエチルホスフェート等が挙げられる。
アニオン性基を有するモノマーは、1種単独で、又は2種以上を混合して用いることができる。
次に、特定高分子化合物における疎水性の構造単位の好ましい例である一般式(B)で表される構造単位について説明する。
一般式(B)中、Lb1は、単結合、-COO-、又は-CON(Rb3)-を表す。Rb3は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
一般式(B)中、Rb2は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
但し、Rb2が水素原子であるときは、Lb1は単結合である。
Lb1として、好ましくは-COO-又は-CON(Rb3)-であり、より好ましくは-COO-又はCONH-であり、特に好ましくは-COO-である。
Rb3において、炭化水素基としては、脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせからなる基等が挙げられる。
ここで、脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせからなる基の例については前述のとおりである。
Rb3において、芳香族炭化水素基の炭素数は、6~16が好ましく、6~14がより好ましく、6~10がさらに好ましく、6が特に好ましい。
Rb3において、脂肪族炭化水素基及び芳香族炭化水素基の組み合わせからなる炭化水素基の炭素数は、7~28が好ましく、7~15がより好ましく、7~12がさらに好ましく、7~9が特に好ましい。
Rb2において、炭化水素基としては、脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせからなる基等が挙げられる。
ここで、脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせからなる基の例については前述のとおりである。
Rb2において、芳香族炭化水素基の炭素数は、6~16が好ましく、6~14がより好ましく、6~10がさらに好ましく、6が特に好ましい。
Rb2において、脂肪族炭化水素基及び芳香族炭化水素基の組み合わせからなる基の炭素数は、7~28が好ましく、7~15がより好ましく、7~12がさらに好ましく、7~9が特に好ましい。
即ち、一般式(B)で表される構造単位を構成するモノマーとして、具体的には、スチレン、α-メチルスチレン、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、アミル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、tert-オクチル(メタ)アクリレート、ステアリル(メタ)クリレート、2-クロロエチル(メタ)アクリレート、2-ブロモエチル(メタ)アクリレート、4-クロロブチル(メタ)アクリレート、シアノエチル(メタ)アクリレート、2-アセトキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、クロロベンジル(メタ)クリレート、メトキシベンジル(メタ)アクリレート、2-クロロシクロヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、フルフリル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、フェニル(メタ)アクリレート、クレジル(メタ)クリレート、ナフチル(メタ)クリレート、2-フェノキシエチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)クリレート、4-ヒドロキシブチル(メタ)クリレート、5-ヒドロキシペンチル(メタ)アクリレート、2,2-ジメチル-3-ヒドロキシプロピル(メタ)アクリレート、トリエチレングリコールモノ(メタ)クリレート、ジプロピレングリコールモノ(メタ)クリレート、2-メトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、メトキシジエチレングリコール(メタ)クリレート、2-iso-プロポキシエチル(メタ)クリレート、2-ブトキシエチル(メタ)アクリレート、2-(2-メトキシエトキシ)エチル(メタ)アクリレート、2-(2-エトキシエトキシ)エチル(メタ)クリレート、2-(2-ブトキシエトキシ)エチル(メタ)アクリレート、2-(3-フェニルプロピルオキシ)エチル(メタ)クリレート、2-アセトキシエチルメタクリレート、2-アセトアセトキシエチルメタクリレート、アリルメタクリレート、グリシジルメタクリレート、1-ブロモ-2-メトキシエチルアクリレート、1,1-ジクロロ-2-エトキシエチルアクリレート、2,2,2-テトラフルオロエチルアクリレート、1H,1H,2H,2H-パーフルオロデシルアクリレート、などが挙げられる。
ここで、(メタ)アクリレートは、アクリレート又はメタクリレートを指す。
その他の構造単位としては、例えば、公知のビニルモノマーに由来する構造単位のうち、一般式(A)で表される構造単位及び一般式(B)で表される構造単位以外の構造単位を用いることができる。
処理液中における特定高分子化合物の含有量が0.1質量%以上であれば、インク滴の広がりをより促進でき、処理液中における特定高分子化合物の含有量が10質量%以下であれば、処理液の増粘をより抑制できる。また、処理液中における特定高分子化合物の含有量が10質量%以下であれば、処理液中の泡に起因する処理液の塗布ムラをより抑制できる。
重合反応は回分式、半連続式、連続式等の公知の操作で行うことができる。重合の開始方法は重合開始剤を用いる方法、光または放射線を照射する方法等がある。これらの重合方法、重合の開始方法は、例えば鶴田禎二「高分子合成方法」改定版(日刊工業新聞社刊、1971)や大津隆行、木下雅悦共著「高分子合成の実験法」化学同人、昭和47年刊、124~154頁に記載されている。
重合温度は生成するポリマーの分子量、開始剤の種類などと関連して設定することができ、通常、0℃~100℃程度であるが、50~100℃の範囲で重合を行うことが好ましい。反応時間は、1~30時間程度が好ましい。得られたポリマーは再沈澱などの精製を行っても良い。
例示化合物A-1~A-29では、aが0~73であり、bが0~90であり、cが10~90であり、dが0~90である組み合わせが好適である。
例示化合物A-1~A-29におけるa/b/c/dの具体的な組み合わせとしては、5/5/90/0、33/33/34/0、17/50/33/0、50/17/33/0、50/20/30/0、56/17/27/0、60/13/27/0、70/3/27/0、90/0/10/0、73/0/27/0、50/0/50/0、20/0/80/0、10/0/90/0、0/90/10/0、0/77/23/0、0/50/50/0、0/20/80/0、40/30/27/3、34/30/27/9、18/40/27/15、が挙げられる。
本発明における処理液は、水を含有する。
水の含有量には特に制限はないが、10質量%~99質量%の範囲が好ましく、より好ましくは50質量%~90質量%であり、更に好ましくは60質量%~80質量%である。
-シリコーンオイル-
処理液は、シリコーンオイルの少なくとも1種を含有することが好ましい。
処理液がシリコーンオイルを含有することにより、処理液中の泡に起因する処理液の塗布ムラを抑制することができる。
一般に、液体中の泡を抑制するために消泡剤が用いられることがあるが、シリコーンオイルをもちいることで、シリコーンオイル以外の消泡剤を用いる場合よりも、処理液の塗布ムラを抑制し易い。
シリコーンオイルとしては特に制限はなく、例えば、ジメチルポリシロキサン等のオルガノポリシロキサン、ポリオキシアルキレン変性オルガノポリシロキサン等の変性オルガノポリシロキサンが挙げられる。これらは、1種単独で用いてもよいし、2種以上を併用してもよい。
また、シリコーンオイルとしては、例えば、特公平07-090128号公報に記載のシリコーンオイルや、特許3976113号公報に記載のシリコーンオイルを用いることもできる。
また、シリコーンオイルとしては、消泡性の観点から、25℃における粘度が100~100,000mm2/sのシリコーンオイルが好ましい。
中でも、シリコーンオイルが界面活性剤により処理液中に分散されている形態(即ち、シリコーンオイルが処理液中に乳化分散されている形態)がより好ましい。
シリコーンオイルが界面活性剤により処理液中に分散されている形態とするための具体的な方法としては、処理液の作製の際、後述するエマルジョン型シリコーン消泡剤を用いる方法が好適である。
シリコーンオイルを分散させる界面活性剤としては特に限定はなく、水を含む処理液中に、シリコーンオイルを乳化分散させ得る界面活性剤の中から適宜選択して用いることができる。
シリコーンオイルを分散させる界面活性剤としてはノニオン性界面活性剤が好適である。
シリコーンオイルを分散させる界面活性剤として、具体的には、例えば、後述する表面張力調整剤として例示する界面活性剤を用いることができる。
ここで、シリコーン消泡剤は、シリコーンオイルを有効成分として含む消泡剤である。
シリコーン消泡剤の形態としては、例えば、オイル型シリコーン消泡剤、コンパウンド型シリコーン消泡剤、エマルジョン型シリコーン消泡剤、自己乳化型シリコーン消泡剤などの各形態が挙げられる。
オイル型シリコーン消泡剤は、シリコーンオイル(親水性シリコーンオイル等の変性シリコーンオイルも含まれる)そのものを指す。親水性シリコーンオイルは、「親水性オイル型シリコーン消泡剤」などとも呼ばれている。
コンパウンド型シリコーン消泡剤は、オイル型シリコーン消泡剤にシリカやアルミナ等の粒子を分散させて消泡性を上げた形態である。
エマルジョン型シリコーン消泡剤は、コンパウンド型シリコーン消泡剤を乳化剤(界面活性剤)によってO/W型のエマルジョンにして水への分散性を上げた形態である。
自己乳化型シリコーン消泡剤は、シリコーンオイルとシリカを含み、水に希釈すると容易にO/W型のエマルジョンになる形態である。
中でも、塗布ムラ抑制の効果が特に顕著である点で、エマルジョン型シリコーン消泡剤が好ましい。
市販品としては、KS-508、KS-531、KS-537、KS-604、KM-72、KM-72F、KM-90、KM-98(以上、信越化学工業(株)製)、SF-8427、SF-8428、SH-3749、SH-8400、FZ-2101、FZ-2104、FZ-2118、FZ-2203、FZ-2207(以上、東レ・ダウコーニング(株)製)、BYK-345、BYK-346、BYK-348(以上、ビッグケミー・ジャパン(株)製)、TSA-739、TSA-7341、TSA-732、TSA-732A、TSA-772、TSA-730、TSA-770、TSA-775、YMA6509、TSA-737、TSA-737F、YSA-6406、TSA-780(以上、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製)などが挙げられる。
処理液中におけるシリコーンオイルの含有量の下限には特に限定はないが、処理液の塗布ムラをより抑制する観点からは、処理液中におけるシリコーンオイルの含有量の下限は、処理液の全量に対し、5ppmが好ましく、10ppmがより好ましく、50ppmが特に好ましい。処理液中におけるシリコーンオイルの含有量の下限は、水溶性高分子化合物の全量に対しては、0.1質量%が好ましく、0.2質量%がより好ましく、1.0質量%が特に好ましい。
なお、本発明において、「ppm」は質量基準である。
本発明における処理液は、無機酸として、リン酸及びリン酸化合物の少なくとも1種をを含有してもよい。これにより、画像の光沢ムラが抑制される。画像の光沢ムラは、記録媒体中の成分(例えば炭酸カルシウム)と処理液中の有機酸性化合物との反応により生じると考えられる。
リン酸化合物としては、例えば、亜リン酸、次亜リン酸、ピロリン酸、メタリン酸、ポリリン酸、またはこれらの塩を用いることができる。
本発明における処理液は、有機溶剤から選択される少なくとも1種を含むことが好ましい。
有機溶剤としては、20℃で100gの水に5g以上溶解する有機溶剤(以下、「水溶性有機溶剤」ともいう。)であることが好ましい。
水溶性有機溶剤としては、後述するインクに含まれる水溶性有機溶剤と同様のものを用いることができる。中でも、カール抑制の観点から、ポリアルキレングリコールまたはその誘導体であることが好ましく、ジエチレングリコールモノアルキルエーテル、トリエチレングリコールモノアルキルエーテル、ジプロピレングリコール、トリプロピレングリコールモノアルキルエーテル、ポリオキシプロピレングリセリルエーテル、ポリオキシエチレンポリオキシプロピレングリコールから選ばれる少なくとも1種であることがより好ましい。
有機溶剤の処理液中における含有率としては、特に制限はされないが、カール抑制の観点から、処理液全体に対して1~30質量%であることが好ましく、5~15質量%であることがより好ましい。
本発明における処理液は、含窒素ヘテロ環化合物及び有機メルカプト化合物から選択される少なくとも1種を含有してもよい。これにより、画像の耐擦性及び記録媒体の搬送性が向上する。中でも、含窒素ヘテロ環化合物を含有することが好ましい。
含窒素ヘテロ環化合物の構造としては、含窒素5員環構造又は6員環構造が好ましく、中でも含窒素5員環構造が好ましい。
ヘテロ環としては、例えばテトラゾール環、トリアゾール環、イミダゾール環、チアジアゾール環、オキサジアゾール環、セレナジアゾール環、オキサゾール環、チアゾール環、ベンズオキサゾール環、ベンズチアゾール環、ベンズイミダゾール環、ピリミジン環、トリアザインデン環、テトラアザインデン環、ペンタアザインデン環等があげられる。
即ち、イミダゾール、ベンゾイミダゾール、ベンゾインダゾール、ベンゾトリアゾール、テトラゾール、ベンゾオキサゾール、ベンゾチアゾール、ピリジン、キノリン、ピリミジン、ピペリジン、ピペラジン、キノキサリン、モルホリンなどが挙げられ、これらは、アルキル基、カルボキシ基、スルホ基、などの置換基を有してよい。
好ましい含窒素6員環化合物の具体例としては、トリアジン、メチルトリアジン、ジメチルトリアジン、ヒドロキシエチルトリアジン環、ピリミジン、4-メチルピリミジン、ピリジン、ピロリンがあげられる。
有機メルカプト化合物としては、アルキルメルカプト化合物や、アリールメルカプト化合物、ヘテロ環メルカプト化合物などが挙げられる。
アルキルメルカプト化合物としては、システインやチオリンゴ酸などが挙げられ、アリールメルカプト化合物としては、チオサリチル酸などが挙げられ、ヘテロ環メルカプト化合物としては、2-フェニル-1-メルカプトテトラゾール、2-メルカプトベンゾイミダゾール、2-メルカプトベンゾチアゾール、2-メルカプトベンゾオキサゾール、2-メルカプトピリミジン、2,4-ジメルカプトピリミジン、2-メルカプトピリジンなどが挙げられ、これらは、アルキル基、カルボキシ基、スルホ基、などの置換基を有してよい。
処理液中における含窒素ヘテロ環化合物及び有機メルカプト化合物の含有量(総含有量)には特に限定はないが、処理液の全量に対し、0.1~5.0質量%であることが好ましく、0.1~3.0質量%であることがより好ましい。
本発明における処理液は、界面活性剤の少なくとも1種を含んでいてもよい。界面活性剤は、表面張力調整剤として用いることができる。表面張力調整剤としては、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤、ベタイン界面活性剤等が挙げられる。
中でも、インク組成物の凝集速度の観点から、ノニオン性界面活性剤またはアニオン性界面活性剤であることが好ましい。
また、特開2003-322926号、特開2004-325707号、特開2004-309806号の各公報に記載のフッ素系(フッ化アルキル系)界面活性剤、シリコーン系界面活性剤等も挙げられる。
また処理液の表面張力は、Automatic Surface Tensiometer CBVP-Z(協和界面科学株式会社製)を用い、プレート法により25℃の条件下で測定されるものである。
本発明における処理液は本発明の効果を損なわない限り、前述の有機酸性化合物に加え、その他の凝集成分を含むことができる。その他の凝集剤としては、多価金属塩およびポリアリルアミン等を挙げることができる。
多価金属塩としては、周期表の第2属のアルカリ土類金属(例えば、マグネシウム、カルシウム)、周期表の第3属の遷移金属(例えば、ランタン)、周期表の第13属からのカチオン(例えば、アルミニウム)、ランタニド類(例えば、ネオジム)の塩、及びポリアリルアミン、ポリアリルアミン誘導体を挙げることができる。金属の塩としては、カルボン酸塩(蟻酸、酢酸、安息香酸塩など)、硝酸塩、塩化物、及びチオシアン酸塩が好適である。中でも、好ましくは、カルボン酸(蟻酸、酢酸、安息香酸塩など)のカルシウム塩又はマグネシウム塩、硝酸のカルシウム塩又はマグネシウム塩、塩化カルシウム、塩化マグネシウム、及びチオシアン酸のカルシウム塩又はマグネシウム塩である。
多価金属塩の処理液中における含有量としては、例えば1~10質量%とすることができる。
本発明における処理液は、さらに、その他の添加剤を含んで構成することができる。
その他の添加剤としては、例えば、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤、pH調整剤、粘度調整剤、分散安定剤、防錆剤、キレート剤等の公知の添加剤が挙げられる。また、本発明の効果を妨げない範囲で、シリコーンオイル以外の消泡剤を含んでいてもよい。
また、本発明における処理液は、顔料等の着色剤を実質的に含まないこと、具体的には処理液全量に対する着色剤の含有量が1質量%未満(より好ましくは0.5質量%以下、更に好ましくは0.1質量%以下)であることが好ましい。
また処理液の粘度としては、インク組成物の凝集速度の観点から、1~30mPa・sの範囲が好ましく、1~20mPa・sの範囲がより好ましく、2~15mPa・sの範囲がさらに好ましく、2~10mPa・sの範囲が特に好ましい。なお、粘度は、VISCOMETER TV-22(TOKI SANGYO CO.LTD製)を用いて25℃の条件下で測定されるものである。
本発明におけるインク付与工程では、画像形成にあたり、処理液付与工程を経た記録媒体の処理液付与面に、顔料とピロリドン誘導体と特定グリセリン系化合物と水とを含むインク組成物を付与する。
特に、記録媒体が、50m/min以上の搬送速度で搬送されるような、画像が外的負荷を受け易い環境においても、本発明の画像形成工程の構成で画像を形成することで、優れた耐擦過性を有し、かつ、高い解像度の画像が形成される。
画像形成の高速化の観点からは、搬送速度はより速いことが好ましく、100m/min以上がより好ましく、150m/min以上が更に好ましい。搬送速度の上限については、特に制限されるものではないが、記録媒体を安定に搬送する必要性の観点から、350m/minが望ましい。
インクジェット法を利用した画像の形成は、エネルギーを供与することで所望の記録媒体にインク組成物を吐出することにより行える。なお、本発明の好ましい画像形成方法として、特開2003-306623号公報の段落番号0093~0105に記載の方法が適用できる。
インクジェット法には、特に制限はなく、公知の方式、例えば、静電誘引力を利用してインクを吐出させる電荷制御方式、電圧の印加により機械的歪を発生する圧電素子を利用してインクを吐出させるピエゾインクジェット方式、電気信号を音響ビームに変えインクに照射して放射圧を利用してインクを吐出させる音響インクジェット方式、及びインクを加熱して気泡を形成し、生じた圧力を利用するサーマルインクジェット(バブルジェット(登録商標))方式等のいずれであってもよい。
なお、インクジェット法には、フォトインクと称する濃度の低いインクを小さい体積で多数射出する方式、実質的に同じ色相で濃度の異なる複数のインクを用いて画質を改良する方式や無色透明のインクを用いる方式が含まれる。
本発明に適用可能なインクジェット法としては、短尺のシリアルヘッドを用いてヘッドを記録媒体の幅方向に走査させながら記録を行うシャトル方式であってもよいが、記録媒体の1辺の全域に対応して記録素子が配列されているラインヘッドを用いたライン方式を適用した態様が好ましい。ライン方式の場合、記録素子の配列方向(主走査方向)と直交する方向(以下、副走査方向と称する場合がある。)に記録媒体を走査させることで、記録媒体の全面に画像記録を行うことができる。
次に、本発明におけるインク組成物の詳細について説明する。
インク付与工程で用いるインク組成物は、顔料、ピロリドン誘導体、特定グリセリン系化合物、及び水を含む。
インク組成物は、必要に応じて、さらに、樹脂粒子等の他の成分を含有していてもよい。
本発明におけるインク組成物は、顔料の少なくとも一種を含有する。
顔料は、目的に応じて適宜選択することができ、有機顔料又は無機顔料のいずれであってもよい。
有機顔料としては、例えば、アゾ顔料、多環式顔料、染料キレート、ニトロ顔料、ニトロソ顔料、アニリンブラック、などが挙げられる。これらの中でも、アゾ顔料、多環式顔料などがより好ましい。アゾ顔料としては、例えば、アゾレーキ、不溶性アゾ顔料、縮合アゾ顔料、キレートアゾ顔料、などが挙げられる。多環式顔料としては、例えば、フタロシアニン顔料、ぺリレン顔料、ぺリノン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、インジゴ顔料、チオインジゴ顔料、イソインドリノン顔料、キノフタロン顔料、などが挙げられる。染料キレートとしては、例えば、塩基性染料型キレート、酸性染料型キレート、などが挙げられる。
無機顔料としては、例えば、酸化チタン、酸化鉄、炭酸カルシウム、硫酸バリウム、水酸化アルミニウム、バリウムイエロー、カドミウムレッド、クロムイエロー、カーボンブラック、などが挙げられる。これらの中でも、カーボンブラックが特に好ましい。なお、カーボンブラックとしては、例えば、コンタクト法、ファーネス法、サーマル法などの公知の方法によって製造されたものが挙げられる。これら顔料の中では、水分散性顔料が好ましい。
(1)カプセル化顔料、即ち、ポリマー微粒子に顔料を含有させてなるポリマー分散物であり、より詳しくは、親水性水不溶性の樹脂で顔料を被覆し、顔料表面の樹脂層にて親水化することで顔料を水に分散可能にした顔料
(2)自己分散顔料、即ち、表面に少なくとも1種の親水基を有し、分散剤の不存在下で水分散性及び水溶性の少なくともいずれかを示す顔料、より詳しくは、主にカーボンブラックなどを表面酸化処理して親水化し、顔料単体が水性媒体に分散するようにした顔料
(3)樹脂分散顔料、即ち、重量平均分子量50,000以下の水溶性高分子化合物により分散された顔料
(4)界面活性剤分散顔料、即ち、界面活性剤により分散された顔料
カプセル化顔料の樹脂は、限定されないが、水と水溶性有機溶剤の混合溶媒中で自己分散能又は溶解能を有し、かつアニオン性基(酸性)を有する高分子化合物であるのが好ましい。この樹脂は、通常は数平均分子量が1,000~100,000の範囲程度のものが好ましく、3,000~50,000の範囲程度の樹脂が特に好ましい。また、この樹脂は、有機溶剤に溶解して溶液となる樹脂が好ましい。樹脂の数平均分子量が3,000~50,000の範囲内であると、樹脂は、顔料における被覆膜として又はインクとした際の塗膜としての機能を発揮することができる。樹脂は、アルカリ金属や有機アミンの塩の形で用いられるのが好ましい。
これら樹脂のうち、アニオン性のアクリル系樹脂は、例えば、アニオン性基を有するアクリルモノマー(以下、「アニオン性基含有アクリルモノマー」という。)及び必要に応じて、アニオン性基含有アクリルモノマーと共重合可能な他のモノマーを溶媒中で重合して得られる。アニオン性基含有アクリルモノマーとしては、例えば、カルボキシ基、スルホン酸基、及びホスホン基からなる群より選ばれる1個以上のアニオン性基を有するアクリルモノマーが挙げられ、中でもカルボキシ基を有するアクリルモノマーが特に好ましい。カルボキシ基を有するアクリルモノマーの具体例としては、アクリル酸、メタクリル酸、クロトン酸、エタアクリル酸、プロピルアクリル酸、イソプロピルアクリル酸、イタコン酸、フマル酸等が挙げられる。これらの中でも、アクリル酸又はメタクリル酸が好ましい。
自己分散顔料を着色剤として含有するインクは、通常、顔料を分散させるために含有させる分散剤を含む必要がないため、分散剤に起因する消泡性の低下による発泡がほとんどなく、吐出安定性に優れるインクを調製しやすい。自己分散顔料の表面に結合される分散性付与基には、-COOH、-CO、-OH、-SO3H、-PO3H2及び第4級アンモニウム並びにそれらの塩が例示でき、分散性付与基は、顔料に物理的処理又は化学的処理を施して、分散性付与基又は分散性付与基を有する活性種を顔料表面に結合(グラフト)させることにより結合される。物理的処理としては、例えば、真空プラズマ処理等が例示できる。また、化学的処理としては、例えば、水中で酸化剤により顔料表面を酸化する湿式酸化法や、p-アミノ安息香酸を顔料表面に結合させることによりフェニル基を介してカルボキシ基を結合させる方法、等が例示できる。
本発明においては、例えば、次亜ハロゲン酸及び/又は次亜ハロゲン酸塩による酸化処理、あるいはオゾンによる酸化処理により表面処理される自己分散顔料を好ましい例として挙げることができる。自己分散顔料として市販品を使用してもよく、具体的には、マイクロジェットCW-1(商品名;オリヱント化学工業(株)製)、CAB-O-JET200、CAB-O-JET300(商品名;キャボット社製)等が挙げられる。
転相乳化法は、基本的には、自己分散能又は溶解能を有する樹脂と顔料との混合溶融物を水に分散させる自己分散(転相乳化)方法である。また、この混合溶融物には、高分子化合物や硬化剤を含んでなるものであってもよい。ここで、混合溶融物とは、溶解せず混合した状態、溶解して混合した状態、又はこれら両者の状態のいずれの状態を含むものをいう。「転相乳化法」のより具体的な製造方法は、特開平10-140065号に記載の方法が挙げられる。
なお、転相乳化法及び酸析法のより具体的な方法については、特開平9-151342号、特開平10-140065号の各公報に記載を参照することができる。
顔料分散剤は、顔料を分散させた際の易分散化及び分散後の分散安定化を図ることができる。顔料分散剤としては、ノニオン性化合物、アニオン性化合物、カチオン性化合物、両性化合物等が挙げられる。例えば、α,β-エチレン性不飽和基を有するモノマーの共重合体等が挙げられる。α,β-エチレン性不飽和基を有するモノマーの例としては、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、酢酸ビニル、酢酸アリル、アクリル酸、メタクリル酸、クロトン酸、クロトン酸エステル、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸ジエステル、フマル酸、フマル酸モノエステル、ビニルスルホン酸、スチレンスルホン酸、スルホン化ビニルナフタレン、ビニルアルコール、アクリルアミド、メタクリロキシエチルホスフェート、ビスメタクリロキシエチルホスフェート、メタクリロキシエチルフェニルアシドホスフェート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、スチレン、α-メチルスチレン、ビニルトルエン等のスチレン誘導体、ビニルシクロヘキサン、ビニルナフタレン、ビニルナフタレン誘導体、芳香族基を置換してもよいアクリル酸アルキルエステル、アクリル酸フェニルエステル、芳香族基を置換してもよいメタクリル酸アルキルエステル、メタクリル酸フェニルエステル、メタクリル酸シクロアルキルエステル、クロトン酸アルキルエステル、イタコン酸ジアルキルエステル、マレイン酸ジアルキルエステル、並びに各化合物の誘導体等が挙げられる。
顔料分散剤の顔料に対する添加量としては、質量基準で顔料の10%以上100%以下の範囲が好ましく、顔料の20%以上70%以下がより好ましく、更に好ましくは顔料の40%以上50%以下である。
また、カルボキシ基含有モノマーのほか、任意に選択した親水性モノマー、疎水性モノマーを共重合成分として用いてもよい。親水性モノマーは、イオン性でもノニオン性でもよい。疎水性モノマーは、特に制限されないが、炭素数1~20のアルキルメタクリレート又は炭素数1~20のアルキルアクリレートが好ましい。
水溶性樹脂の酸価(水溶性樹脂1gを中和するに必要なKOHのmg数)は、顔料の分散性、分散安定性の観点から、135mgKOH/g~250mgKOH/gであることが好ましく、135mgKOH/g~200mgKOH/gであることがより好ましく、135mgKOH/g~180mgKOH/gが特に好ましい。
(1)顔料及び水溶性樹脂を、水又は極性溶媒の水溶液中に分散して顔料分散液を得る分散工程
(2)(1)で得られた顔料分散液に架橋剤を加えて加熱し、架橋反応させて顔料表面を架橋されたポリマーで被覆する架橋工程
(3)架橋されたポリマーで被覆された樹脂被覆顔料を精製する工程
これら工程のほか、他の工程を必要に応じて適宜設けてもよい。工程(1)において、極性溶媒等は公知のものを適宜用いることができる。
顔料のインク組成物中における含有量としては、色濃度、粒状性、インク安定性、吐出信頼性の観点から、インクの全質量に対して、0.1質量%~15質量%となる量が好ましく、0.5質量%~12質量%となる量がより好ましく、1質量%~10質量%となる量が特に好ましい。
本発明におけるインク組成物は、ピロリドン誘導体の少なくとも一種を含有する。後述する特定グリセリン系化合物を含む組成に、さらにピロリドン誘導体が含有されることにより、インクの裏抜け現象を防ぎつつ画像の擦過耐性が向上し、高速で多数枚処理するような場合に画像に傷が付く等の擦過故障が防止される。
アルキル基、アリール基、及びアルケニル基は、置換基を有していても置換基を有していなくてもよいが、置換基を有していないことが好ましい。
アルキル基が置換基を有する場合の置換基としては、例えば、炭素数1~8のアルコキシ基、炭素数6~14のアリール基、ヒドロキシル基、カルボキシ基、ハロゲン原子(フッ素原子、塩素原子、ヨウ素原子等)等が挙げられる。
アリール基が置換基を有する場合の置換基としては、例えば、炭素数1~8のアルコキシ基、炭素数1~10のアルキル基、ヒドロキシル基、カルボキシ基、ハロゲン原子(フッ素原子、塩素原子、ヨウ素原子等)等が挙げられる。
アルケニル基が置換基を有する場合の置換基としては、例えば、炭素数1~8のアルコキシ基、炭素数6~14のアリール基、ヒドロキシル基、カルボキシ基、ハロゲン原子(フッ素原子、塩素原子、ヨウ素原子等)等が挙げられる。
一般式(P-1)におけるR2は、水素原子又は炭素数1~4のアルキル基であることが好ましく、水素原子であることが特に好ましい。
ピロリドン誘導体の含有量が3.0質量%以上であることで、画像の耐擦性をより向上させることができる。また、ピロリドン誘導体の含有量が20.0質量%以下であると、インク組成物の安定に保持するのに有利である。
含有比率p/sとしては、同様の理由から、0.09以上3.5以下の範囲がより好ましく、0.11以上3.2以下の範囲が特に好ましい。
本発明におけるインク組成物は、一般式(II)で表される化合物(特定グリセリン系化合物)の少なくとも一種を含有する。
特定グリセリン系化合物は、一般式(II)で表されるグリセリンのアルキレンオキシド付加体である。特定グリセリン系化合物をインク組成物に含有することによって、インクの記録媒体への浸透を、画像の擦過性を大きく損なわない程度に抑制することができる。
(AO=EO又はPO(EO:PO=1:1)、SP値=20.1)
・nC4H9O(AO)10-H
(AO=EO又はPO(EO:PO=1:1)、SP値=18.8)
・HO(A’O)40-H
(A’O=EO又はPO(EO:PO=1:3)、SP値=18.7)
・HO(A’’O)55-H
(A’’O=EO又はPO(EO:PO=5:6)、SP値=18.8)
・HO(PO)3-H(SP値=24.7)
・HO(PO)7-H(SP値=21.2)
・1,2-ヘキサンジオール(SP値=27.4)
なお、EO、POは各々、エチレンオキシ基、プロピレンオキシ基を表す。
また、インク組成物は特定グリセリン系化合物以外の他の水溶性有機溶剤を更に含んでもよい。この場合、インク組成物中に含まれる特定グリセリン系化合物及び他の水溶性有機溶剤の総量の70質量%以上は、SP値が27.5以下であることが好ましい。SP値が27.5以下であることで、画像形成後の様々な環境湿度下でのカールの発生がより抑制される。また、後述する樹脂粒子を含むときには、樹脂粒子と相互作用して定着性が向上し、特にSP値の比較的低い(≦27.5)成分が多いことで、画像の耐擦性をより向上させることができる。また、オフセットの抑制にも効果的である。
特定グリセリン系化合物の含有量が5.0質量%以上であることで、インク組成物の記録媒体に対する浸透性を緩和し、インクの裏抜けがより防止される。
本発明におけるインク組成物は、更に、樹脂粒子の少なくとも一種を含有することが好ましい。樹脂粒子を含有すると、画像形成後に熱処理する等により画像の耐擦性をより向上させることができる。
1/Tg=Σ(Xi/Tgi) ・・・(1)
ここで、計算対象となるポリマーはi=1からnまでのn種のモノマー成分が共重合しているとする。Xiはi番目のモノマーの質量分率(ΣXi=1)、Tgiはi番目のモノマーの単独重合体のガラス転移温度(絶対温度)である。但し、Σはi=1からnまでの和をとる。尚、各モノマーの単独重合体ガラス転移温度の値(Tgi)は、Polymer Handbook(3rd Edition)(J. Brandrup, E. H. Immergut著(Wiley-Interscience、1989))の値を採用する。
樹脂粒子の平均粒径は、10nm~1μmの範囲が好ましく、10~200nmがより好ましく、20~100nmが更に好ましく、20~50nmが特に好ましい。
樹脂粒子を含有する場合、樹脂粒子のインク組成物中における量は、定着性、耐擦過性、インク組成物の粘度の観点から、インク組成物の全質量に対して、固形分で0.5~20質量%が好ましく、3~20質量%がより好ましく、5~15質量%が更に好ましい。
本発明におけるインク組成物は、水を含有するものであるが、水の量には特に制限はない。中でも、水の量は、安定性及び吐出信頼性確保の点から、インク組成物の全質量に対して、好ましくは10質量%以上99質量%以下であり、より好ましくは20質量%以上80質量%以下であり、更に好ましくは、30質量%以上70質量%以下であり、40質量%以上60質量%以下であることが特に好ましい。
本発明におけるインク組成物は、更に他の成分として、必要に応じて、浸透溶剤、保湿剤、防腐剤、防黴剤、pH調整剤、キレート化剤等の添加剤を含有することができる。これら添加剤の詳細については、特開2010-90266号公報の[0067]~[0076]の記載を参照することができる。
本発明の画像形成方法は、インク付与工程で付与されたインクを乾燥する乾燥工程が設けられてもよい。乾燥により、記録媒体上に付着されたインク組成物中に含有される液媒体、具体的には水、ピロリドン誘導体、他の水溶性有機溶剤が蒸発、飛散し、着色された樹脂皮膜が形成される。これにより、記録媒体上に傷や剥れ等の画像欠陥の少ない高画質な画像を高速に形成することができる。
本発明の画像形成方法は、乾燥工程で一旦加熱して乾燥させた後、記録媒体を冷却する冷却工程を設けてもよい。
冷却方法としては、記録媒体の温度を積極的に下げることができる冷却工程であればいずれの方法であってもよい。冷却方法の例としては、冷却ゾーンに記録媒体を通過させる方法、冷風を記録媒体にあてる方法、冷却した物体に記録媒体を接触させる方法などが挙げられる。
本発明の画像形成方法は、必要に応じて、インク付与工程の後に記録媒体上のインク組成物を加熱定着する加熱定着工程を更に設けてもよい。加熱定着工程は、インク組成物の付与により形成された画像を加熱し、記録媒体に定着させる(加熱定着処理)。加熱定着処理により、記録媒体上の画像の定着が施され、画像の耐擦過性をより向上させることができる。
加熱の方法は、特に制限されないが、ニクロム線ヒーター等の発熱体で加熱する方法、温風又は熱風を供給する方法、ハロゲンランプ、赤外線ランプ等で加熱する方法など、非接触で乾燥させる方法を好適に挙げることができる。また、加熱加圧の方法は、特に制限はないが、例えば、熱板を記録媒体の画像形成面に押圧する方法や、一対の加熱加圧ローラ、一対の加熱加圧ベルト、あるいは記録媒体の画像記録面側に配された加熱加圧ベルトとその反対側に配された保持ローラとを備えた加熱加圧装置を用い、対をなすローラ等を通過させる方法など、接触させて加熱定着を行う方法が好適に挙げられる。
既述の処理液と、既述のインク組成物とを組み合わせて、インクセットとしてもよい。
すなわち、本発明のインクセットは、一般式(I)で表される有機酸性化合物、水溶性高分子化合物、及び水を含有する処理液と、顔料、ピロリドン誘導体、一般式(II)で表される化合物、及び水を含有するインク組成物とを有する。
本発明のインクセットを用いて画像形成を行えば、優れた耐擦過性を有し、かつ、高い解像度の画像を得ることができる。
インクセットが有する処理液とインク組成物との詳細および好ましい態様は、本発明の画像形成方法で用いられる処理液とインク組成物との詳細および好ましい態様と同様である。
〔水溶性高分子化合物(水溶性ポリマー)の準備〕
処理液中の成分として用いる水溶性高分子化合物(水溶性ポリマー1)を以下のようにして準備した。
水溶性ポリマー1の構造を下記に示す。
なお、下記に示した水溶性ポリマー1において、各構成単位の右下の数字は質量比(質量%)を表し、Mwは重量平均分子量を表す。以降の各ポリマーの構造式に関しても同様である。
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を備えた200ミリリットル三口フラスコに、イソプロピルアルコール30.0gを仕込んで、窒素雰囲気下に、65℃まで昇温した。
次に、メチルメタクリレート(以下、「MMA」ともいう)(30.0g)、エチルアクリレート(以下、「EA」ともいう)(6.5g)、アクリルアミド-2-メチルプロパンスルホン酸(以下、「AMPS」ともいう)(13.5g)、イソプロピルアルコール(30g)、水(15g)、及び「V-601」(和光純薬工業(株)製の重合開始剤)(2.97g(0.0129モル);モノマーの総モル数(0.430モル)に対して3モル%)を、2時間で滴下が完了するように等速で滴下した。
滴下完了後2時間攪拌し、その後そこへ、「V-601」(モノマーの総モル数に対して1.5モル%(1.48g))及びイソプロピルアルコール(3.0g)を加え、2時間攪拌を行った。
得られたポリマー溶液を、用いたアクリルアミド-2-メチルプロパンスルホン酸と等モル数の水酸化ナトリウムの水溶液とで中和し、減圧濃縮によってイソプロピルアルコールを留去し、ポリマー溶液の総量が310gになるまで水を加え、水溶性ポリマー1を16質量%含むポリマー水溶液を得た。
得られた水溶性ポリマー1の重量平均分子量(Mw)は45000(ゲルパーミエーションクロマトグラフィー(GPC)によりポリスチレン換算で算出、使用カラムはTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ200(東ソー社製))であった。
下記スキームにしたがって、以下に示すようにしてポリマー分散剤P-1を合成した。
得られた樹脂の組成は、1H-NMRで確認し、GPCより求めた重量平均分子量(Mw)は44,600であった。さらに、JIS規格(JISK0070:1992)に記載の方法により酸価を求めたところ、65.2mgKOH/gであった。
(シアン分散液の調製)
シアン顔料であるピグメント・ブルー15:3(フタロシアニンブルーA220、大日精化株式会社製)10部と、ポリマー分散剤P-1を5部と、メチルエチルケトン42部と、1規定 NaOH水溶液5.5部と、イオン交換水87.2部と、を混合し、ビーズミルにより0.1mmφジルコニアビーズを用いて2~6時間分散した。
得られた分散物を減圧下、55℃でメチルエチルケトンを除去し、更に一部の水を除去した。その後、更に、高速遠心冷却機7550(久保田製作所製)を用いて、50mL遠心管を使用し、8000rpmで得られた分散物を30分間遠心処理し、沈殿物以外の上澄み液を回収した。その後、吸光度スペクトルから顔料濃度を求め、顔料濃度が10.2質量%の樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(シアン分散液C)を得た。得られたシアン分散液Cの平均粒径は105nmであった。
シアン分散液の調製において、ピグメント・ブルー15:3(フタロシアニンブルーA220、大日精化株式会社製)の代わりに、マゼンタ顔料であるピグメント・レッド122を用いた以外はシアン分散液の調製と同様にして、樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(マゼンタ分散液M)を調製した。得られたマゼンタ分散液Mの平均粒径は85nmであった。
シアン分散液の調製において、ピグメント・ブルー15:3(フタロシアニンブルーA220、大日精化株式会社製)の代わりに、イエロー顔料であるピグメント・イエロー74を用いた以外はシアン分散液の調製と同様にして、樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(イエロー分散液Y)を調製した。得られたイエロー分散液Yの平均粒径は82nmであった。
シアン分散液の調製において、ピグメント・ブルー15:3(フタロシアニンブルーA220、大日精化株式会社製)の代わりに、ブラック顔料であるカーボンブラック(デグッサ社製NIPEX160-IQ)を用いた以外はシアン分散液の調製と同様にして、樹脂被覆顔料粒子(ポリマー分散剤で被覆された顔料)の分散物(ブラック分散液K)を調製した。得られたブラック分散液Kの平均粒径は130nmであった。
得られた各顔料分散液(シアン分散液C,マゼンタ分散液M,イエロー分散液Y,ブラック分散液K)及び自己分散性樹脂粒子B-01を用い、下記表1に示すインクの組成となるように各成分を混合し、各インク組成物(マゼンタインク組成物M1、ブラックインク組成物K1、シアンインク組成物C1、イエローインク組成物Y1)をそれぞれ調製した。
調製した各インク組成物をプラスチック製ディスポーサブルシリンジにて、PVDF5μmフィルター(ミリポア社製Millex SV、直径25mm)で濾過して完成インク(マゼンタインクM1、ブラックインクK1、シアンインクC1、イエローインクY1)とした。
下記組成となるように各成分を混合し、試料101の処理液を作製した。
-試料101の処理液の組成-
・ジエチレングリコールモノエチルエーテル ・・・・・・・4%
・トリプロピレングリコールモノメチルエーテル ・・・・・・・4%
・有機酸性化合物 ・・・・・・18%
〔マロン酸/リンゴ酸/プロパントリカルボン酸=30/30/40(質量比)〕
・無機酸性化合物(リン酸) ・・・・・4.3%
・水溶性ポリマー1 ・・・・・0.5%
・ベンゾトリアゾール ・・・・・・・1%
・消泡剤 ・・・・・・・シリコーンオイルの量として100ppm
〔モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製TSA-739(15%);エマルジョン型シリコーン消泡剤〕
・イオン交換水 ・・・・・・・・・・・・・・合計で100%となる残量
各完成インク(ブラックインクK1、シアンインクC1、マゼンタインクM1、イエローインクY1)の組み合わせと、試料101の処理液とを組み合わせ、試料101のインクセットを作製した。
試料101のインクセットの作製において、組成を表2に示すように変更したこと以外は、試料101のインクセットの作製と同様にして、試料102~試料110および試料113~試料117の(インクセット)を作製した。試料111および試料112においては、処理液を用意せず、表2に示す組成のインク組成物のみを作製した。
試料102~試料110および試料113~試料117における各処理液の組成は、試料101の処理液の組成において、有機酸性化合物の種類と量を表2に示すように変更したものである。
富士フイルムダイマティックス社製のダイマティクス・マテリアル・プリンターDMP-2831を用い、カートリッジに上記のように調製した各試料(インクセット)を順次装填し、搬送速度100m/minで画像形成した。形成された画像に対して、以下の評価を行った。
カートリッジには10pl吐出用(DMC-11610)を用い、これに外部から液供給し、搬送速度100m/minで描画できるようにプリンターを改造して画像形成を行った。描画には、インクジェット専用紙として、三菱製紙社製のIJ-PDW70、日本製紙社製のNpiフォームNEXT-IJ 70を用いた。
なお、画像形成では、処理液付与工程の後、10秒以内にインク打滴が開始されるようにした。
記録媒体へのインク付与の直前に、処理液を、塗布バーを用いて、塗工量1.0g/m2になるように記録媒体表面に塗設した。
処理液が付与された記録媒体上に、4色シングルパス画像形成を行った。具体的には、処理液が付与された記録媒体の該処理液上に、各色のインクを付与(打滴)して画像を形成した。
(1)耐擦性
インク塗設量が6g/m2となる量にて、「優(UTF-8:E584AAで表される文字)、並(UTF-8:E4B8A6で表される文字)、劣(UTF-8:E58AA3で表される文字)」の通常の文字(図1(a)に示す日本の漢字)と、「優(UTF-8:E584AAで表される文字)、並(UTF-8:E4B8A6で表される文字)、劣(UTF-8:E58AA3で表される文字)」の中抜き文字(図1(b)に示す日本の漢字)とからなる画像を、インクジェット専用紙であるIJ-PDW70(三菱製紙社製)、NpiフォームNEXT-IJ70(日本製紙社製)の各用紙に描画した。描画後1時間経過した後、0.15kg/cm2の圧力で押し付けながら描画面同士を20回擦った。この操作を各用紙に対して各々10回実施し、5人の評価者により下記の評価基準にしたがって官能評価を行い、5人の平均点を求めて評価指標とした。評価結果は、表2に示した。
5:通常の文字及び中抜き文字のいずれにも画像のボケや滲みがなく、良好な画像品質が得られた。
4:通常の文字及び中抜き文字ともに画像のボケや滲みが僅かに発生していたが、画像品質上許容できる程度であった。
3:通常の文字及び中抜き文字ともに画像のボケや滲みが時折発生していたが、文字の判別が可能で実用上許容できる品質であった。
2:通常の文字及び中抜き文字ともに画像のボケや滲みが発生しており、特に滲みの影響で中抜き文字の判別が不可能である等、実用上支障を来たす品質であった。
1:通常の文字及び中抜き文字ともに画像のボケや滲みが発生しており、通常の文字及び中抜き文字ともに滲みの影響で判別が不可能である等、実用上支障を来たす品質であった。
インク塗設量が6g/m2となる量にて、6pt、10pt、14ptの明朝体フォントを用いて、図2に示すように「優(UTF-8:E584AAで表される文字)」の通常の文字(図2(a)に示す日本の漢字)と、「優(UTF-8:E584AAで表される文字)」の中抜き文字(図2(b)に示す日本の漢字)とからなる画像を、インクジェット専用紙であるIJ-PDW70(三菱製紙社製)、NpiフォームNEXT-IJ70(日本製紙社製)の各用紙に50m連続描画した。この画像を目視観察し、5人の評価者により下記の評価基準にしたがって評価を行い、5人の平均点を求めて評価指標とした。評価結果は、表2に示した。
5:通常の文字及び中抜き文字のいずれにも画像のボケや滲みがなく、高い文字解像性を有する良好な画像品質が得られた。
4:通常の文字及び中抜き文字ともに画像のボケや滲みが僅かに発生していたが、画像品質上許容できる程度であった。
3:通常の文字及び中抜き文字ともに画像のボケや滲みが時折発生して、線や点で重なっている部分が発生したが、文字の判別が可能で実用上許容できる品質であった。
2:通常の文字及び中抜き文字ともに画像のボケや滲みが発生しており、特に線や点で重なっている影響で中抜き文字の判別が不可能である等、実用上支障を来たす品質であった。
1:通常の文字及び中抜き文字ともに画像のボケや滲みが発生しており、通常の文字及び中抜き文字ともに文字の解像性が低く、判別が不可能である等、実用上支障を来たす品質であった。
実施例1における試料101のインクセットの作製において、試料101の処理液中のシリコーンオイルを用いずに処理液を調製したほかは、試料101のインクセットの作製と同様にして、試料201のインクセットを作製した。
実施例1と同様に耐擦性、解像性を評価したところ、試料201でも実施例1の試料101と同様の耐擦性、解像性の改善効果が認められた。ただし、試料201においては、処理液の泡に起因すると考えられる塗布ムラが発生しており、安定した解像性という観点からは、試料101の方が優れていた。
これより、処理液は、シリコーンオイルを含有することによって、塗布ムラを発生しにくくすることができ、シリコーンオイルを含有する処理液を用いて画像形成することで、安定した解像性の画像が得られることが分かった。
実施例1における試料101のインクセットの作製において、試料101の処理液中の有機酸性化合物を、表3に示す有機酸性化合物に変更したこと以外は、試料101のインクセットの作製と同様にして、試料301~303のインクセットを作製した。
実施例1における試料101のインクセットの作製において、試料101の組成中の2-ピロリドンを、表4に示すピロリドン誘導体に変更したこと以外は、試料101のインクセットの作製と同様にして、試料401~405のインクセットを作製した。
実施例1における試料101のインクセットの作製において、試料101の組成中の水溶性ポリマー1を表5に示す水溶性ポリマー2~9に変更したこと以外は同様にして、試料501~試料508のインクセットを作製した。
水溶性ポリマー1の合成において、モノマー種及び混合比率を変更したこと以外は水溶性ポリマー1の合成と同様にして、表5に示す下記化学式の水溶性ポリマー2~水溶性ポリマー9を合成した。
水溶性ポリマー2~水溶性ポリマー9の化学式において、Meはメチル基であり、Etはエチル基であり、nBuはノルマルブチル基であり、tBuはターシャリーブチル基である。
なお、表5では、水溶性ポリマーのモノマー成分に着目し、水溶性ポリマー2を「MMA/AMPS」と、水溶性ポリマー3を「MMA/SPA(K)」と、水溶性ポリマー4を「MMA/BMA/AMPS」と、水溶性ポリマー5を「MMA/TBMA/AMPS」と、水溶性ポリマー6を「MMA/IBOMA/AMPS」と、水溶性ポリマー7を「MMA/CHMA/AMPS」と、水溶性ポリマー8を「MMA/BzMA/AMPS」と、水溶性ポリマー9を「MMA/PEMA/AMPS」と、それぞれ表記する。
SPA(K)は、スルホプロピルアクリレート カリウム塩を表し、TBMAは、tert-ブチルメタクリレートを表し、IBOMAは、イソボルニルメタクリレートを表し、CHMAは、シクロヘキシルメタクリレートを表し、BzMAは、ベンジルメタクリレートを表し、PEMAは、2-フェノキシエチルメタクリレートを表す。
Claims (10)
- 前記処理液は、更にシリコーンオイルを含有する請求項1に記載の画像形成方法。
- 前記インク付与工程は、50m/min以上の搬送速度で前記記録媒体を搬送する請求項1または請求項2に記載の画像形成方法。
- 前記ピロリドン誘導体が、2-ピロリドン及びN-メチル-2-ピロリドンの少なくとも一方である請求項1~請求項3のいずれか1項に記載の画像形成方法。
- 前記インク組成物中の前記ピロリドン誘導体の含有量が、前記インク組成物の全質量に対して、3.0質量%~20.0質量%である請求項1~請求項4のいずれか1項に記載の画像形成方法。
- 前記処理液中の前記有機酸性化合物の含有量が、前記処理液の全質量に対して、0.5質量%~20.0質量%である請求項1~請求項5のいずれか1項に記載の画像形成方法。
- 前記一般式(II)中のAOが、プロピレンオキシである請求項1~請求項6のいずれか1項に記載の画像形成方法。
- 前記水溶性高分子化合物が、下記一般式(A)で表される構造単位と下記一般式(B)で表される構造単位とを含む請求項1~請求項7のいずれか1項に記載の画像形成方法。
一般式(A)中、La1は、単結合、-COO-、又は-CON(Ra3)-を表す。Ra3は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
一般式(A)中、La2は、単結合、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の2価の連結基を表す。
一般式(A)中、Aaはイオン性基を表す。
一般式(B)中、Lb1は、単結合、-COO-、又は-CON(Rb3)-を表す。Rb3は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
一般式(B)中、Rb2は、水素原子、又は、エーテル結合、チオエーテル結合、及びエステル結合の少なくとも1種を含んでいてもよい炭素数1~30の1価の基を表す。
但し、前記Rb2が水素原子であるときは、前記Lb1は単結合である。 - 前記Rb2が、直鎖の炭素数1~12の脂肪族炭化水素基、分岐構造を有する炭素数3~12の脂肪族炭化水素基、環構造を有する炭素数3~12の脂肪族炭化水素基、炭素数7~12のアラルキル基、又は炭素数7~12のアリールオキシアルキル基である請求項8に記載の画像形成方法。
- 前記Ra1が水素原子であり、前記La1が-COO-又は-CONH-であり、前記La2が炭素数1~12のアルキレン基であり、前記Aaがスルホン酸基又はその塩であり、
前記Rb1が水素原子又はメチル基であり、前記Lb1が-COO-であり、前記Rb2が、直鎖の炭素数1~12の脂肪族炭化水素基、分岐構造を有する炭素数3~12の脂肪族炭化水素基、環構造を有する炭素数3~12の脂肪族炭化水素基、炭素数7~12のアラルキル基、又は炭素数7~12のアリールオキシアルキル基である請求項8または請求項9に記載の画像形成方法。
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