CN1814678A - 模版印刷用水性油墨和模版印刷方法 - Google Patents
模版印刷用水性油墨和模版印刷方法 Download PDFInfo
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- CN1814678A CN1814678A CNA2006100023475A CN200610002347A CN1814678A CN 1814678 A CN1814678 A CN 1814678A CN A2006100023475 A CNA2006100023475 A CN A2006100023475A CN 200610002347 A CN200610002347 A CN 200610002347A CN 1814678 A CN1814678 A CN 1814678A
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- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
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- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
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- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
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- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000019443 glyceryl diacetate Nutrition 0.000 description 1
- 235000019442 glyceryl monoacetate Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
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- 238000006703 hydration reaction Methods 0.000 description 1
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 230000035515 penetration Effects 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical class CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- UMHSKYSHOIGDPE-UHFFFAOYSA-N pyridine;quinoline Chemical compound C1=CC=NC=C1.N1=CC=CC2=CC=CC=C21 UMHSKYSHOIGDPE-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000019259 sodium dehydroacetate Nutrition 0.000 description 1
- 229940079839 sodium dehydroacetate Drugs 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940079832 sodium starch glycolate Drugs 0.000 description 1
- 239000008109 sodium starch glycolate Substances 0.000 description 1
- 229920003109 sodium starch glycolate Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/24—Stencils; Stencil materials; Carriers therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
本发明公开一种模版印刷用水性油墨,其包含在20℃下为液态的缔合型增稠剂。通过使用该油墨,将印刷机放置在不使用状态下之后重新印刷时,可以快速消除印刷图像的模糊。
Description
技术领域
本发明涉及一种模版印刷用水性油墨、特别涉及适用于旋转式数字模版印刷机中的模版印刷用水性油墨和使用该油墨的模版印刷方法。
背景技术
与胶版印刷、凹版印刷、凸版印刷这样的印刷方式相比,模版印刷方法具有优良的操作性、简便性,如,不需要在使用后进行洗涤等复杂的操作,不需要专业的操作人员等。自从使用将热印刷头用作部件的感热制版方式以来,由于在模版印刷方式中可以实现图像处理的数字化,并可以以短时间简便地得到高品质的印刷品,因此其作为信息处理终端的便利性越来越被认可。
可自动控制模版底纸的制版、装版、排版操作、供应油墨的操作和印刷操作等的旋转式模版印刷机,以数字式模版印刷机等的名称广泛用于办公室、学校等地方。
作为模版印刷用油墨,以往通常使用油包水型(W/O)乳化油墨。W/O型乳化油墨具有这样的功能,即,将印刷机置于非使用状态下时,即便印刷机内部的油墨与空气接触,也能抑制油墨的成分组成和物性的变化。也就是说,作为乳化油墨的内相成分的水被作为外相成分的油覆盖,因此可抑制水分的蒸发。
用W/O型乳化油墨印刷的印刷品中,油墨的干燥可以认为是通过这样进行的:油墨渗透到作为被印刷体(印刷介质)的印刷用纸的纸纤维之间;以及,通过与纸纤维的接触,乳剂缓慢分离为油相与水相,作为油墨的主成分的水与空气接触而蒸发。不过,在印刷后的短时间内,转移到被印刷体上的油墨中的水无法与空气接触,因此,刚印刷之后的干燥性依赖于渗透干燥,而W/O型乳化油墨的粘度在一定程度上被设计得较高,因此渗透速度不快,进而刚印刷之后的油墨干燥性不能说是充分的。
另外,从环境维护性、安全性的观点出发,已开发出用于模版印刷的水性油墨,已知有一种模版印刷方法,其在刚印刷之后的印刷表面上加入碱基,提高水性油墨对纸的渗透性(日本专利特开2001-302955号公报)。
在水性油墨中,从确保一定的初期粘度的观点出发,通常使用增稠剂。另一方面,由于构成油墨的水直接排出到空气中,水的蒸发较快,所以如果将油墨放置在印刷机内部的开放体系中,则会存在如下问题:由于水的蒸发会使油墨的粘度变得过高,经过长时间后再开始印刷时,印刷图像模糊,印刷后必须清洗机器。针对这些问题,尝试过添加防水分蒸发剂等的方法,但是希望有进一步改进。
发明内容
本发明涉及一种模版印刷用水性油墨,其包含:在20℃下为液态的非离子性的缔合型增稠剂。
本发明的另一发明涉及一种模版印刷方法,其使用上述本发明相关的模版印刷用水性油墨。
实施本发明的最佳方式
本发明的模版印刷用水性油墨(以下,将模版印刷用水性油墨简称为“油墨”),其特征在于:包含水与着色剂,包含在20℃下为液态的缔合型增稠剂。这里,所谓的“在20℃下为液态”是指在20℃下为液体,其可以是粘稠的,也可以是不粘稠的,但是优选其自身的粘度低的物质。
本发明的油墨由于含有在20℃下为液态的缔合型增稠剂,因此,即使在放置于印刷机内部的开放体系期间水分会蒸发,也能减少油墨的粘度变化。从而,在印刷机置于非使用状态下之后重新印刷时,能够迅速消除印刷图像的模糊(blurring)。
本发明所述的缔合型增稠剂是指这样的增稠剂:在水性介质中,分子之间通过疏水性相互作用彼此缔合,物理地交联,犹如作为一个巨大的分子而行动,从而使体系增稠。通常,增稠剂优选使用含有亲水性部位和疏水性部位的(共)聚合物,且分子量为3000以上~5万以下左右的物质。进一步,从抑制油墨放置时的油墨成分的分离的观点出发,作为增稠剂优选使用亲水亲油平衡(HLB)值为10或10以上左右的增稠剂,或者水溶性的增稠剂。
作为疏水性相互作用为人所知的力是一种两个疏水基在水中相对时该疏水基之间所产生的引力,其机理被理解为是熵的效果。也就是,如果在水中加入疏水性原子,由于水分子无法与作为溶质的疏水性原子形成氢键,所以水分子之间形成氢键以包围溶质,从而使熵稳定化。然而,这种状态与本体状态相比,结构自由度小、熵较低,因此,溶液整体的自由能高、不稳定。因此,通过溶质分子的聚集来减少被限制在水合壳上的水分子的数目(减少疏水性原子的表面积),提高熵,降低体系的自由能。
作为缔合型增稠剂的化学结构,有:进行疏水性相互作用的疏水基位于亲水性聚合物主链的末端上的远螯(telechelic)型结构,以及在亲水性主链上疏水基以侧链形式共聚而成的接枝型结构,任何一种结构都可以。
在体系中存在疏水性粒子时,缔合型增稠剂还可以通过疏水基吸附在粒子表面上形成物理交联,从而显示出同样的增稠作用。
在模版印刷机中,供应到印刷中的油墨在到进行下次印刷之前的期间内被放置在模版印刷鼓内部的开放体系中,因此会由于水分的蒸发而总量减少。目前,被作为增稠剂使用的水溶性高分子,当其浓度伴随水分的蒸发而上升时,高分子链的缠绕就会变强,导致粘度急剧升高。
相对于此,如前所述,本发明的缔合型增稠剂在水性介质中通过疏水性相互作用进行缔合,而使体系增稠,因此当油墨中的水分因蒸发而消失掉,或者水分减少使基于保湿性的观点而添加的水溶性有机溶剂的比例变高,则由于疏水性相互作用消失,而不再起到增稠剂的功能。因此,降低油墨粘度,或者在使用颜料作为着色剂时,消除颜料固态成分浓度的上升所引起的粘度上升的影响,抑制油墨的粘度变化。
此外,本发明的特征在于:使用在20℃下其自身为液态的(在20℃下为液体)的缔合型增稠剂。本发明者们以前开发出了一种含有非离子性聚合物的模版印刷用水性油墨,其中非离子性聚合物在两末端具有疏水基,且在分子骨架中具有由聚环氧烷链构成的亲水性部分(日本专利特愿2004-294155号)。在该专利申请中,混合常温下为固体的非离子性聚合物进行了研究,而进一步开展研究的结果,明确了这样的事实,即,通过使用液态的缔合型增稠剂,在水分蒸发后,油墨也不会固化,可以抑制油墨粘度的升高,对油墨赋予流动性。还明确了:使用该液态的缔合型增稠剂所带来的对粘度上升的抑制效果,与只增加油墨中水溶性有机溶剂的量的效果相比,更加显著。因此,根据本发明,可以认为即使将油墨放置在鼓内部的开放体系中,也可进一步防止油墨的粘度变化和固化,在放置后重新印刷时,图像可以更加迅速地恢复。
缔合型增稠剂的疏水基优选为烷基、环烷基、烯基、环烯基、芳基、烷基取代的芳基、芳基取代的烷基等的任意的烃基。从增稠作用的观点出发(碳原子数越大,疏水性相互作用越高,吸附作用越强),其碳原子数优选为6或6以上,更优选为10或10以上。另一方面,增加碳原子数超过某一程度后,增稠作用也没有大的差别,所以碳原子数优选为24或24以下左右,从常温下保持液态的必要性出发,更优选为18或18以下左右。
作为疏水基的烃基特别优选烷基。烷基还可以带有支链。
从提高增稠作用的观点出发,作为缔合型增稠剂,优选在分子骨架中含有尿烷基(氨基甲酸酯基)的物质。尿烷基被推测为与其它的有机结合基相比,分子内聚能较强,加强分子间的疏水性相互作用。
构成尿烷基的二异氰酸酯没有特别的限制,可以列举四亚甲基二异氰酸酯、六亚甲基二异氰酸酯等的脂肪族二异氰酸酯;对苯二异氰酸酯、2,4-甲苯二异氰酸酯、苯二甲撑二异氰酸酯等的芳香族二异氰酸酯;1,4-环己撑二异氰酸酯、4,4′-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯等的脂环式二异氰酸酯。其中,优选使用六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯。
从增稠剂在水中的稳定性良好、并且即使水分蒸发增稠剂也保持液态、能防止油墨固化的观点出发,成为缔合型增稠剂的亲水性部位或者亲水性主链的聚合物优选为非离子性、且在常温下为液态的物质。
具体地,优选环氧乙烷与碳原子数为3~4的环氧烷的共聚物等,但是并不限于此。
作为含上述尿烷基的缔合型增稠剂的一个例子,可以列举具有如下结构的物质:烷基-环氧烷基(例如,环氧乙烷-环氧丙烷)-尿烷基-环氧烷基(同上)-烷基。
上述缔合型增稠剂可以单独使用,可以组合多种来使用。其在油墨中的含量,在使用多种的情况下,以其总量计,优选为1~15重量%,更优选为3~10重量%。小于1重量%,就无法得到足够的增稠作用,而即使混和超过15重量%,也看不出效果的差异。
上述缔合型增稠剂优选与少量的丙烯酸类水溶性高分子等的不饱和羧酸类水溶性高分子一起使用。
不饱和羧酸类水溶性高分子,尽管其增稠作用较强,但如果添加量增加,则可能会导致在开放体系中放置时的油墨粘度的显著升高。另一方面,缔合型增稠剂的增稠作用如上所述是基于疏水性相互作用的,因此其增稠作用较弱,但是可以抑制在开放体系中放置时的油墨粘度的升高。因此,通过同时使用两者,可以容易地使油墨的转移量合理化,并且可以抑制放置后的油墨粘度的升高。
不饱和羧酸类水溶性高分子的含量根据其种类和所希望的油墨粘度等而异,通常相对于油墨总量,优选为0.05~5.0重量%,更优选为0.1~3.0重量%。若小于0.05重量%,则可能无法得到足够的增稠作用,若超过5.0重量%,则可能会导致在开放体系中放置时的油墨粘度的显著升高,所以不优选。
在本发明中,不饱和羧酸类水溶性高分子是指包含下式(1)所示重复单元的水溶性高分子。
式中,R1,R2、R3各自独立地表示H、CH3、(CH2)nCOOH,其中n表示0或1的整数。在包含2个或2个以上羧基时,它们也可以形成酸酐。形成共聚物时的共聚形式可以是无规型、交替型、嵌段型、接枝型等的任何形态。另外,高分子链的结构可以是直链型,也可以是在分子内具有交联结构的交联型。
作为该不饱和羧酸类增稠剂,例如可以列举在主链中包含选自下组中的1种或1种以上不饱和羧酸的水溶性高分子,也可以包含它们的盐:丙烯酸或甲基丙烯酸(以下,将两者合并称作“(甲基)丙烯酸”)、马来酸酐、马来酸、富马酸、巴豆酸和衣康酸。更具体地,可以列举聚(甲基)丙烯酸、丙烯酸-甲基丙烯酸共聚物、(甲基)丙烯酸-马来酸共聚物、(甲基)丙烯酸-磺酸类单体共聚物、(甲基)丙烯酸-衣康酸共聚物、(甲基)丙烯酸酯-马来酸共聚物、(甲基)丙烯酸-(甲基)丙烯酰胺共聚物、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、(甲基)丙烯酸-乙烯基吡咯烷酮共聚物、聚马来酸、聚富马酸、聚巴豆酸、聚衣康酸、马来酸酐-烷基乙烯基醚共聚物、以及它们的盐等。
作为盐,优选一价金属盐、胺盐,例如如果是聚丙烯酸,则作为它们的盐可以列举聚丙烯酸钠、聚丙烯酸钾、聚丙烯酸胺、聚丙烯酸三乙醇胺等。另外,也可以使用将未中和型的不饱和羧酸类增稠剂与氢氧化钠、氢氧化钾、三乙醇胺、二异丙醇胺等碱性中和剂在水中混和进行中和而成的水溶液。
除了上述不饱和羧酸类水溶性高分子以外,也可以使用1种或1种以上其它的水溶性高分子类增稠剂、粘土矿物类增稠剂。
作为其它的水溶性高分子类增稠剂,例如可以使用阿拉伯胶、卡拉胶、瓜耳豆胶、刺槐豆胶、果胶、黄蓍胶、谷物淀粉、魔芋葡苷聚糖、琼脂等植物类天然高分子;普鲁兰糖、黄原胶、糊精等微生物类天然高分子;明胶、酪蛋白、动物胶等动物类天然高分子;乙基纤维素、羧甲基纤维素、羟乙基纤维素、羟丙基纤维素、甲基纤维素、羟丙基甲基纤维素等纤维素类半合成高分子;羟乙基淀粉、羧甲基淀粉钠、环糊精等淀粉类半合成高分子;藻酸钠、藻酸丙二酯等藻酸类半合成高分子;透明质酸钠;聚乙烯基吡咯烷酮、聚乙烯醇、聚乙烯基甲基醚、聚N-乙烯基乙酰胺、聚丙烯酰胺、聚环氧乙烷、聚乙烯亚胺、聚氨酯等合成高分子。
作为粘土矿物类增稠剂,例如可以使用蒙脱石、锂蒙脱石、皂石等蒙脱石类粘土矿物。
另外,作为增稠剂例示的上述水溶性高分子,根据其种类和用量,除了用作油墨的增稠剂以外,还可以用作着色剂对印刷用纸的定影剂等。另外,在使用颜料作为着色剂时,也可以用作颜料的分散剂。
从提高印刷品的干燥性的观点出发,优选在油墨中含有50重量%或50重量%以上的水,更优选含有65重量%或65重量%以上的水。油墨中所含有的水可以在印刷后立即蒸发到大气中。此外,通过在印刷时油墨被压入、渗透到印刷用纸的纤维之间,在印刷用纸内部,油墨与空气的表面积急速扩大,水变得容易蒸发,因此,可以认为增大水的量就可以进一步提高印刷品的干燥性。另一方面,水的混合量的上限没有特别的定义,优选根据与其它混和成分的平衡而适当设定。
从防止印刷中的模版底纸的穿孔部的干燥等观点出发,优选在油墨中进一步混和水溶性有机溶剂。
作为水溶性有机溶剂,可以使用室温下为液体、并可溶于水的有机化合物。例如,可以使用甲醇、乙醇、1-丙醇、异丙醇、1-丁醇、2-丁醇、异丁醇、2-甲基-2-丙醇等低级醇类;乙二醇、二甘醇、三甘醇、四甘醇、五甘醇、丙二醇、二丙二醇、三丙二醇等二醇类;甘油;乙酸甘油酯类(单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯);三甘醇单甲基醚、三甘醇单乙基醚、三甘醇单丙基醚、三甘醇单丁基醚、四甘醇单甲基醚、四甘醇单乙基醚、四甘醇二甲基醚、四甘醇二乙基醚等二醇类衍生物;三乙醇胺、β-硫代乙二醇、环丁砜。也可以使用平均分子量为200、300、400、600等的平均分子量在190~630的范围内的聚乙二醇、平均分子量为400等的平均分子量在200~600的范围内的二醇型聚丙二醇、平均分子量为300、700等的平均分子量在250~800的范围内的三醇型聚丙二醇等的低分子量聚亚烷基二醇。这些水溶性有机溶剂可以单独使用,或组合2种或2种以上使用。
水溶性有机溶剂在油墨中的含量优选为5重量%或5重量%以上,更优选为10重量%或10重量%以上。关于其含量的上限,并没有特别的限定,但为了减少图像的渗墨,优选为45重量%或45重量%以下左右,更优选为35重量%或35重量%以下左右。通过在油墨中含有5重量%或5重量%以上的水溶性有机溶剂,其中该水溶性有机溶剂的沸点比水的更高,更优选为150℃或150℃以上,可以有效地防止印刷中的模版底纸穿孔部的干燥,所以优选。
作为着色剂可以使用颜料或染料,也可以同时使用2种或2种以上。作为颜料,例如可以使用偶氮类、酞菁类、染料类、缩合多环类、硝基类、亚硝基类等的有机染料(亮胭脂红6B、色淀红C、颜料红、双偶氮黄、汉撒黄、酞菁蓝、酞菁绿、碱性蓝和苯胺黑等);钴、铁、铬、铜、锌、铅、钛、钒、锰、镍等金属类、金属氧化物及硫化物,以及黄土、群青和绀青等的无机颜料;炉黑、灯黑、乙炔黑、槽黑等的碳黑类。作为染料,例如可以使用碱性染料、酸性染料、直接染料、可溶性瓮染料、酸性媒染染料、媒染染料、反应染料、瓮染料、硫化染料等中的水溶性染料以及通过还原等成为水溶性的水溶性染料。颜料、染料的任一者或两者都可用作着色剂,但是优选使用颜料,这是因为使用颜料可以形成图像的渗色(bleeding)和渗墨(image show through)少、耐气候性也优异的油墨。
油墨中的着色剂的含量优选为1~20重量%,更优选为3~10重量%,为了进一步提高印刷品的印刷浓度,进一步优选为5重量%或5重量%以上。
在本发明的油墨中除了含有上述成分之外,还可以适当含有颜料分散剂、定影剂、消泡剂、表面张力降低剂、pH调节剂、抗氧化剂、防腐剂等。
在油墨中含有碱溶性树脂,可以作为着色剂对印刷用纸等被印刷体的定影剂使用。使用颜料作为着色剂时,也可以使用碱溶性树脂作为颜料的分散剂。
作为碱溶性树脂,例如可以使用苯乙烯-丙烯酸共聚物、苯乙烯-α-甲基苯乙烯-丙烯酸共聚物、苯乙烯-甲基丙烯酸共聚物、苯乙烯-丙烯酸酯-丙烯酸共聚物、苯乙烯-马来酸酐共聚物、乙烯基萘-丙烯酸共聚物、乙烯基萘-马来酸共聚物、异丁烯-马来酸酐共聚物、丙烯酸酯-丙烯酸共聚物、甲基丙烯酸酯-丙烯酸共聚物、丙烯酸酯-甲基丙烯酸共聚物、甲基丙烯酸酯-甲基丙烯酸共聚物、丙烯酸酯-甲基丙烯酸酯-丙烯酸共聚物,也可以同时使用2种或2种以上。这些碱溶性树脂可以用氢氧化钠、氢氧化钾等碱金属氢氧化物、氨水、三乙醇胺等烷醇胺等的任意的碱中和,成为水可溶性后使用。
如果大量含有碱溶性树脂,则可能会对印刷机不使用后的印刷性能产生障碍,因此以固态成分计,优选在油墨中以5重量%或5重量%以下的范围含有碱溶性树脂,更优选含有3重量%或3重量%以下。
在油墨中含有水包油(O/W)型树脂乳剂,可以用作着色剂对印刷用纸等被印刷体(印刷介质)的定影剂等。在使用颜料作为着色剂时,也可以将该树脂乳剂用作颜料的分散剂。
作为水包油(O/W)型树脂乳剂,例如可以使用聚醋酸乙烯酯、乙烯-醋酸乙烯酯共聚物、醋酸乙烯酯-丙烯酸酯共聚物、聚丙烯酸酯、聚甲基丙烯酸酯、聚苯乙烯、苯乙烯-丙烯酸酯共聚物、苯乙烯-丁二烯共聚物、偏氯乙烯-丙烯酸酯共聚物、聚氯乙稀、氯乙烯-醋酸乙烯酯共聚物、聚氨酯等树脂乳剂。也可以同时使用它们的2种或2种以上。
如果大量含有树脂乳剂,则可能会对印刷机不使用后的印刷性能产生障碍,因此以固态成分计,优选在油墨中以5重量%或5重量%以下的范围含有树脂乳剂,更优选含有2重量%或2重量%以下。
为了提高印刷品的画质,可以在油墨中含有体质颜料。
作为体质颜料,例如可以使用白土、滑石、粘土、硅藻土、碳酸钙、碳酸钡、硫酸钡、矾土白、硅石、高岭土、云母、氢氧化铝,也可以同时使用它们的2种或2种以上。
如果大量含有体质颜料,则可能会阻碍着色剂对被印刷体的定影,或者可能会对印刷机不使用后的印刷性能产生障碍,因此优选以5重量%或5重量%以下的范围含有体质颜料,更优选含有2重量%或2重量%以下。
此外,作为颜料分散剂、消泡剂、表面张力降低剂等,可以在油墨中含有阴离子表面活性剂、阳离子表面活性剂、两性表面活性剂、非离子表面活性剂、或者高分子类、硅酮类、氟类表面活性剂。
为了调节油墨的粘度和pH,还可以在油墨中混合电解质。作为电解质,例如可以列举硫酸钠、磷酸氢钾、柠檬酸钠、酒石酸钾、硼酸钠,也可以同时使用2种或2种以上。硫酸、硝酸、醋酸、氢氧化钠、氢氧化钾、氢氧化氨、三乙醇胺等也可以作为油墨的增稠助剂和pH调节剂使用。
通过混合抗氧化剂,可以防止油墨成分的氧化,提高油墨的保存稳定性。作为抗氧化剂,例如可以使用L-抗坏血酸、L-抗坏血酸钠、异抗坏血酸钠、亚硫酸钾、亚硫酸钠、硫代硫酸钠、连二亚硫酸钠、焦亚硫酸钠。
通过混合防腐剂,可以防止油墨腐坏,提高保存稳定性。作为防腐剂,例如可以使用5-氯-2-甲基-4-异噻唑啉-3-酮、2-甲基-4-异噻唑啉-3-酮、2-正辛基-4-异噻唑啉-3-酮、1,2-苯并异噻唑啉-3-酮等异噻唑酮类防腐剂;六氢-1,3,5-三(2-羟乙基)-s-三嗪等三嗪类防腐剂;1-氧化-2-吡啶硫醇钠、8-羟基喹啉等吡啶·喹啉类防腐剂;二甲基二硫代氨基甲酸钠等二硫代氨基甲酸盐类防腐剂;2,2-二溴-3-腈基丙酰胺、2-溴-2-硝基-1,3-丙二醇、2,2-二溴-2-硝基乙醇、1,2-二溴-2,4二氰基丁烷等有机溴类防腐剂;对-羟基苯甲酸甲酯、对-羟基苯甲酸乙酯、山梨酸钾、脱氢醋酸钠、水杨酸。
本发明的油墨可以将水、着色剂、上述缔合型增稠剂、以及根据需要适当混合的上述成分进行混合而制造。例如,可以将部分的水、颜料和颜料分散剂混合,使用球磨、珠磨等分散装置使颜料分散,另一方面,将剩余的水和增稠剂、水溶性有机溶剂混合,然后将两者混合到一起。
油墨的粘度,其适合的范围根据印刷装置的印刷压力等而不同,通常为约0.5Pa·s~约20Pa·s(在20℃、剪切速率为100s-1下的粘度),并且为(拟)塑性流动性的,适用于模版印刷中。
其次,本发明涉及的模版印刷方法可以使用上述本发明的油墨来进行。具体地,包括如下工序:准备已制版的模版底纸;通过使已制版的模版底纸与被印刷体压接,使本发明的油墨从模版底纸的穿孔部通过而转移到被印刷体上。
所使用的模版印刷机没有特别的限定,从操作性优异方面出发,优选使用数字式模版印刷机。
实施例
以下,通过实施例对本发明进行更详细的说明,但是本发明并不限于此。以下,将“重量%”简称为“%”。
实施例1
如表1所示,将5.0%作为着色剂的(1)碳黑(三菱化学株式会社制造的“CF9”)、3.3%(表中的值是固态成分换算值)作为颜料分散剂的(2)丙烯酸铵-丙烯酸酯共聚物(聚丙烯酸酯共聚物;日本纯药工业株式会社制造的“Jurymer AT210”,固态成分30%)和16.7%离子交换水进行混合,通过珠磨使其充分分散,制备颜料分散液。将0.5%作为增稠剂的(3)羧基乙烯基聚合物(BF Goodrich公司制造的“Carbopol 940”)溶于14.0%的离子交换水中,向其中添加0.5%的(8)三乙醇胺进行中和后,加入先前制备的颜料分散液、22.0%的(7)二甘醇、剩余量的离子交换水(35.0%)、以及3.0%作为液态缔合型增稠剂的(4)尿烷改性的聚环氧烷(=环氧乙烷和环氧丙烷)二烷基醚(Akzo Nobel公司制造的“BermodolPUR2110”)进行混合,得到实施例1的油墨。
实施例2~4、比较例1、2
除了采用表1所示的配方以外,与实施例1同样地进行,得到各实施例和比较例的油墨。在表1中,(5)的尿烷改性的聚环氧烷(=环氧乙烷和环氧丙烷)二烷基醚是Akzo Noble公司制造的“Elfacos T212”,(6)的尿烷改性的聚环氧烷二烷基醚是旭电化工业株式会社制造的“Adekanol UH420”(固态成分30%,表中的值为固态成分换算值)。
缔合型增稠剂(4)~(6)的性状(是液体还是固体),在为含水的产品(6)时,将水分蒸发,以100%的有效成分的状态确认。
使用上述实施例1~4和比较例1和2制造的各油墨(模版印刷用水性油墨),分别通过模版印刷机(Risograph RP370,理想科学工业株式会社制造),在印刷用纸(理想科学工业株式会社制造的“理想轻质纸”)上进行印刷。印刷结束后,维持原有状态地,在23℃、50%RH的环境下,将印刷机放置15个小时。之后,使用放置后的印刷机卷绕新制造的版,重新开始印刷,观察所得图像的状态。
重新开始印刷后的图像的质量(放置后的图像恢复)根据以下基准进行评价。
○:在10张以内,可以得到不存在模糊的图像,
×:即使印刷50张,图像也存在模糊。
所得的结果如表1所示。
实施例的油墨,任一个都可以在10张以内得到不存在模糊的图像。相对于此,比较例的油墨即使印刷50张,图像也存在模糊。
表1
混合量/重量% | 实施例 | 比较例 | ||||||
1 | 2 | 3 | 4 | 1 | 2 | |||
着色剂 | 碳黑 | (1) | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
颜料分散剂 | 聚丙烯酸酯共聚物 | (2) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
增稠剂 | 羧基乙烯基聚合物 | (3) | 0.5 | 0.3 | 0.2 | - | 0.5 | 0.5 |
液态非离子性缔合型增稠剂(远螯型) | 尿烷改性的聚环氧烷二烷基醚 | (4) | 3.0 | 7.0 | - | 15.0 | - | - |
尿烷改性的聚环氧烷二烷基醚 | (5) | - | - | 5.0 | - | - | - | |
固体非离子性缔合型增稠剂(远螯型) | 尿烷改性的聚环氧烷二烷基醚 | (6) | - | - | - | - | - | 3.0 |
水溶性有机溶剂 | 二甘醇 | (7) | 22.0 | 18.0 | 20.0 | 10.0 | 25.0 | 22.0 |
中和剂 | 三乙醇胺 | (8) | 0.5 | 0.3 | 0.2 | - | 0.5 | 0.5 |
离子交换水 | 68.0 | 68.4 | 68.6 | 69.0 | 68.0 | 68.0 | ||
总计 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | ||
评价 | 放置后的图像恢复 | ○ | ○ | ○ | ○ | × | × |
Claims (5)
1.一种模版印刷用水性油墨,其包含在20℃下为液态的非离子性的缔合型增稠剂。
2.根据权利要求1所述的模版印刷用水性油墨,前述非离子性的缔合型增稠剂是在分子骨架中含有尿烷基的增稠剂。
3.根据权利要求1所述的模版印刷用水性油墨,其中,前述非离子性的缔合型增稠剂的含量为1~15重量%。
4.根据权利要求1所述的模版印刷用水性油墨,进一步含有不饱和羧酸类水溶性高分子。
5.一种模版印刷方法,该方法使用权利要求1所述的模版印刷用水性油墨。
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CN115595024A (zh) * | 2021-07-08 | 2023-01-13 | 武汉苏泊尔炊具有限公司(Cn) | 复合不粘涂料及其制备方法和烹饪器具 |
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GB2422610B (en) | 2009-06-24 |
CN100575432C (zh) | 2009-12-30 |
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