CN108624216B - Water-based laser aluminizing transfer coating and preparation method thereof - Google Patents
Water-based laser aluminizing transfer coating and preparation method thereof Download PDFInfo
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- CN108624216B CN108624216B CN201810569463.8A CN201810569463A CN108624216B CN 108624216 B CN108624216 B CN 108624216B CN 201810569463 A CN201810569463 A CN 201810569463A CN 108624216 B CN108624216 B CN 108624216B
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- 238000000576 coating method Methods 0.000 title claims abstract description 92
- 239000011248 coating agent Substances 0.000 title claims abstract description 87
- 238000012546 transfer Methods 0.000 title claims abstract description 83
- 238000005269 aluminizing Methods 0.000 title claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 239000006184 cosolvent Substances 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 30
- -1 aminopropyl Chemical group 0.000 claims description 29
- 239000013530 defoamer Substances 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000005375 organosiloxane group Chemical group 0.000 claims description 13
- 238000007747 plating Methods 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002216 antistatic agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
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- 239000002904 solvent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004203 carnauba wax Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 230000003678 scratch resistant effect Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 abstract description 13
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- 230000000694 effects Effects 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 6
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- 230000000052 comparative effect Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000123 paper Substances 0.000 description 5
- 238000010017 direct printing Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 230000036541 health Effects 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 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 2
- 238000012856 packing Methods 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000007774 anilox coating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
Abstract
In order to solve the problems that the existing aqueous laser aluminizing transfer coating has poor plate adhesion, poor release capacity and insufficient adhesive force with UV ink and needs varnish before printing, the invention provides an aqueous laser aluminizing transfer coating which comprises the following components: waterborne polyurethane, cosolvent, water, defoaming agent and leveling agent; the preparation raw materials of the waterborne polyurethane comprise polyol and polyisocyanate, wherein the Tg point of the polyol is between (-80 ℃ to-20 ℃); in the aqueous polyurethane, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups is between 1.1 and 1.5. Meanwhile, the invention also discloses a preparation method of the water-based laser aluminizing transfer coating. The water-based laser aluminizing transfer coating provided by the invention has the advantages of good process adaptability, good aluminizing brightness, excellent color fastness to aluminum, good mould pressing effect, capability of directly carrying out offset printing and good adhesive force with ink.
Description
Technical Field
The invention belongs to the technical field of water-based transfer coatings, and particularly relates to a water-based laser aluminizing transfer coating and a preparation method thereof.
Background
At present, in the domestic packaging industry, the aluminum foil compounding process is slowly replaced by a transfer aluminum plating process due to difficult recycling, great environmental pollution and great resource loss. The transfer aluminum plating process is to coat transfer paint on a PET transfer film, stick the PET transfer film and paper together by composite glue after aluminum plating, and finally strip off the PET transfer film to prepare the transfer aluminum plated paper. The transfer aluminum plating paper is easy to degrade, convenient to recover and environment-friendly, and a carrier PET film can be repeatedly utilized, so that the transfer aluminum plating process is popular, wherein the transfer aluminum plating process is divided into a light silver transfer aluminum plating process and a laser transfer aluminum plating process.
The laser aluminizing transfer process is to coat a laser transfer layer on a PET transfer film through an anilox roller to prepare a pre-coating film; then, carrying out laser mould pressing on the pre-coating film at high temperature and high pressure, and repeatedly engraving interference fringes on a laser plate on the pre-coating film to form a laser information layer to prepare a mould pressing film; and aluminizing the molded film to form an aluminum layer on the information layer, thereby preparing the PET laser aluminizing transfer film. The finished product has exquisite appearance, clear pattern and excellent anti-counterfeiting effect.
The laser aluminizing transfer coating on the market at present generally adopts solvent-type polyacrylic resin, cellulose resin, nitrocotton resin, a large amount of organic solvents such as ketones, esters and benzenes, and in the production process, a large amount of organic solvents volatilize, so that on one hand, serious atmospheric pollution is caused to the surrounding environment, on the other hand, serious harm is caused to the body health of field production workers, and on the other hand, the organic solvents are all flammable and explosive products, obvious potential safety hazards exist in the construction and storage processes, fire accidents are easily caused, and the loss caused by safety problems reaches hundreds of millions every year. Along with the soundness of national environmental laws and regulations, law enforcement departments have increasingly greater punishment on illegal environmental pollution, VOCs emission tax is superimposed, and the production cost of solvent-based coatings is higher and higher, so that the research focus at present is gradually focused on water-based coatings, and the water-based coatings have obvious environmental protection advantages because the water-based coatings are mainly dispersed in water, and are superior to oil-based release materials in the aspects of physical health of field operators in the use process, storage safety, production emission and the like
The existing water-based laser aluminizing transfer coating on the market has a plurality of defects, such as insufficient laser brightness, poor plate adhesion, insufficient mould pressing pressure resistance, unclean release from a PET film and the like. In some cases, UV ink needs to be applied to the surface of the water-based laser aluminizing transfer coating after the PET film is separated, and the existing water-based laser aluminizing transfer coating has insufficient adhesive force with the UV ink and needs to be coated with varnish before printing.
Disclosure of Invention
The invention provides a water-based laser aluminizing transfer coating, aiming at the problems that the existing water-based laser aluminizing transfer coating is poor in plate adhesion, poor in release capacity, insufficient in adhesion with UV ink and required to be coated with a varnish before printing.
The technical scheme adopted by the invention for solving the technical problems is as follows:
on one hand, the invention provides a water-based laser aluminizing transfer coating, which comprises the following components:
waterborne polyurethane, cosolvent, water, defoaming agent and leveling agent;
the preparation raw materials of the waterborne polyurethane comprise polyol and polyisocyanate, wherein the Tg point of the polyol is between-80 ℃ and-20 ℃;
in the aqueous polyurethane, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups is between 1.1 and 1.5.
According to the water-based laser aluminizing transfer coating provided by the invention, the adhesion between the UV ink and a coating formed by the water-based laser aluminizing transfer coating can be effectively improved by selecting the polyol with the Tg point in the range of-80 ℃ to-20 ℃ and simultaneously controlling the ratio of the mole number of the isocyanate group to the mole number of the hydroxyl group to be in a lower level, at the moment, the soft segment in the water-based polyurethane has a higher proportion, and a prepress varnish does not need to be additionally coated on the coating formed by the water-based laser aluminizing transfer coating, so that the direct printing effect of the UV ink is realized. Meanwhile, the water-based laser aluminizing transfer coating provided by the invention has good release property with PET, good mould pressing pressure resistance, mould pressing temperature range of 150-180 ℃, clear mould pressing patterns and wide application in packing paper of cigarettes, cosmetics, wine boxes and the like.
Optionally, the aqueous laser aluminizing transfer coating comprises the following components in parts by mass: 40-60 parts of waterborne polyurethane, 5-15 parts of cosolvent, 25-40 parts of water, 0.05-0.2 part of defoaming agent and 0.1-0.5 part of flatting agent.
Optionally, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups in the aqueous polyurethane is between 1.1 and 1.25.
Optionally, the preparation raw material of the waterborne polyurethane further comprises an aminopropyl polysiloxane monomer, and the mass fraction of the aminopropyl polysiloxane monomer is 0.5-2% based on 100% of the mass of the waterborne polyurethane.
Optionally, the softening point of the waterborne polyurethane is 120-170 ℃, and the average particle size is less than or equal to 150 nm.
Optionally, the cosolvent comprises one or more of ethanol, isopropanol, n-butanol, propylene glycol monomethyl ether, dimethylformamide and dimethylacetamide.
Optionally, the defoamer comprises one or more of a mineral oil defoamer, a polyether defoamer, an organosiloxane defoamer and a polyether modified organosiloxane defoamer.
Optionally, the leveling agent includes one or more of a polyether-modified organosiloxane, a fluorine-modified siloxane leveling agent, a polyester-modified organosiloxane, an acrylic leveling agent, and a polyether-modified organosiloxane leveling agent.
Optionally, the aqueous laser aluminizing transfer coating further comprises the following components in parts by mass:
0.1-0.5 part of other auxiliary agents;
the other auxiliary agents comprise one or more of thickening agents, dispersing agents, rheological agents, hand feeling agents, scratch and abrasion resistant agents and antistatic agents.
Optionally, the thickener comprises one or more of polyurethane thickener, polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone;
the dispersing agent comprises one or more of polyvinyl alcohol and derivatives thereof, polymethacrylate and polyacrylate;
the rheological agent comprises one or more of waterborne polyurethane rheological agent, polyether rheological agent and polyamide rheological agent;
the hand feeling agent comprises one or more of polyether modified organic siloxane, polyester modified organic siloxane and alkyl modified organic siloxane;
the scratch-resistant and wear-resistant agent comprises one or more of high-density polyethylene wax, polypropylene wax, fluorine modified polyolefin, palm wax, polytetrafluoroethylene wax and polydimethylsiloxane;
the antistatic agent comprises an alkyl sodium sulfonate antistatic agent.
In another aspect, the invention provides a preparation method of the aqueous laser aluminizing transfer coating, which comprises the following steps:
preparation of a prepolymer: dehydrating the polyhydric alcohol with the Tg point of-80 to-20 ℃ in vacuum for 1 to 2 hours at the temperature of 110 to 120 ℃ to ensure that the water content is lower than 0.5 percent; adding polyisocyanate and a catalyst at 50-60 ℃, and reacting for 2-3 h at 70-90 ℃ to obtain a prepolymer;
chain extension: cooling the prepolymer to 40-60 ℃, slowly adding a hydrophilic chain extender, then heating to 80-90 ℃ to react for 2-4 h, and sampling to determine the molar content of NCO in the system; when the ratio of the mole number of the isocyanate group to the mole number of the hydroxyl group in the waterborne polyurethane is 1.1-1.5, adding a solvent to adjust the viscosity of the prepolymer to obtain a polymer;
neutralization and emulsification: controlling the temperature of the polymer at 20-60 ℃, adding a neutralizing agent to form salt, stirring, adding water to adjust the solid content to 25-40%, and dispersing at a high speed to obtain waterborne polyurethane;
and mixing the waterborne polyurethane, the cosolvent, water, the defoaming agent and the flatting agent to obtain the waterborne laser aluminizing transfer coating.
Optionally, the step of mixing the waterborne polyurethane, the cosolvent, the water, the defoaming agent and the leveling agent to obtain the waterborne laser aluminizing transfer coating comprises the following steps:
putting the cosolvent and the leveling agent into a reaction kettle, blending and uniformly stirring to obtain a mixture A;
adding water into the reaction kettle under the stirring state to obtain a mixture B;
slowly adding waterborne polyurethane into a reaction kettle under a stirring state to obtain a mixture C;
and adding a defoaming agent under a stirring state, uniformly stirring, and filtering to obtain the aqueous laser aluminizing transfer coating.
Optionally, aminopropylpolysiloxane monomers are added to synthesize polyurethane segments with siloxane groups prior to polymer neutralization.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention discloses a water-based laser aluminizing transfer coating, which comprises the following components:
waterborne polyurethane, cosolvent, water, defoaming agent and leveling agent;
the preparation raw materials of the waterborne polyurethane comprise polyol and polyisocyanate, wherein the Tg point of the polyol is between-80 ℃ and-20 ℃;
in the aqueous polyurethane, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups is between 1.1 and 1.5.
According to the water-based laser aluminizing transfer coating, the polyol with the Tg point (glass transition temperature) in the range of-80 ℃ to-20 ℃ is selected, and the ratio of the mole number of the isocyanate group to the mole number of the hydroxyl group is controlled at a lower level, so that the soft segment in the water-based polyurethane has a higher proportion, the adhesive force between the UV ink and a coating formed by the water-based laser aluminizing transfer coating can be effectively improved, a prepress varnish does not need to be additionally coated on the coating formed by the water-based laser aluminizing transfer coating, and the direct printing effect of the UV ink is realized. Meanwhile, the water-based laser aluminizing transfer coating provided by the invention has good parting property with PET (polyethylene terephthalate), good mould pressing pressure resistance, mould pressing temperature range of 150-180 ℃, and can be widely applied to packing paper of cigarettes, cosmetics, wine boxes and the like.
In some embodiments, the aqueous laser aluminizing transfer coating comprises the following components by mass: 40-60 parts of waterborne polyurethane, 5-15 parts of cosolvent, 25-40 parts of water, 0.05-0.2 part of defoaming agent and 0.1-0.5 part of flatting agent.
The lower the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups in the aqueous polyurethane, the higher the soft segment proportion, the more favorable the UV direct printing effect, in a more preferred embodiment, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups in the aqueous polyurethane is between 1.1 and 1.25.
In some embodiments, the preparation raw material of the aqueous polyurethane further comprises an aminopropyl polysiloxane monomer, and the mass fraction of the aminopropyl polysiloxane monomer is 0.5-2% based on 100% of the mass of the aqueous polyurethane.
The aminopropyl polysiloxane monomer can react with the waterborne polyurethane for grafting, a polyurethane chain segment containing siloxane groups is formed on the waterborne polyurethane, and the adhesive force between the waterborne laser aluminizing transfer coating and the UV printing ink is improved to a certain extent.
In some embodiments, the softening point of the aqueous polyurethane is 120 ℃ to 170 ℃ and the average particle size is less than or equal to 150 nm.
The cosolvent is used for improving the solubility and dispersity of insoluble substances in the aqueous laser aluminizing transfer coating, and is beneficial to improving the solid content of the coating.
In some embodiments, the co-solvent comprises one or more of ethanol, isopropanol, n-butanol, propylene glycol monomethyl ether, dimethylformamide, and dimethylacetamide.
The defoaming agent is used for reducing bubbles generated in the preparation process or the surface application process of the aqueous laser aluminizing transfer coating, and preventing the surface of the coating from being uneven.
In some embodiments, the defoamer comprises one or more of a mineral oil type defoamer, a polyether type defoamer, an organosiloxane type defoamer, and a polyether modified organosiloxane type defoamer.
The leveling agent is used for improving the leveling performance of the aqueous laser aluminizing transfer coating.
In some embodiments, the leveling agent includes one or more of a polyether modified organosiloxane, a fluorine modified siloxane leveling agent, a polyester modified organosiloxane, an acrylic leveling agent, and a polyether modified organosiloxane-based leveling agent.
In some embodiments, the aqueous laser aluminizing transfer coating further comprises the following mass components:
0.1-0.5 part of other auxiliary agents;
the other auxiliary agents comprise one or more of thickening agents, dispersing agents, rheological agents, hand feeling agents, scratch and abrasion resistant agents and antistatic agents.
Specifically, the thickener comprises one or more of polyurethane thickener, polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone.
The dispersing agent comprises one or more of polyvinyl alcohol and derivatives thereof, polymethacrylate and polyacrylate.
The rheological agent comprises one or more of waterborne polyurethane rheological agents, polyether rheological agents and polyamide rheological agents.
The hand feeling agent comprises one or more of polyether modified organic siloxane, polyester modified organic siloxane and alkyl modified organic siloxane.
The scratch and wear resistant agent comprises one or more of high density polyethylene wax, polypropylene wax, fluorine modified polyolefin, palm wax, polytetrafluoroethylene wax and polydimethylsiloxane.
The antistatic agent comprises an alkyl sodium sulfonate antistatic agent.
In another embodiment, the invention provides a preparation method of the aqueous laser aluminum plating transfer coating, which comprises the following steps:
preparation of a prepolymer: dehydrating the polyhydric alcohol with the Tg point of-80 to-20 ℃ in vacuum for 1 to 2 hours at the temperature of 110 to 120 ℃ to ensure that the water content is lower than 0.5 percent; adding polyisocyanate and a catalyst at 50-60 ℃, and reacting for 2-3 h at 70-90 ℃ to obtain a prepolymer;
chain extension: cooling the prepolymer to 40-60 ℃, slowly adding a hydrophilic chain extender, then heating to 80-90 ℃ to react for 2-4 h, and sampling to determine the molar content of NCO in the system; when the ratio of the mole number of the isocyanate group to the mole number of the hydroxyl group in the waterborne polyurethane is 1.1-1.5, adding a solvent to adjust the viscosity of the prepolymer to obtain a polymer;
neutralization and emulsification: controlling the temperature of the polymer at 20-60 ℃, adding a neutralizing agent to form salt, stirring, adding water to adjust the solid content to 25-40%, and dispersing at high speed for 20-30 minutes to obtain waterborne polyurethane;
and mixing the waterborne polyurethane, the cosolvent, water, the defoaming agent and the flatting agent to obtain the waterborne laser aluminizing transfer coating.
In some embodiments, the "mixing the aqueous polyurethane, the cosolvent, the water, the defoamer, and the leveling agent to obtain the aqueous laser aluminum plating transfer coating" includes:
putting the cosolvent and the leveling agent into a reaction kettle, blending and uniformly stirring to obtain a mixture A;
adding water into the reaction kettle under the stirring state to obtain a mixture B;
slowly adding waterborne polyurethane into a reaction kettle under a stirring state to obtain a mixture C;
and adding a defoaming agent under a stirring state, uniformly stirring, and filtering to obtain the aqueous laser aluminizing transfer coating.
The stirring speed in the stirring state is 400-800 revolutions per minute.
In some embodiments, the aminopropylpolysiloxane-based monomer is added to synthesize a polyurethane segment with siloxane groups prior to neutralization of the polymer.
The present invention will be further illustrated by the following examples.
Example 1
The embodiment is used for explaining the aqueous laser aluminizing transfer coating and the preparation method thereof, and the preparation method comprises the following steps:
carrying out vacuum dehydration on 0.05mol of polyethylene glycol adipate diol (Tg is-50 ℃) at 110 ℃ to ensure that the water content is lower than 0.5%, adding 0.39mol of isophorone diisocyanate (IPDI) and 0.0001mol of di-n-butyltin dilaurate at 60 ℃, heating to 80 ℃ and reacting for 2 hours to obtain a polyurethane prepolymer; and cooling to 50 ℃, slowly adding 0.05mol of Trihydroxy Methyl Propane (TMP) and 0.2mol of diethylene glycol, heating, continuously reacting at 70 ℃ for 3 hours, sampling and measuring an NCO value (molar weight), wherein the NCO value is close to a design value R which is the ratio of the molar number of total NCO groups in the system to the molar number of total OH groups in the system to be 1.2, reducing the temperature, and adding a small amount of acetone to adjust the viscosity of the prepolymer to obtain the polyurethane polymer. Cooling to 20 ℃, adding a neutralizing agent triethylamine to neutralize and form salt, adding a proper amount of deionized water under the condition of high-speed stirring, adjusting the solid content to be 30%, and then removing acetone through reduced pressure distillation to obtain the waterborne polyurethane emulsion.
The raw materials of the components and the contents (parts by weight) of example 1 in table 1 were prepared.
And (3) mixing the water-insoluble components, the flatting agent and the cosolvent in the other auxiliaries in a reaction kettle, stirring at a low speed for 5-10min, and controlling the stirring speed to be 200-300 rpm.
The stirring speed is increased to 400-600rpm, and deionized water is added into the reaction kettle under the stirring state for 5 min.
And increasing the stirring speed to 600-800rpm, adding the aqueous polyurethane emulsion into the reaction kettle in a stirring state, and stirring for 5 min.
And (4) keeping the stirring speed, adding the defoaming agent into the reaction kettle in a stirring state, and stirring for 10 min.
Filtering by using a 200-mesh and 300-mesh filter screen to obtain the aqueous laser aluminizing transfer coating.
Example 2
This embodiment is used to illustrate a water-based laser aluminizing transfer coating and a preparation method thereof disclosed by the present invention, including the steps as in embodiment 1, except that:
adding 0.5-2% of aminopropyl polysiloxane monomer by mass percent before the polyurethane polymer is neutralized to synthesize a polyurethane chain segment with siloxane groups.
The raw materials of the components and the contents (parts by weight) of example 2 in Table 1 are adopted for material preparation.
Example 3
This embodiment is used to illustrate a water-based laser aluminizing transfer coating and a preparation method thereof disclosed by the present invention, including the steps as in embodiment 1, except that:
the raw materials of the components and the contents (parts by weight) of example 3 in Table 1 are adopted for material preparation.
Comparative example 1
The comparative example is used for comparative illustration of the aqueous laser aluminizing transfer coating and the preparation method thereof disclosed by the invention, and comprises the steps as in example 1, and the difference is that:
dehydrating 0.05mol of a polybenzoate polyol (Tg of-10 ℃) in vacuum at 120 ℃ to ensure that the water content is lower than 0.5%, adding 1.5mol of isophorone diisocyanate and 0.0001mol of di-n-butyltin dilaurate at 65 ℃, and heating to 80 ℃ to react for 2 hours to obtain a polyurethane prepolymer; and cooling to 50 ℃, adding 0.05mol of Trihydroxy Methyl Propane (TMP) and 0.2mol of 1, 4-butanediol, heating, continuing to react at 70 ℃ for 2 hours, sampling and measuring an NCO value (molar weight), wherein R is the ratio of the number of moles of total NCO groups in the system to the number of moles of total OH groups in the system after the NCO value is close to a design value R of 2.3, reducing the temperature, and adding a small amount of acetone to adjust the viscosity of the prepolymer to obtain the polyurethane polymer. Cooling to 20 ℃, adding a neutralizing agent triethylamine to neutralize and form salt, adding a proper amount of deionized water under the condition of high-speed stirring, adjusting the solid content to 25%, and then removing acetone through reduced pressure distillation to obtain the waterborne polyurethane emulsion.
The raw materials of the components and the content (parts by weight) of the comparative example 1 in the table 1 are prepared.
Comparative example 2
This comparative example provides a commercially available solvent-based laser transfer coating.
Performance testing
The following performance tests were performed on the aqueous laser aluminum plating transfer coating prepared in the above examples 1 to 3 and the laser aluminum plating transfer coating provided in the comparative examples 1 and 2:
the method for testing the performance index of the product comprises the following steps:
(1) the coating effect test method comprises the following steps: the leveling effect was tested on a coater using a 200 mesh ceramic roller.
(2) Peel force test method: the test was carried out on a tape peel force tester PT-501C.
(3) The coating plate sticking performance test method comprises the following steps: and (3) coating a laser layer on the PET film, carrying out high-temperature plate leaning test on a small-sized molding press, and observing the plate sticking degree of the coating.
(4) The coating pressure resistance test method comprises the following steps: and (3) coating a laser layer on the PET film, carrying out long-time mould pressing on a small mould pressing machine, and observing the brightness change degree of the mould pressing of the coating.
(5) The testing method of the residual VOCs of the solvent comprises the following steps: and (4) counting the residual quantity of various solvents on the coating film by using a headspace gas chromatograph.
(6) The placing stability test method comprises the following steps: after 150g of the paint sample was placed in a 50 ℃ oven for 15 days, the presence of bleeding or viscosity increase was observed.
(7) The adhesion test method of the transferred coating and offset UV ink comprises the following steps: after aluminizing the laser coating, compounding the laser coating on the paperboard through glue, removing the PET film, printing UV ink on the release layer through a small offset press, fully curing, drawing hundreds of grids, and testing the proportion of the ink removed by glue through a 3M adhesive tape.
The test results obtained are filled in Table 1.
TABLE 1
The test results of the comparative examples 1-3 and the comparative examples 1 and 2 show that the aqueous laser aluminizing transfer coating prepared by the technical scheme provided by the invention completely conforms to the catalogue of materials allowed for tobacco in terms of VOCs (volatile organic chemicals), has good coating leveling property and stripping property, has good mould pressing effect and excellent pressure resistance, has good matching property for offset printing, has good adhesive force with UV (ultraviolet) curing ink, can really realize direct printing, and is an ideal environment-friendly substitute for the existing solvent-based laser transfer coating.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (13)
1. The water-based laser aluminizing transfer coating is characterized by comprising the following components:
waterborne polyurethane, cosolvent, water, defoaming agent and leveling agent;
the preparation raw materials of the waterborne polyurethane comprise polyol and polyisocyanate, wherein the Tg point of the polyol is between-80 ℃ and-20 ℃;
in the aqueous polyurethane, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups is between 1.1 and 1.5.
2. The aqueous laser aluminizing transfer coating of claim 1, wherein the aqueous laser aluminizing transfer coating comprises the following components by mass: 40-60 parts of waterborne polyurethane, 5-15 parts of cosolvent, 25-40 parts of water, 0.05-0.2 part of defoaming agent and 0.1-0.5 part of flatting agent.
3. The aqueous laser aluminizing transfer coating according to claim 1, wherein a ratio of a mole number of isocyanate groups to a mole number of hydroxyl groups in the aqueous polyurethane is between 1.1 and 1.25.
4. The aqueous laser aluminizing transfer coating according to claim 1, wherein the raw material for preparing the aqueous polyurethane further includes an aminopropyl polysiloxane monomer, and the mass fraction of the aminopropyl polysiloxane monomer is 0.5-2% based on 100% by mass of the aqueous polyurethane.
5. The aqueous laser aluminizing transfer coating of claim 1, wherein the softening point of the aqueous polyurethane is 120-170 ℃ and the average particle size is less than or equal to 150 nm.
6. The aqueous laser aluminizing transfer coating of claim 1, wherein the cosolvent includes one or more of ethanol, isopropanol, n-butanol, propylene glycol monomethyl ether, dimethylformamide, and dimethylacetamide.
7. The aqueous laser aluminizing transfer coating of claim 1, wherein the defoamer includes one or more of a mineral oil defoamer, a polyether defoamer, and an organosiloxane defoamer.
8. The aqueous laser aluminizing transfer coating of claim 1, wherein the leveling agent includes one or more of a fluorine-modified silicone leveling agent, a polyester-modified organosiloxane, an acrylic leveling agent, and a polyether-modified organosiloxane leveling agent.
9. The aqueous laser aluminizing transfer coating of claim 2, further comprising the following components by mass:
0.1-0.5 part of other auxiliary agents;
the other auxiliary agents comprise one or more of thickening agents, dispersing agents, rheological agents, hand feeling agents, scratch and abrasion resistant agents and antistatic agents.
10. The aqueous laser aluminizing transfer coating of claim 9, wherein the thickener includes one or more of a polyurethane thickener, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone;
the dispersing agent comprises one or more of polyvinyl alcohol and derivatives thereof, polymethacrylate and polyacrylate;
the rheological agent comprises one or more of waterborne polyurethane rheological agent, polyether rheological agent and polyamide rheological agent;
the hand feeling agent comprises one or more of polyether modified organic siloxane, polyester modified organic siloxane and alkyl modified organic siloxane;
the scratch-resistant and wear-resistant agent comprises one or more of high-density polyethylene wax, polypropylene wax, fluorine modified polyolefin, palm wax, polytetrafluoroethylene wax and polydimethylsiloxane;
the antistatic agent comprises an alkyl sodium sulfonate antistatic agent.
11. The method for preparing the aqueous laser aluminum plating transfer coating according to any one of claims 1 to 10, comprising the following steps:
preparation of a prepolymer: dehydrating the polyhydric alcohol with the Tg point of-80 to-20 ℃ in vacuum for 1 to 2 hours at the temperature of 110 to 120 ℃ to ensure that the water content is lower than 0.5 percent; adding polyisocyanate and a catalyst at 50-60 ℃, and reacting for 2-3 h at 70-90 ℃ to obtain a prepolymer;
chain extension: cooling the prepolymer to 40-60 ℃, slowly adding a hydrophilic chain extender, then heating to 80-90 ℃ to react for 2-4 h, and sampling to determine the molar content of NCO in the system; when the ratio of the mole number of the isocyanate group to the mole number of the hydroxyl group in the waterborne polyurethane is 1.1-1.5, adding a solvent to adjust the viscosity of the prepolymer to obtain a polymer;
neutralization and emulsification: controlling the temperature of the polymer at 20-60 ℃, adding a neutralizing agent to form salt, stirring, adding water to adjust the solid content to 25-40%, and dispersing at a high speed to obtain waterborne polyurethane;
and mixing the waterborne polyurethane, the cosolvent, water, the defoaming agent and the flatting agent to obtain the waterborne laser aluminizing transfer coating.
12. The preparation method of the aqueous laser aluminizing transfer coating according to claim 11, wherein the step of mixing the aqueous polyurethane, the cosolvent, the water, the defoamer and the leveling agent to obtain the aqueous laser aluminizing transfer coating comprises the following steps:
putting the cosolvent and the leveling agent into a reaction kettle, blending and uniformly stirring to obtain a mixture A;
adding water into the reaction kettle under the stirring state to obtain a mixture B;
slowly adding waterborne polyurethane into a reaction kettle under a stirring state to obtain a mixture C;
and adding a defoaming agent under a stirring state, uniformly stirring, and filtering to obtain the aqueous laser aluminizing transfer coating.
13. The method for preparing the aqueous laser aluminizing transfer coating according to claim 11, wherein an aminopropyl polysiloxane monomer is added to synthesize a polyurethane segment with a siloxane group before the polymer is neutralized.
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