CN102010631B - Single-fluid general type plastic intaglio alcohol-water soluble composite ink and preparation method thereof - Google Patents
Single-fluid general type plastic intaglio alcohol-water soluble composite ink and preparation method thereof Download PDFInfo
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- CN102010631B CN102010631B CN 200910216018 CN200910216018A CN102010631B CN 102010631 B CN102010631 B CN 102010631B CN 200910216018 CN200910216018 CN 200910216018 CN 200910216018 A CN200910216018 A CN 200910216018A CN 102010631 B CN102010631 B CN 102010631B
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- 229920003023 plastic Polymers 0.000 title claims abstract description 40
- 239000004033 plastic Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000012530 fluid Substances 0.000 title claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 50
- 239000004814 polyurethane Substances 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 239000012046 mixed solvent Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 6
- 239000012860 organic pigment Substances 0.000 claims abstract description 6
- 229920000573 polyethylene Polymers 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000976 ink Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 24
- 229920002125 Sokalan® Polymers 0.000 claims description 22
- 239000004584 polyacrylic acid Substances 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000012856 packing Methods 0.000 claims description 13
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002318 adhesion promoter Substances 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003556 assay Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 abstract description 9
- 229920006255 plastic film Polymers 0.000 abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 229920000058 polyacrylate Polymers 0.000 abstract 3
- 239000002415 cerumenolytic agent Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 235000019439 ethyl acetate Nutrition 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229920005749 polyurethane resin Polymers 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 125000005594 diketone group Chemical group 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229920001470 polyketone Polymers 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 4
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000209128 Bambusa Species 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- RFAFBXGYHBOUMV-UHFFFAOYSA-N calcium chromate Chemical compound [Ca+2].[O-][Cr]([O-])(=O)=O RFAFBXGYHBOUMV-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Abstract
The invention relates to plastic intaglio composite ink, in particular to single-fluid general type plastic intaglio alcohol-water soluble composite ink and a preparation method thereof. The single-fluid general type plastic intaglio alcohol-water soluble composite ink takes (methyl) acrylic esters, vinyl acetic esters, polymerizable polyurethane macromonomers and active functional monomers as raw materials and comprises polyurethane graft polyacrylate copolymers, alcohol-water soluble acrylate copolymers, alcohol-water soluble polyurethane resins, organic/inorganic pigments, dispersing agents, adhesive force accelerants, polyethylene wax and mixed solvents, wherein the polyurethane graft polyacrylate copolymer is obtained through the radical polymerization of a solution; and the single-fluid general type intaglio alcohol-water soluble composite ink has good alcohol-water solubility and solvent release and good adhesive force on various plastic film base materials due to the introduction of polyurethane and the synergistic effect of the polyurethane graft polyacrylate copolymer. The invention has good printing effect and high adaptability and composite intensity and can be used for the printing of various plastic base materials; and in addition, the invention has low cost and environmental protection compared with pure polyurethane ink and higher performance and printing adaptability compared with pure acrylate copolymer ink.
Description
Technical field
The present invention relates to plastic rotogravure composite ink, particularly single-fluid general plastic gravure alcohol-soluble and water-soluble composite China ink and preparation method thereof.
Technical background
In recent years, along with the continuous lifting of living standards of the people, not only drive the growth at full speed of packaging industry, also promoted the development in plastics base gravure ink technology and market.The plastics base gravure ink has obtained to use very widely in plastic wrapping at present, and such as all types of plastic film substrate packing in industries such as food, medicine, agricultural byproducts, daily necessities, its range of application has almost been included all packaging fields.For adapting to social development to the pursuit of " green and environmental protection ", plastics base gravure ink enterprise and correlative study mechanism are devoted to the research and development of " environmental protection " printing ink in recent years always, in the hope of substituting traditional benzene soluble ink with cleanliness without any pollution or oligosaprobic alcohol-soluble and water-soluble or pure molten printing ink, thereby alleviate to the pollution of environment with to the threat of HUMAN HEALTH.The pure aqueous composite ink that is used for intaglio plate is disclosed such as number of patent application CN200610022514.2, number of patent application CN200510044632.9 discloses a kind of environment protection plastic printing ink and preparation method thereof, and intaglio plate carton Preprinted ink and paper that number of patent application CN200410012541.2 and CN200610020124.1 then disclose respectively pure dissolubility stamp gloss oil.
In view of printing ink is by resin binder, pigment, auxiliary agent and solvent composition, and the fundamental property of printing ink, provided by the resin binder in its component such as solvent system selection, base material sticking power, compound ability etc., therefore, for promoting the development of pure molten and alcohol-soluble and water-soluble printing ink, make it adapt to the molten and pure water-soluble solvent system of alcohol, and the sticking power of raising printing ink on all types of plastic film substrate, satisfy the service requirementss of different multiple film colloids system, also obtained corresponding research as the resin binder of plastics base gravure ink core component.Ink resin that is used for intaglio printing and preparation method thereof is disclosed such as number of patent application CN200810104378.0, number of patent application CN00126683.7 discloses a kind of preparation method of polyamide resin used for alcohol-soluble ink, and number of patent application CN20081001855.3 discloses a kind of alcohol-soluble polyurethane soluble in water and preparation method thereof.The printing ink of these printing ink and the preparation of these resin binders is compared with traditional benzene dissolubility plastics base gravure ink, has good environment-friendly advantage.
But, the single-liquid type of the preparation alcohol aqueous composite ink take polyacrylic ester as resin binder, because of the polyacrylic ester molecular polarity a little less than, main applicable BOPP plastic film substrate and alcohol-soluble composite film adhesive, when the PET plastic film substrate uses, then sticking power is relatively poor, and poor with the multiple film glue consistency of the molten type of ester, and combined strength bination is lower; And urethane is the single-liquid type alcohol aqueous composite ink of resin binder preparation, then because of the strong polarity of polyurethane molecular, main applicable PET plastic film substrate and ester soluble composite film adhesive, when the BOPP plastic film substrate uses, then sticking power is relatively poor, and poor with the multiple film glue consistency of ethanol-soluble type, combined strength bination is lower.
If but the single-liquid type that will prepare take polyacrylic ester as resin binder merely alcohol aqueous composite ink and urethane carry out mechanically mixing as the pure aqueous composite ink of the single-liquid type of resin binder preparation, preparation single-fluid general plastic gravure composite printing ink then can cause printing performance significantly to reduce because of the greatest differences of two kinds of resin binder molecular structures.For avoiding above-mentioned the deficiencies in the prior art part, the invention provides a kind of environment-friendly type alcohol-soluble and water-soluble single-fluid general plastic gravure composite printing ink and preparation method thereof, effectively to adapt to all kinds of film substrates and multiple film glue, obtain desirable printing and composite effect, satisfy packaging industry to the demand of single-fluid general plastic intaglio plate alcohol aqueous composite ink.
Summary of the invention
The object of the present invention is to provide a kind of single-fluid general plastic intaglio plate alcohol aqueous composite ink and preparation method thereof, by the large monomer of Polymerizable Polyurethane and (methyl) acrylate, vinyl acetate, the Solution Free Radical copolymerization of active function monomer, polyurethane branch chains is introduced the polyacrylic ester molecular backbone chain, polarity with effective adjusting gained molecular resin, obtain the polyurethane grafting polyacrylic acid ester copolymer, and utilize it to improve the consistency of acrylic copolymer and urethane resin, thereby make the printing ink by acrylic copolymer and urethane resin preparation not only have good alcohol-soluble and water-soluble and solvent release, simultaneously because the synergy of polyurethane grafting polyacrylic acid ester copolymer, make it to all types of plastic film substrate (BOPP, PET, PA, PVC, PE, PC etc.) has good sticking power, printing effect is good, strong adaptability, adapt to all kinds of multiple film glue (the molten types of ester, ethanol-soluble type), combined strength bination is high, can be used for the printing of all types of plastic base material, and the inexpensive environmental protection of purer polyurethane ink, more simple acrylate copolymer ink performance is higher, printing adaptability is stronger.
The objective of the invention is to realize by the following technical solutions:
Single-fluid general plastic intaglio plate of the present invention alcohol aqueous composite ink and preparation method thereof is to be raw material by (methyl) acrylate, vinyl acetate, the large monomer of Polymerizable Polyurethane and active function monomer, the polyurethane grafting polyacrylic acid ester copolymer and alcohol-soluble and water-soluble acrylate copolymer, alcohol-soluble and water-soluble urethane resin, organic/inorganic pigment, dispersion agent, adhesion promoter, polyethylene wax and the mixed solvent that get by solution free radical polymerization form, and the weight proportion of each component is:
Polyurethane grafting polyacrylic acid ester copolymer 2～10
Alcohol-soluble and water-soluble acrylate copolymer 15～30
Alcohol-soluble and water-soluble urethane resin 2～10
Organic/inorganic pigment 6～35
Dispersion agent 0.5～3
Adhesion promoter 0.5～3
Polyethylene wax 0.1～0.5
Mixed solvent 30～60
Wherein the polyurethane grafting polyacrylic acid ester copolymer is to prepare by the following method:
1) first vulcabond is added, be warmed up to 30～80 ℃, the adding monomer weighs the oil-soluble catalyst of 0.01～0.2wt%, after mixing 10～30 minutes, add hydroxy acrylate, reacted 1～4 hour, then add polyester diol, at 30～80 ℃, continue reaction 2～5 hours, cooling namely gets the large monomer of Polymerizable Polyurethane;
2) initiator and the 50wt% solvent with 50wt% adds reactor, after stirring, is warming up to 50～85 ℃; Behind temperature-stable, (methyl) acrylate, vinyl acetate, active function monomer, the large monomer of Polymerizable Polyurethane are mixed, in 3～8 hours, evenly be added dropwise to reactor, drip simultaneously the initiator solution that initiator and 30wt% solvent by 50wt% form; After dropwising, keep 50～85 ℃ of temperature, continue to stir 2～5 hours, then cooling adds the residual solvent dilution; After being down to room temperature, packing namely makes the polyurethane grafting polyacrylic acid ester copolymer.
Each weight proportion that forms is in the aforesaid method:
(methyl) acrylate 10～80
Vinyl acetate 10～80
The large monomer 5～40 of Polymerizable Polyurethane
Active function monomer 2～8
Initiator 0.1～2.0
Solvent 50～500
Wherein: the active function monomer is vinylformic acid, acrylamide, methacrylic acid, maleic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, glycidyl acrylate, hydroxyethyl methylacrylate, Rocryl 410, the mixture of one or more above compositions; (methyl) acrylate is methyl acrylate, ethyl propenoate, butyl acrylate, the own ester of ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, the own ester of β-dimethyl-aminoethylmethacrylate, the mixture of one or more above compositions; Initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; Solvent is the ethanol that water content is not higher than 5wt%, ethyl acetate or both mixtures; Oil-soluble catalyst is dibutyl tin laurate; Hydroxy acrylate is Hydroxyethyl acrylate or Propylene glycol monoacrylate; Vulcabond is different Buddhist diketone vulcabond or tolylene diisocyanate.
And the preparation technology of single-fluid general plastic gravure alcohol-soluble and water-soluble composite China ink is:
1) ethanol and the water that water content are not higher than 5wt% are made mixed solvent in 9: 1～2: 1 ratio;
2) polyurethane grafting polyacrylic acid ester copolymer, alcohol-soluble and water-soluble acrylate copolymer, alcohol-soluble and water-soluble urethane resin and pigment, dispersion agent, adhesion promoter, wax powder and mixed solvent are added blender loader, stirred 20～30 minutes with high speed dispersor, it is mixed;
3) material that mixes is taken out, send into sand mill and carry out sand milling, be lower than 10 microns until fineness and take out afterwards, filter; Through after the assay was approved, packing namely makes the single-fluid general plastic gravure alcohol-soluble and water-soluble composite China ink.
Wherein: pigment is common organic or inorganic pigment, select Rutile type Titanium Dioxide such as white pigment, black pigment is selected carbon black, yellow ultramarine is selected benzidine yellow G and benzidine yellow 10G to piece together and is used, redness is selected lithol that dark red 243, blueness selects the phthalein mountain valley with clumps of trees and bamboo blue, take paint as recommendation pigment, but is not limited only to above-mentioned pigment in actual the use; The wax powder is the polyethylene wax of high molecular; Adhesion promoter is polyketone resin, and above promotor is recommendation promotor, but is not limited only to above-mentioned promotor in actual the use; Dispersion agent is BYK-191, CA-600, and above dispersion agent is recommended hour powder, but is not limited only to above-mentioned dispersion agent in actual the use.
The advantage of maximum of the present invention is to introduce by the polyurethane grafting polyacrylic acid ester copolymer, utilize its synergy, make alcohol-soluble and water-soluble acrylate copolymer and urethane resin possess good consistency, thereby satisfied the requirement of single-fluid general plastic intaglio plate alcohol aqueous composite ink high-performance and high printing adaptability.Prepared printing ink not only has good alcohol-soluble and water-soluble and solvent release, simultaneously because the synergy of polyurethane grafting polyacrylic acid ester copolymer, make it have good sticking power to all types of plastic film substrate (BOPP, PET, PA, PVC, PE, PC etc.), printing effect is good, strong adaptability, adapt to all kinds of multiple film glue (the molten type of ester, ethanol-soluble type), combined strength bination is high, can be used for the printing of all types of plastic base material, and the inexpensive environmental protection of purer polyurethane ink, more simple acrylate copolymer ink performance is higher, printing adaptability is stronger.
Single-fluid general plastic intaglio plate alcohol aqueous composite ink preparation method of the present invention is simple, and good, the strong adaptability of the compound oil ink printing effect of preparation can be used for the printing of all types of plastic base material; Need not use crosslinking component, easy to operate, combined strength bination is high; Printing ink is alcohol-soluble and water-soluble, economic environmental protection, thereby have broad application prospects in the plastic rotogravure composite ink field.
Embodiment:
Embodiment one
The preparation of the compound white ink of single-fluid general plastic intaglio plate alcohol water-based
The instruments such as 500ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To the different Buddhist diketone vulcabond (IPDI) with adding 85.5g in the 500ml four-necked bottle of agitator, thermometer, be heated to 50 ℃ under stirring, add the dibutyl tin laurate of 0.03g, mix 10 minutes, then drip the 50.0g Propylene glycol monoacrylate.It is 400 polyester diol that 50 ℃ of reactions add the 153.9g molecular weight after 3 hours again, and 50 ℃ are continued reaction 4 hours.Then be cooled to 30 ℃, discharging namely makes the large monomer of Polymerizable Polyurethane.
Diisopropyl azodicarboxylate, 120g vinyl acetic monomer and the 130g dehydrated alcohol of 2.5g are added reactor, after stirring, be warming up to 75 ℃; Behind temperature-stable, beginning evenly drip monomer mixture (by the butyl acrylate of 235g, 200g vinyl acetate, the large monomer of Polymerizable Polyurethane of 50g, the Hydroxyethyl acrylate of 15g evenly mix) and initiator solution (evenly being mixed by the Diisopropyl azodicarboxylate of 2.5g, the vinyl acetic monomer of 150g); The time for adding of monomer mixture and initiator solution is 3 hours, and keeping temperature during the dropping is 75 ℃; After dropwising, keep 75 ℃ of temperature, continue to stir 4 hours, then cooling adds the dilution of 100g dehydrated alcohol simultaneously; After being down to room temperature, packing, namely making solid content is the alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymer of 50wt%.
The ethanol and the water that water content are not higher than 5wt% are made mixed solvent in 9: 1 ratio; 50 gram alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymers and 220 gram alcohol-soluble and water-soluble acrylate copolymers, 80 gram alcohol-soluble and water-soluble urethane resins and 350 gram Rutile type Titanium Dioxides, 20 gram BYK-191 dispersion agents, 10 gram polyketone resins, 1.0 gram High molecular weight polyethylene wax powder and the 350 gram mixed solvents of above-mentioned technological process preparation are added blender loader, stirred 30 minutes with high speed dispersor, it is mixed; The material that mixes is taken out, send into sand mill and carry out sand milling, be lower than 10 microns until fineness and take out afterwards, filter; Through after the assay was approved, packing namely makes the compound white ink of single-fluid general plastic intaglio plate alcohol water-based.
Embodiment two
The preparation of the compound Yellow ink of single-fluid general plastic intaglio plate alcohol water-based
The instruments such as 500ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To the different Buddhist diketone vulcabond (IPDI) with adding 95.8g in the 500ml four-necked bottle of agitator, thermometer, be heated to 60 ℃ under stirring, add the dibutyl tin laurate of 0.06g, mix 15 minutes, then drip the 50.0g Hydroxyethyl acrylate.It is 400 polyester diol that 60 ℃ of reactions add the 172.4g molecular weight after 1 hour again, and 60 ℃ are continued reaction 2 hours.Then be cooled to 30 ℃, discharging namely makes the large monomer of Polymerizable Polyurethane.
Benzoyl peroxide, 100g vinyl acetic monomer and the 60g dehydrated alcohol of 2.0g are added reactor, after stirring, be warming up to 80 ℃; Behind temperature-stable, beginning evenly drip monomer mixture (by the ethyl propenoate of 240g, 144g vinyl acetate, the large monomer of Polymerizable Polyurethane of 52g, the acrylamide of 24g evenly mix) and initiator solution (evenly being mixed by the benzoyl peroxide of 2.0g, the vinyl acetic monomer of 64g); The time for adding of monomer mixture and initiator solution is 4 hours, and keeping temperature during the dropping is 80 ℃; After dropwising, keep 80 ℃ of temperature, continue to stir 4 hours, then cooling adds the dilution of 235g dehydrated alcohol simultaneously; After being down to room temperature, packing, namely making solid content is the alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymer of 50wt%.
The ethanol and the water that water content are not higher than 5wt% are made mixed solvent in 9: 1 ratio; 80 gram alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymers and 200 gram alcohol-soluble and water-soluble acrylate copolymers, 70 gram alcohol-soluble and water-soluble urethane resins and 50 gram benzidine yellow Gs, 30 gram benzidine yellow 10Gs, 20 gram CA-600 dispersion agents, 15 gram polyketone resins, 1.0 gram High molecular weight polyethylene wax powder and the 500 gram mixed solvents of above-mentioned technological process preparation are added blender loader, stirred 30 minutes with high speed dispersor, it is mixed; The material that mixes is taken out, send into sand mill and carry out sand milling, be lower than 10 microns until fineness and take out afterwards, filter; Through after the assay was approved, packing namely makes the compound Yellow ink of single-fluid general plastic intaglio plate alcohol water-based.
Embodiment three
The preparation of the compound red ink of single-fluid general plastic intaglio plate alcohol water-based
The instruments such as 500ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To the different Buddhist diketone vulcabond (IPDI) with adding 85.5g in the 500ml four-necked bottle of agitator, thermometer, be heated to 50 ℃ under stirring, add the dibutyl tin laurate of 0.08g, mix 10 minutes, then drip the 50.0g Propylene glycol monoacrylate.It is 600 polyester diol that 50 ℃ of reactions add the 230.8g molecular weight after 1 hour again, and 50 ℃ are continued reaction 45 hours.Then be cooled to 30 ℃, discharging namely makes the large monomer of Polymerizable Polyurethane.
Diisopropyl azodicarboxylate, 100g vinyl acetic monomer and the 50g dehydrated alcohol of 1.2g are added reactor, after stirring, be warming up to 80 ℃; Behind temperature-stable, beginning evenly drip monomer mixture (by the butyl acrylate of 120g, 200g vinyl acetate, the large monomer of Polymerizable Polyurethane of 60g, the vinylformic acid of 20g evenly mix) and initiator solution (evenly being mixed by the Diisopropyl azodicarboxylate of 1.2g, the vinyl acetic monomer of 130g); The time for adding of monomer mixture and initiator solution is 4 hours, and keeping temperature during the dropping is 80 ℃; After dropwising, keep 80 ℃ of temperature, continue to stir 3 hours, then cooling adds the dilution of 120g dehydrated alcohol simultaneously; After being down to room temperature, packing, namely making solid content is the alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymer of 50wt%.
The ethanol and the water that water content are not higher than 5wt% are made mixed solvent in 9: 1 ratio; 50 gram alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymers and dark red 243, the 20 gram CA-600 dispersion agents of 290 gram alcohol-soluble and water-soluble acrylate copolymers, 60 gram alcohol-soluble and water-soluble urethane resins and 80 Ke Lisuoer, 10 gram polyketone resins, 1.0 gram High molecular weight polyethylene wax powder and the 500 gram mixed solvents of above-mentioned technological process preparation are added blender loader, stirred 30 minutes with high speed dispersor, it is mixed; The material that mixes is taken out, send into sand mill and carry out sand milling, be lower than 10 microns until fineness and take out afterwards, filter; Through after the assay was approved, packing namely makes the compound red ink of single-fluid general plastic intaglio plate alcohol water-based.
Embodiment four
The preparation of single-fluid general plastic intaglio plate alcohol water-based compound blue printing ink
The instruments such as 500ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To the different Buddhist diketone vulcabond (IPDI) with adding 76.64g in the 500ml four-necked bottle of agitator, thermometer, be heated to 60 ℃ under stirring, add the dibutyl tin laurate of 0.08g, mix 20 minutes, then drip the 40.0g Hydroxyethyl acrylate.It is 600 polyester diol that 60 ℃ of reactions add the 206.8g molecular weight after 2 hours again, and 60 ℃ are continued reaction 3 hours.Then be cooled to 30 ℃, discharging namely makes the large monomer of Polymerizable Polyurethane.
Diisopropyl azodicarboxylate, 150g vinyl acetic monomer and the 100g dehydrated alcohol of 1.75g are added reactor, after stirring, be warming up to 75 ℃; Behind temperature-stable, beginning evenly drip monomer mixture (by the butyl acrylate of 205g, 200g vinyl acetate, the large monomer of Polymerizable Polyurethane of 70g, the Propylene glycol monoacrylate of 25g evenly mix) and initiator solution (evenly being mixed by the Diisopropyl azodicarboxylate of 1.75g, the vinyl acetic monomer of 150g); The time for adding of monomer mixture and initiator solution is 4 hours, and keeping temperature during the dropping is 75 ℃; After dropwising, keep 75 ℃ of temperature, continue to stir 5 hours, then cooling adds the dilution of 100g dehydrated alcohol simultaneously; After being down to room temperature, packing, namely making solid content is the alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymer of 50wt%.
The ethanol and the water that water content are not higher than 5wt% are made mixed solvent in 9: 1 ratio; With 40 gram alcohol-soluble and water-soluble polyurethane grafting polyacrylic acid ester copolymers of above-mentioned technological process preparation and 280 gram alcohol-soluble and water-soluble acrylate copolymers, 30 gram alcohol-soluble and water-soluble urethane resins and the 80 gram phthalein mountain valley with clumps of trees and bamboos are blue, 20 gram CA-600 dispersion agents, 10 gram polyketone resins, 1.0 gram High molecular weight polyethylene wax powder and 500 gram mixed solvents add blender loaders, stirred 30 minutes with high speed dispersor, it is mixed; The material that mixes is taken out, send into sand mill and carry out sand milling, be lower than 10 microns until fineness and take out afterwards, filter; Through after the assay was approved, packing namely makes single-fluid general plastic intaglio plate alcohol water-based compound blue printing ink.
The key technical indexes of the single-fluid general plastic intaglio plate alcohol aqueous composite ink that makes is as shown in the table:
| Test item | National standard | Detected value | The result |
| Fineness (μ m) (scraper plate instrument) | ≤25 | ≤10 | Qualified |
| Tinting strength (%) | 95～110 | 98～105 | Qualified |
| Viscosity (s) (4# cup/25 ℃) | 25～70 | 28～50 | Qualified |
| Just do (mm) (30s/25 ℃) | 25～50 | 28～38 | Qualified |
| Attachment fastness (%) (adhesive tape method) | ≥85 | 93～98 | Qualified |
| Benzene content (ppm) | / | Nothing | Qualified |
Above detected result is according to the QB/T2024-1994 standard testing.
Claims (1)
1. single-fluid general plastic gravure alcohol-soluble and water-soluble composite China ink, it is characterized in that: this Water Soluble Compound printing ink is to be raw material by (methyl) acrylate, vinyl acetate, the large monomer of Polymerizable Polyurethane and active function monomer, the polyurethane grafting polyacrylic acid ester copolymer and alcohol-soluble and water-soluble acrylate copolymer, alcohol-soluble and water-soluble urethane resin, organic/inorganic pigment, dispersion agent, adhesion promoter, polyethylene wax and the mixed solvent that get by solution free radical polymerization form, and the weight proportion of each component is:
Polyurethane grafting polyacrylic acid ester copolymer 2～10
Alcohol-soluble and water-soluble acrylate copolymer 15～30
Alcohol-soluble and water-soluble urethane resin 2～10
Organic/inorganic pigment 6～35
Dispersion agent 0.5～3
Adhesion promoter 0.5～3
Polyethylene wax 0.1～0.5
Mixed solvent 30～60
Wherein the specific preparation method of polyurethane grafting polyacrylic acid ester copolymer is:
1) first vulcabond is added, be warmed up to 30～80 ℃, the adding monomer weighs the oil-soluble catalyst of 0.01～0.2wt%, after mixing 10～30 minutes, add hydroxy acrylate, reacted 1～4 hour, then add polyester diol, at 30～80 ℃, continue reaction 2～5 hours, cooling namely gets the large monomer of Polymerizable Polyurethane;
2) initiator and the 50wt% solvent with 50wt% adds reactor, after stirring, is warming up to 50～85 ℃; Behind temperature-stable, (methyl) acrylate, vinyl acetate, active function monomer, the large monomer of Polymerizable Polyurethane are mixed, in 3～8 hours, evenly be added dropwise to reactor, drip simultaneously the initiator solution that initiator and 30wt% solvent by 50wt% form; After dropwising, keep 50～85 ℃ of temperature, continue to stir 2～5 hours, then cooling adds the residual solvent dilution; After being down to room temperature, packing namely makes the polyurethane grafting polyacrylic acid ester copolymer;
Wherein each weight proportion that forms is:
(methyl) acrylate 10～80
Vinyl acetate 10～80
The large monomer 5～40 of Polymerizable Polyurethane
Active function monomer 2～8
Initiator 0.1～2.0
Solvent 50～500
And the specific preparation technology of single-fluid general plastic gravure alcohol-soluble and water-soluble composite China ink is:
1) ethanol and the water that water content are not higher than 5 wt% are made mixed solvent in the ratio of 9:1～2:1;
2) polyurethane grafting polyacrylic acid ester copolymer, alcohol-soluble and water-soluble acrylate copolymer, alcohol-soluble and water-soluble urethane resin and pigment, dispersion agent, adhesion promoter, wax powder and mixed solvent are added blender loader, stirred 20～30 minutes with high speed dispersor, it is mixed;
3) material that mixes is taken out, send into sand mill and carry out sand milling, be lower than 10 microns until fineness and take out afterwards, filter; Through after the assay was approved, packing namely makes the single-fluid general plastic gravure alcohol-soluble and water-soluble composite China ink;
Described active function monomer is vinylformic acid, acrylamide, methacrylic acid, maleic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, glycidyl acrylate, hydroxyethyl methylacrylate, Rocryl 410, the mixture of one or more above compositions.
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| CN102010485B (en) * | 2010-06-03 | 2012-08-01 | 成都市新津托展油墨有限公司 | Preparation method of integrated plastic gravure alcohol-soluble aqueous composite ink resin |
| CN103725086A (en) * | 2014-01-15 | 2014-04-16 | 云南侨通包装印刷有限公司 | High-performance water-based golden ink for gravure printing and preparation method thereof |
| CN106280701A (en) * | 2016-08-08 | 2017-01-04 | 惠州市至上新材料有限公司 | A kind of aqueous, environmental protective sand streak gravure ink |
| CN108047387B (en) * | 2017-12-29 | 2019-10-29 | 天津华彩顺成装饰材料有限公司 | Modified polyamide resin and preparation method thereof and water-based ink comprising the modified polyamide resin |
| CN108641468A (en) * | 2018-07-23 | 2018-10-12 | 张家港市汇鼎新材料科技有限公司 | A kind of formula of alcohol aqueous composite ink |
| CN113025113A (en) * | 2019-12-25 | 2021-06-25 | 广东德康化工实业有限公司 | Treatment-free PE film aqueous gravure ink and preparation method thereof |
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| CN1970657A (en) * | 2005-09-16 | 2007-05-30 | 三菱麻铁里亚尔株式会社 | Printing oil ink and production method of coating film using the oil ink |
| CN101205275A (en) * | 2006-12-18 | 2008-06-25 | 钟文军 | Alcohol water-soluble resin and method for making same |
| CN101230220A (en) * | 2007-12-26 | 2008-07-30 | 宁波工程学院 | Emulsion bridging agent for aqueous ink and preparation method thereof |
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| US9234068B2 (en) * | 2007-10-02 | 2016-01-12 | The Hong Kong University of Science and Technologhy | Method for preparing aqueous polyacrylate modified polyurethane dispersions |
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| CN101205275A (en) * | 2006-12-18 | 2008-06-25 | 钟文军 | Alcohol water-soluble resin and method for making same |
| CN101230220A (en) * | 2007-12-26 | 2008-07-30 | 宁波工程学院 | Emulsion bridging agent for aqueous ink and preparation method thereof |
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