CN117247731B - Temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum and preparation method thereof - Google Patents
Temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 74
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 47
- 239000011248 coating agent Substances 0.000 title claims abstract description 46
- 239000000839 emulsion Substances 0.000 claims abstract description 106
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 87
- -1 acrylic ester Chemical class 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 38
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011737 fluorine Substances 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims abstract description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims description 37
- 125000005442 diisocyanate group Chemical group 0.000 claims description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 29
- 229920000570 polyether Polymers 0.000 claims description 29
- 229920005862 polyol Polymers 0.000 claims description 29
- 150000003077 polyols Chemical class 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003094 microcapsule Substances 0.000 claims description 18
- 230000002441 reversible effect Effects 0.000 claims description 18
- 239000013530 defoamer Substances 0.000 claims description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000011258 core-shell material Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 2
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 72
- 230000000052 comparative effect Effects 0.000 description 24
- 239000011257 shell material Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- 230000001976 improved effect Effects 0.000 description 13
- 238000007639 printing Methods 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 239000011162 core material Substances 0.000 description 7
- 239000011087 paperboard Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical group [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VJWGHGJYLCJIEK-UHFFFAOYSA-N 1,4-bis(6-methylheptoxy)-1,4-dioxobutane-2-sulfonic acid Chemical compound CC(C)CCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCC(C)C VJWGHGJYLCJIEK-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- 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
- C09D5/26—Thermosensitive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The application discloses a temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum and a preparation method thereof, belonging to the field of electrochemical aluminum. The temperature-sensitive color-changing aqueous color layer coating for the electrochemical aluminum comprises the following components in percentage by weight: 8-15% of a closed isocyanate curing agent; 25-40% of aqueous hydroxyl-containing polyurethane emulsion; 10-30% of aqueous acrylic emulsion; 5-15% of a temperature-sensitive color-changing material; 0.5-2% of a leveling agent; 0.1-1% of a defoaming agent; the balance being water; the aqueous acrylic emulsion comprises the following preparation raw materials: the polyurethane comprises an aqueous polyurethane dispersion, acrylic acid, a fluorine-containing acrylic ester monomer, a fluorine-free acrylic ester monomer, N- (hydroxymethyl) acrylamide, an initiator, an emulsifier and water. The application has the effect of improving the stability and durability of the electrochemical aluminum color layer.
Description
Technical Field
The application relates to the field of electrochemical aluminum, in particular to a temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum and a preparation method thereof.
Background
The electrochemical aluminum is generally referred to as electrochemical aluminum foil, is a thermoprinting material, and can rapidly transfer and bond a surface decoration layer on the surface of a thermoprinted object in a heating and pressurizing mode, so that the electrochemical aluminum foil has many applications in the packaging and decoration fields.
The color layer coating is formed on the electrochemical aluminum foil, and has the functions of displaying color and protecting the aluminized layer. The existing electrochemical aluminum color layer coating can not change once the color phase during production is determined in the coating process.
Aiming at the situation, people try to add a temperature-sensitive color-changing material into the color layer coating to obtain the temperature-sensitive color-changing color layer coating, different hues are presented according to different temperature environments, however, the added temperature-sensitive color-changing material is easy to gather and precipitate in the color layer coating, the stability and the durability of the color layer are affected, and the development of the temperature-sensitive color-changing electrochemical aluminum is limited.
Disclosure of Invention
In order to improve the stability and durability of a color layer, the application provides a temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum and a preparation method thereof.
In a first aspect, the application provides a temperature-sensitive color-changing electrochemical aluminum aqueous color layer coating, which adopts the following technical scheme:
the temperature-sensitive color-changing aqueous color layer coating for the electrochemical aluminum comprises the following components in percentage by weight:
8-15% of a closed isocyanate curing agent;
25-40% of aqueous hydroxyl-containing polyurethane emulsion;
10-30% of aqueous acrylic emulsion;
5-15% of temperature-sensitive color-changing material;
0.5 to 2 percent of leveling agent;
0.1 to 1 percent of defoaming agent;
The balance being water;
The aqueous acrylic emulsion comprises the following preparation raw materials: the polyurethane comprises an aqueous polyurethane dispersion, acrylic acid, a fluorine-containing acrylic ester monomer, a fluorine-free acrylic ester monomer, N- (hydroxymethyl) acrylamide, an initiator, an emulsifier and water.
By adopting the technical scheme, the aqueous polyurethane emulsion and the aqueous acrylic emulsion are used as the main film forming body of the color layer, so that the stability of the color layer is ensured, and the closed isocyanate curing agent can react with the aqueous acrylic emulsion and also react with the aqueous hydroxyl-containing polyurethane emulsion to polymerize into a cross-linked network structure, so that the performance of the color layer is ensured.
In the aqueous acrylic emulsion, aqueous polyurethane dispersoid is used as a core material, acrylic acid, fluorine-containing acrylic ester monomer, fluorine-free acrylic ester monomer and N- (hydroxymethyl) acrylamide are used as shell materials, so that an aqueous acrylic emulsion structure with a core-shell structure is formed, a temperature-sensitive color-changing material can enter between the core and the shell, aggregation and precipitation of the temperature-sensitive color-changing material are not easy to occur, the overall stability is improved, N- (hydroxymethyl) acrylamide is used as a functional monomer, good reactivity with a closed isocyanate curing agent is achieved, an interpenetrating cross-linking structure is formed around the shell structure, and the stability, particularly the low temperature resistance, of the temperature-sensitive color-changing material entering between the core and the shell are improved when the color layer is formed, so that the stability and durability of the color layer are ensured on the basis of obtaining the temperature-sensitive color-changing effect.
In addition, the aqueous acrylic emulsion takes polyurethane as a core, so that the flexibility is good, the aqueous acrylic emulsion is matched with aqueous polyurethane emulsion, a crosslinked network structure is formed, the durability of a color layer is improved, and the heat resistance of the aqueous acrylic emulsion is improved due to the addition of the fluorine-containing acrylic ester monomer into the shell material, so that the weather resistance of the color layer coating is improved.
Optionally, the aqueous acrylic emulsion comprises the following preparation raw materials in parts by weight:
80-100 parts of aqueous polyurethane dispersoid;
acrylic acid 1.2-1.8 parts;
5-8 parts of fluorine-containing acrylic ester monomer;
16-22 parts of fluorine-free acrylic ester monomer;
1 to 1.5 portions of N- (hydroxymethyl) acrylamide;
0.3 to 0.6 part of initiator;
1.5-3 parts of emulsifying agent;
60-120 parts of water.
By adopting the technical scheme, the addition ratio of the fluorine-containing acrylic ester monomer and the N- (hydroxymethyl) acrylamide is controlled, and the surface modification structure of the aqueous acrylic emulsion particles can be adjusted, so that the stability of the color layer structure is maintained, and the color layer is not easily damaged by external force application.
Optionally, the fluorine-containing acrylate monomer is selected from one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate and dodecafluoroheptyl methacrylate.
By adopting the technical scheme, the fluorine-containing acrylic ester monomer has good modification effect on the core-shell structure of the aqueous acrylic emulsion, is beneficial to the temperature-sensitive color-changing material to enter between the core and the shell, and improves the dispersion stability of the temperature-sensitive color-changing material.
Optionally, the fluorine-free acrylic ester monomer is selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate.
By adopting the technical scheme, the fluorine-free acrylic ester monomer is selected as a shell skeleton of the aqueous acrylic emulsion, so that the particle stability of the aqueous acrylic emulsion is better.
Optionally, the temperature-sensitive color-changing material is a temperature-sensitive reversible microcapsule, and the average grain diameter of the temperature-sensitive reversible microcapsule is 0.5-5 mu m.
By adopting the technical scheme, the average particle size of the temperature-sensitive reversible microcapsule is controlled, so that the temperature-sensitive reversible microcapsule can enter a core-shell structure of the aqueous acrylic emulsion, and therefore, the dispersibility is improved, and agglomeration and deposition are not easy to occur.
Optionally, the preparation raw materials of the aqueous polyurethane dispersoid comprise diisocyanate, polyether polyol, a chain extender, hydroxyethyl acrylate and water, wherein the chain extender is sulfamic acid type chain extender, and the mol ratio of the diisocyanate, the polyether polyol, the chain extender and the hydroxyethyl acrylate is 1 (0.8-0.9) (0.15-0.25) (0.05-0.15).
By adopting the technical scheme, the sulfamic acid chain extender enables polyurethane to be dispersed in water, and the surface of polyurethane particles is modified by the access of hydroxyethyl acrylate, so that the connection of a core layer and a shell layer is facilitated, a stable water-based acrylic emulsion core-shell structure is formed, the wear resistance of a color layer is improved, and the stability of a temperature-sensitive color-changing material in the core-shell structure is further improved.
Optionally, the preparation raw materials of the aqueous hydroxyl-containing polyurethane emulsion comprise diisocyanate, polyether polyol, a chain extender and water, wherein the chain extender is selected from hydroxycarboxylic acid type chain extender, and the molar ratio of the diisocyanate to the polyether polyol to the chain extender is 1 (1.2-1.4) (0.7-0.8).
By adopting the technical scheme, the proportion of diisocyanate and polyether polyol is controlled, and the polyurethane emulsion containing hydroxyl is obtained.
Optionally, the leveling agent is one or two selected from an aqueous organic silicon leveling agent and an acetylene glycol leveling agent; and/or the defoamer is selected from one or two of aqueous mineral oil defoamer and aqueous molecular-grade defoamer.
Optionally, the initiator is potassium persulfate or ammonium persulfate.
Optionally, the emulsifier is selected from polyoxyethylene nonylphenol ether or diisooctyl sulfosuccinate sodium salt.
In a second aspect, the preparation method of the temperature-sensitive color-changing electrochemical aluminum water-based color layer coating provided by the application adopts the following technical scheme:
A preparation method of a temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum comprises the following steps:
Preparation of aqueous acrylic emulsion:
mixing and stirring acrylic acid, fluorine-containing acrylic ester monomer, fluorine-free acrylic ester monomer, N- (hydroxymethyl) acrylamide, part of emulsifier and part of water to obtain shell emulsion;
Mixing and stirring 10-25wt% of aqueous polyurethane dispersion, residual emulsifying agent and residual water, heating to 70-80 ℃, adding the residual aqueous polyurethane dispersion, then dropwise adding shell emulsion and initiator, continuing to perform heat preservation reaction for 80-120 min after the dropwise adding is finished, cooling, filtering and discharging to obtain aqueous acrylic emulsion;
Preparing an electrochemical aluminum water-based color layer coating:
mixing and stirring the aqueous hydroxyl-containing polyurethane emulsion, the aqueous acrylic emulsion and water, then adding the leveling agent, the temperature-sensitive color-changing material and part of the defoaming agent, mixing and stirring, then adding the closed isocyanate curing agent and the rest of the defoaming agent, mixing and stirring, filtering and discharging to obtain the electrochemical aluminum aqueous color layer coating.
By adopting the technical scheme, after the aqueous hydroxyl-containing polyurethane emulsion and the aqueous acrylic emulsion are mixed in advance, the temperature-sensitive color-changing material is added, so that the temperature-sensitive color-changing material can be uniformly dispersed.
Optionally, the preparation method of the aqueous polyurethane dispersion comprises the following steps:
Mixing diisocyanate and polyether polyol, heating to 75-85 ℃ for reaction for 1-2 hours, then adding a chain extender, monitoring NCO content in the reaction process, and adding hydroxyethyl acrylate until the NCO content is lower than 0.1wt% when the NCO content is 1.5-2.5 wt%, and stopping the reaction to obtain polyurethane prepolymer;
and then adding the polyurethane prepolymer into water for dispersion to obtain the aqueous polyurethane dispersion.
By adopting the technical scheme, the hydroxyethyl acrylate is accessed when the NCO content is lower, so that the access condition of the hydroxyethyl acrylate is controlled at the addition amount and the addition time of the hydroxyethyl acrylate, and the core material matched with the shell material is obtained.
In summary, the application has the following beneficial effects:
1. The application adopts the aqueous polyurethane emulsion and the aqueous acrylic emulsion as the main film forming body of the color layer, ensures the stability of the color layer, and ensures the performance of the color layer by the polymerization of the closed isocyanate curing agent which can react with the aqueous acrylic emulsion and the aqueous hydroxyl-containing polyurethane emulsion; and the aqueous acrylic emulsion structure with the core-shell structure is formed, and the temperature-sensitive color-changing material can enter between the core and the shell, so that the temperature-sensitive color-changing material is not easy to aggregate and precipitate, and the overall stability is improved.
2. The surface of the waterborne polyurethane dispersion particles is modified by the access of the hydroxyethyl acrylate, which is favorable for the connection of a core layer and a shell layer, and a stable waterborne acrylic emulsion core-shell structure is formed, so that the wear resistance of a color layer is improved, and the stability of the temperature-sensitive color-changing material in the core-shell structure is further improved.
Detailed Description
The present application will be described in further detail below.
Preparation example
Preparation example 1
The aqueous hydroxyl-containing polyurethane emulsion comprises the following raw materials:
The polyurethane foam comprises diisocyanate, polyether polyol, a chain extender and water, wherein the amount of the diisocyanate is 1000g, the amount of the water is 2000g, and the molar ratio of the diisocyanate, the polyether polyol and the chain extender is 1:1.2:0.7.
Wherein the diisocyanate is toluene-2, 4-diisocyanate, the polyether polyol is polytetramethylene glycol, the molecular weight of polytetramethylene glycol is 1200, and the chain extender is dimethylolpropionic acid.
The preparation method of the aqueous hydroxyl-containing polyurethane emulsion comprises the following steps:
And (3) stirring and mixing diisocyanate and polyether polyol for 10min, heating to 85 ℃, reacting at the temperature of 1.5h, adding a chain extender, reacting for 1.5h, monitoring the NCO content, and stopping reacting when the NCO content is lower than 0.1wt%, thus obtaining the hydroxyl-containing polyurethane prepolymer.
The hydroxyl-containing polyurethane prepolymer was added to water and dispersed at a rate of 600rpm to obtain an aqueous hydroxyl-containing polyurethane emulsion.
Preparation example 2
The difference between this preparation and preparation 1 is that the aqueous hydroxyl-containing polyurethane emulsion is different in the raw materials.
Specifically, the aqueous hydroxyl-containing polyurethane emulsion comprises the following raw materials:
The polyurethane foam comprises diisocyanate, polyether polyol, a chain extender and water, wherein the amount of the diisocyanate is 1000g, the amount of the water is 2000g, and the molar ratio of the diisocyanate, the polyether polyol and the chain extender is 1:1.4:0.8.
Wherein the diisocyanate is toluene-2, 4-diisocyanate, the polyether polyol is polytetramethylene glycol, the molecular weight of polytetramethylene glycol is 1200, and the chain extender is dimethylolpropionic acid.
Preparation example 3
An aqueous polyurethane dispersion comprising the following raw materials:
The molar ratio of diisocyanate, polyether polyol and chain extender is 1:0.8:0.15.
Wherein the diisocyanate is toluene-2, 4-diisocyanate, the polyether polyol is polypropylene glycol, the molecular weight of polytetramethylene glycol is 1500, and the chain extender is sodium sulfamate.
A method for preparing an aqueous polyurethane dispersion comprising the steps of:
and (3) stirring and mixing diisocyanate and polyether polyol for 10min, heating to 85 ℃, preserving heat and reacting for 1h, then adding a chain extender, monitoring the NCO content after reacting for 1h, and stopping reacting when the NCO content is lower than 0.1wt%, thus obtaining the polyurethane prepolymer.
The polyurethane prepolymer was added to water and dispersed at a rate of 1000rpm to obtain an aqueous polyurethane dispersion.
Preparation example 4
An aqueous polyurethane dispersion comprising the following raw materials:
The polyurethane foam comprises diisocyanate, polyether polyol, a chain extender, hydroxyethyl acrylate and water, wherein the dosage of the diisocyanate is 1000g, the dosage of the water is 2000g, and the molar ratio of the diisocyanate, the polyether polyol, the chain extender and the hydroxyethyl acrylate is 1:0.8:0.15:0.05.
Wherein the diisocyanate is toluene-2, 4-diisocyanate, the polyether polyol is polypropylene glycol, the molecular weight of polytetramethylene glycol is 1500, and the chain extender is sodium sulfamate.
A method for preparing an aqueous polyurethane dispersion comprising the steps of:
And (3) stirring and mixing diisocyanate and polyether polyol for 10min, heating to 85 ℃, preserving heat and reacting for 1h, then adding a chain extender, monitoring the NCO content after reacting for 1h, adding hydroxyethyl acrylate when the NCO content is reduced to 1.5wt%, continuing reacting until the NCO content is lower than 0.1wt%, and stopping reacting to obtain the polyurethane prepolymer.
The polyurethane prepolymer was added to water and dispersed at a rate of 1000rpm to obtain an aqueous polyurethane dispersion.
Preparation example 5
An aqueous polyurethane dispersion comprising the following raw materials:
The polyurethane foam comprises diisocyanate, polyether polyol, a chain extender, hydroxyethyl acrylate and water, wherein the dosage of the diisocyanate is 1000g, the dosage of the water is 2000g, and the molar ratio of the diisocyanate, the polyether polyol, the chain extender and the hydroxyethyl acrylate is 1:0.9:0.25:0.15.
Wherein the diisocyanate is toluene-2, 4-diisocyanate, the polyether polyol is polypropylene glycol, the molecular weight of polytetramethylene glycol is 1500, and the chain extender is sodium sulfamate.
A method for preparing an aqueous polyurethane dispersion comprising the steps of:
And (3) stirring and mixing diisocyanate and polyether polyol for 10min, heating to 75 ℃, preserving heat and reacting for 2h, then adding a chain extender, monitoring the NCO content after reacting for 1h, adding hydroxyethyl acrylate when the NCO content is reduced to 2.5wt%, continuing to react until the NCO content is lower than 0.1wt%, and stopping reacting to obtain the polyurethane prepolymer.
The polyurethane prepolymer was added to water and dispersed at a rate of 1000rpm to obtain an aqueous polyurethane dispersion.
Preparation example 6
The aqueous acrylic emulsion comprises the following raw materials:
800g of aqueous polyurethane dispersion, 12g of acrylic acid, 50g of fluorine-containing acrylic ester monomer, 160g of fluorine-free acrylic ester monomer, 10g of N- (hydroxymethyl) acrylamide, 3g of initiator, 15g of emulsifier and 600g of water.
The aqueous polyurethane dispersion is prepared by a preparation example 3, wherein the fluorine-containing acrylic ester monomer is hexafluorobutyl methacrylate, the fluorine-free acrylic ester monomer is butyl acrylate, the initiator is ammonium persulfate, and the emulsifier is nonylphenol polyoxyethylene ether.
The preparation method of the aqueous acrylic emulsion comprises the following steps:
acrylic acid, a fluorine-containing acrylic ester monomer, a fluorine-free acrylic ester monomer, N- (hydroxymethyl) acrylamide, 5g of an emulsifier and 300g of water are mixed and stirred to obtain a shell emulsion.
The initiator was mixed with 100g of water and stirred to obtain an initiator solution.
Mixing 80g of aqueous polyurethane dispersion, 10g of emulsifier and 200g of water, stirring, heating to 70 ℃, adding the rest 720g of aqueous polyurethane dispersion, then dropwise adding shell emulsion and initiator solution, continuing to perform heat preservation reaction for 120min after 60min dropwise adding, cooling, filtering and discharging by a 200-mesh sieve, and obtaining the aqueous acrylic emulsion.
Preparation example 7
The aqueous acrylic emulsion comprises the following raw materials:
1000g of aqueous polyurethane dispersion, 18g of acrylic acid, 80g of fluorine-containing acrylic ester monomer, 220g of fluorine-free acrylic ester monomer, 15g of N- (hydroxymethyl) acrylamide, 6g of initiator, 30g of emulsifier and 1200g of water.
The aqueous polyurethane dispersion is prepared by a preparation example 3, wherein the fluorine-containing acrylic ester monomer is hexafluorobutyl methacrylate, the fluorine-free acrylic ester monomer is butyl acrylate, the initiator is ammonium persulfate, and the emulsifier is nonylphenol polyoxyethylene ether.
The preparation method of the aqueous acrylic emulsion comprises the following steps:
Acrylic acid, a fluorine-containing acrylic ester monomer, a fluorine-free acrylic ester monomer, N- (hydroxymethyl) acrylamide, 15g of an emulsifier and 600g of water are mixed and stirred to obtain a shell emulsion.
The initiator was mixed with 100g of water and stirred to obtain an initiator solution.
250G of aqueous polyurethane dispersion, 15g of emulsifier and 500g of water are mixed and stirred, heated to 80 ℃, the rest 750g of aqueous polyurethane dispersion is added, then shell emulsion and initiator solution are added dropwise, the heat preservation reaction is continued for 80min after 75min dropwise addition is finished, cooling is carried out, and filtering and discharging are carried out by a 200-mesh sieve, so that the aqueous acrylic emulsion is obtained.
Preparation example 8
The difference between this preparation and preparation 6 is that the aqueous acrylic emulsion is different in the raw materials.
Specifically, the aqueous acrylic emulsion comprises the following raw materials:
800g of aqueous polyurethane dispersion, 12g of acrylic acid, 50g of fluorine-containing acrylic ester monomer, 160g of fluorine-free acrylic ester monomer, 10g of N- (hydroxymethyl) acrylamide, 3g of initiator, 15g of emulsifier and 600g of water.
Wherein the aqueous polyurethane dispersion is obtained in preparation example 3, the fluorine-containing acrylic ester monomer is trifluoroethyl methacrylate, the fluorine-free acrylic ester monomer is methyl methacrylate, the initiator is potassium persulfate, and the emulsifier is diisooctyl sulfosuccinate sodium salt.
Preparation example 9
The difference between this preparation and preparation 6 is that the aqueous acrylic emulsion is different in the raw materials.
800G of aqueous polyurethane dispersion, 12g of acrylic acid, 50g of fluorine-containing acrylic ester monomer, 160g of fluorine-free acrylic ester monomer, 10g of N- (hydroxymethyl) acrylamide, 3g of initiator, 15g of emulsifier and 600g of water.
The aqueous polyurethane dispersion is prepared by a preparation example 4, wherein the fluorine-containing acrylic ester monomer is hexafluorobutyl methacrylate, the fluorine-free acrylic ester monomer is butyl acrylate, the initiator is ammonium persulfate, and the emulsifier is nonylphenol polyoxyethylene ether.
Preparation example 10
The difference between this preparation and preparation 6 is that the aqueous acrylic emulsion is different in the raw materials.
800G of aqueous polyurethane dispersion, 12g of acrylic acid, 50g of fluorine-containing acrylic ester monomer, 160g of fluorine-free acrylic ester monomer, 10g of N- (hydroxymethyl) acrylamide, 3g of initiator, 15g of emulsifier and 600g of water.
The aqueous polyurethane dispersion is prepared by a preparation example 5, wherein the fluorine-containing acrylic ester monomer is hexafluorobutyl methacrylate, the fluorine-free acrylic ester monomer is butyl acrylate, the initiator is ammonium persulfate, and the emulsifier is nonylphenol polyoxyethylene ether.
Comparative preparation example
Comparative preparation example 1
The aqueous acrylic emulsion comprises the following raw materials:
12g of acrylic acid, 50g of fluorine-containing acrylic ester monomer, 160g of fluorine-free acrylic ester monomer, 10g of N- (hydroxymethyl) acrylamide, 3g of initiator, 15g of emulsifier and 600g of water.
Wherein the fluorine-containing acrylic ester monomer is hexafluorobutyl methacrylate, the fluorine-free acrylic ester monomer is butyl acrylate, the initiator is ammonium persulfate, and the emulsifier is nonylphenol polyoxyethylene ether.
The preparation method of the aqueous acrylic emulsion comprises the following steps:
Mixing and stirring acrylic acid, fluorine-containing acrylic ester monomer, fluorine-free acrylic ester monomer, N- (hydroxymethyl) acrylamide, emulsifier and water, heating to 70 ℃, dropwise adding initiator solution, continuously preserving heat for 90min after 60min dropwise adding, cooling, filtering and discharging by a 200-mesh sieve, and obtaining the aqueous acrylic emulsion.
Comparative preparation example 2
The aqueous acrylic emulsion comprises the following raw materials:
400g of methyl methacrylate, 12g of acrylic acid, 50g of fluorine-containing acrylic ester monomer, 160g of fluorine-free acrylic ester monomer, 10g of N- (hydroxymethyl) acrylamide, 3g of initiator, 15g of emulsifier and 600g of water.
Wherein the fluorine-containing acrylic ester monomer is hexafluorobutyl methacrylate, the fluorine-free acrylic ester monomer is butyl acrylate, the initiator is ammonium persulfate, and the emulsifier is nonylphenol polyoxyethylene ether.
The preparation method of the aqueous acrylic emulsion comprises the following steps:
acrylic acid, a fluorine-containing acrylic ester monomer, a fluorine-free acrylic ester monomer, N- (hydroxymethyl) acrylamide, 5g of an emulsifier and 300g of water are mixed and stirred to obtain a shell emulsion.
The initiator was mixed with 100g of water and stirred to obtain an initiator solution.
Mixing and stirring 100g of methyl methacrylate, 10g of emulsifier and 200g of water, heating to 70 ℃, adding the rest 300g of methyl methacrylate, then dropwise adding the shell emulsion and the initiator solution, continuing to perform heat preservation reaction for 120min after 60min dropwise adding, cooling, filtering and discharging by a 200-mesh sieve, and obtaining the aqueous acrylic emulsion.
Comparative preparation example 3
The comparative preparation example differs from preparation example 6 in that the raw material of the aqueous acrylic emulsion does not include N- (hydroxymethyl) acrylamide, and the addition amount of the fluorine-free acrylic monomer is changed to 170g.
Comparative preparation example 4
The comparative preparation example differs from preparation example 6 in that the raw material of the aqueous acrylic emulsion does not include the fluorine-containing acrylic acid ester monomer, and the addition amount of the fluorine-containing acrylic acid ester monomer is changed to 210g.
Examples
Example 1
The temperature-sensitive color-changing aqueous color layer coating for the electrochemical aluminum comprises the following raw materials:
150g of closed isocyanate curing agent, 400g of aqueous hydroxyl-containing polyurethane emulsion, 220g of aqueous acrylic emulsion, 80g of temperature-sensitive color-changing material, 20g of flatting agent, 5g of defoaming agent and 125g of water.
Wherein the blocked isocyanate curing agent is TDI type isocyanate curing agent, the deblocking temperature is 120 ℃, and the blocked isocyanate curing agent is selected from green-linked (Jining) chemical technology Co., ltd; the aqueous hydroxyl-containing polyurethane emulsion is derived from preparation example 1; the aqueous acrylic emulsion was derived from preparation 6; the temperature-sensitive color-changing material is a temperature-sensitive reversible microcapsule, the temperature-sensitive reversible microcapsule is selected from Chongyu technology and technology Co., ltd, the color number at 25 ℃ is 186C, the color-changing temperature is 25-40 ℃, and the grain diameter is 0.5-2 mu m; the leveling agent is an aqueous organic silicon leveling agent, namely Digao Glide B1484; the defoamer is an aqueous molecular defoamer, which is used for winning Surfynol DF-110L.
The preparation method of the temperature-sensitive color-changing aqueous color layer coating for the electrochemical aluminum comprises the following steps:
Adding aqueous hydroxyl-containing polyurethane emulsion, aqueous acrylic emulsion and water into a dispersing kettle, mixing and stirring for 10min at the speed of 40rpm, then adding a leveling agent, a temperature-sensitive color-changing material and 2g of defoamer, mixing and stirring for 30min, then adding a closed isocyanate curing agent and the rest 3g of defoamer, mixing and stirring for 10min, filtering and discharging by a 200-mesh sieve, and obtaining the electric aluminum aqueous color layer coating.
Example 2
This example differs from example 1 in that the starting materials of the temperature-sensitive color-changing aqueous color layer coating material for the electrochemical aluminum are different.
Specifically, the temperature-sensitive color-changing aqueous color layer coating for the electrochemical aluminum comprises the following raw materials:
110g of closed isocyanate curing agent, 320g of aqueous hydroxyl-containing polyurethane emulsion, 100g of aqueous acrylic emulsion, 50g of temperature-sensitive color-changing material, 15g of flatting agent, 10g of defoaming agent and 395g of water.
Wherein the blocked isocyanate curing agent is TDI type isocyanate curing agent, the deblocking temperature is 120 ℃, and the blocked isocyanate curing agent is selected from green-linked (Jining) chemical technology Co., ltd; the aqueous hydroxyl-containing polyurethane emulsion was derived from preparation 2; the aqueous acrylic emulsion was derived from preparation 6; the temperature-sensitive color-changing material is a temperature-sensitive reversible microcapsule, the temperature-sensitive reversible microcapsule is selected from Chongyu technology and technology Co., ltd, the color number at 25 ℃ is 186C, the color-changing temperature is 25-40 ℃, and the grain diameter is 4-5 mu m; the leveling agent is an acetylenic diol leveling agent, and is winning Dynol 800,800; the defoamer is an aqueous mineral oil defoamer, which wins Surfynol DF220.
Example 3
This example differs from example 1 in that the starting materials of the temperature-sensitive color-changing aqueous color layer coating material for the electrochemical aluminum are different.
Specifically, the temperature-sensitive color-changing aqueous color layer coating for the electrochemical aluminum comprises the following raw materials:
80g of closed isocyanate curing agent, 250g of aqueous hydroxyl-containing polyurethane emulsion, 300g of aqueous acrylic emulsion, 150g of temperature-sensitive color-changing material, 5g of flatting agent, 7g of defoaming agent and 218g of water.
Wherein the blocked isocyanate curing agent is TDI type isocyanate curing agent, the deblocking temperature is 120 ℃, and the blocked isocyanate curing agent is selected from green-linked (Jining) chemical technology Co., ltd; the aqueous hydroxyl-containing polyurethane emulsion is derived from preparation example 1; the aqueous acrylic emulsion was derived from preparation 6; the temperature-sensitive color-changing material is a temperature-sensitive reversible microcapsule, the temperature-sensitive reversible microcapsule is selected from Chongyu technology and technology Co., ltd, the color number at 25 ℃ is 186C, the color-changing temperature is 25-40 ℃, and the grain diameter is 0.5-2 mu m; the leveling agent is an aqueous organic silicon leveling agent, namely Digao Glide B1484; the defoamer is an aqueous molecular defoamer, which is used for winning Surfynol DF-110L.
Examples 4 to 7
Examples 4 to 7 differ from example 1 in that the sources of the aqueous acrylic emulsion in the raw materials of the temperature-sensitive color-changing electro-chemical aluminum aqueous color layer coating materials are different as shown in table 1.
TABLE 1
| Sources of aqueous acrylic emulsions | |
| Example 4 | Preparation example 7 |
| Example 5 | Preparation example 8 |
| Example 6 | Preparation example 9 |
| Example 7 | Preparation example 10 |
Comparative example
Comparative example 1
This comparative example differs from example 1 in that the starting materials of the temperature-sensitive color-changing aqueous color layer coating material for electric aluminum are different.
Specifically, the temperature-sensitive color-changing aqueous color layer coating for the electrochemical aluminum comprises the following raw materials:
150g of closed isocyanate curing agent, 620g of aqueous acrylic emulsion, 80g of temperature-sensitive color-changing material, 20g of flatting agent, 5g of defoaming agent and 125g of water.
Wherein the blocked isocyanate curing agent is TDI type isocyanate curing agent, the deblocking temperature is 120 ℃, and the blocked isocyanate curing agent is selected from green-linked (Jining) chemical technology Co., ltd; the aqueous acrylic emulsion was derived from preparation 6; the temperature-sensitive color-changing material is a temperature-sensitive reversible microcapsule, the temperature-sensitive reversible microcapsule is selected from Chongyu technology and technology Co., ltd, the color number at 25 ℃ is 186C, the color-changing temperature is 25-40 ℃, and the grain diameter is 0.5-2 mu m; the leveling agent is an aqueous organic silicon leveling agent, namely Digao Glide B1484; the defoamer is an aqueous molecular defoamer, which is used for winning Surfynol DF-110L.
In addition, the preparation method of the temperature-sensitive color-changing electrochemical aluminum aqueous color layer coating is also free from adding aqueous hydroxyl-containing polyurethane emulsion.
Comparative examples 2 to 5
Comparative examples 2 to 5 are different from example 1 in that the sources of the aqueous acrylic emulsion in the raw materials of the aqueous color layer coating material for temperature-sensitive color-changing alumite are different as shown in table 2.
TABLE 2
| Sources of aqueous acrylic emulsions | |
| Comparative example 2 | Comparative preparation example 1 |
| Comparative example 3 | Comparative preparation example 2 |
| Comparative example 4 | Comparative preparation example 3 |
| Comparative example 5 | Comparative preparation example 4 |
Performance detection
The temperature-sensitive color-changing aqueous color layer paint of the electrochemical aluminum prepared in each example and comparative example is respectively taken.
Selecting a PET film, coating water-based wax with the solid content of 20wt% on the film, and drying to form a release layer; then coating the color layer paint on the release layer, wherein the coating amount is 1.4g/m 2, the coating speed is 180m/min, and the drying temperature parameter is as follows: 1 region 75 ℃,2 region 110 ℃,3 region 125 ℃,4 region 130 ℃,5 region 105 ℃ to form a color layer; and then aluminizing to form an aluminized layer, wherein the OD value of the aluminized layer is 2.0, finally coating an adhesive, and drying to form an adhesive layer to obtain the electrochemical aluminum film.
Temperature-sensitive color change test: and (3) thermoprinting the prepared electrochemical aluminum film on the surface of a printing stock at 125 ℃ to form a thermoprinting layer, tearing off the film, specifically packaging paperboard, placing the printing stock in a 45 ℃ and 55RH% environment, observing whether the thermoprinting layer changes color, and observing the observation result to show that the thermoprinting layers of the examples 1-7 all finish the color change.
Heat resistance test: and (3) thermoprinting the prepared electrochemical aluminum film on the surface of a printing stock at 150 ℃ to form a thermoprinting layer, tearing off a film, wherein the printing stock is specifically packaging paperboard, the thermoprinting pattern is square patterns with the area of 50mm multiplied by 50mm, and the glossiness of the square patterns is observed after thermoprinting is finished and recorded in a table 3. The brighter the gloss, the better the heat resistance.
Cold resistance test: and (3) thermoprinting the prepared electrochemical aluminum film on the surface of a printing stock at 125 ℃ to form a thermoprinting layer, tearing off the film, specifically packaging paperboard, placing the printing stock in an environment of-20 ℃ and 50RH% for 24 hours, placing the printing stock at room temperature, observing whether the thermoprinting layer is cracked, and recording and table 3. No cracking represents good cold resistance.
Endurance adhesion test: the prepared electrochemical aluminum film is thermoprinted on the surface of a printing stock at 125 ℃ to form a thermoprinting layer, a film is torn off, the printing stock is specifically a packaging paperboard, the pattern of the thermoprinting layer is square patterns with the area of 50mm multiplied by 50mm, the printing stock is placed in an environment of 70 ℃ and 85RH% for 12 hours after thermoprinting is finished so as to simulate an accelerated ageing scene, then a 3M adhesive tape is adhered on the packaging paperboard and covers the thermoprinting pattern, then the 3M adhesive tape is torn off to separate the 3M adhesive tape from the packaging paperboard, the area occupation ratio of the thermoprinting pattern which does not fall off is calculated, and the area occupation ratio is recorded in a table 3. The larger the area ratio of the pattern that is not peeled off represents the better durable adhesion.
Abrasion resistance test: the produced alumite film is hot stamped on the surface of a printing stock at 125 ℃ to form a hot stamping layer, the film is torn off, the printing stock is specifically packaging paperboard, then the hot stamping layer is subjected to wear resistance test according to the wear resistance of the hot stamping layer of 4.5.2 of GB 10456-1989 electric alumite hot stamping foil, and the wear resistance As is measured and recorded in Table 3. Higher abrasion resistance As represents better abrasion resistance.
TABLE 3 Table 3
In combination with the test results of table 3, the color layer coating prepared in example 1 is applied to an electrochemical aluminum film, not only realizes the effect of temperature-induced discoloration, but also has good stability and durability, and is particularly characterized by high gloss after hot stamping, no cracking after bending under low-temperature environment, good adhesion after accelerated aging, and good wear resistance, so that the application prospect is good. Examples 2-7 also have good stability and durability.
By combining example 1 with comparative example 1, it can be seen that the aqueous hydroxyl-containing polyurethane emulsion and the aqueous acrylic emulsion cooperate to form a network structure that can greatly improve the stability and durability of the color layer.
By combining example 1 with comparative examples 2 to 3, it can be seen that the aqueous acrylic emulsion of the core-shell structure plays an obvious role in improving the stability and durability of the color layer, and the aqueous acrylic emulsion of the core-shell structure is likely to stabilize the temperature-sensitive reversible microcapsules and improve the dispersibility of the temperature-sensitive reversible microcapsules, thereby making the temperature-sensitive reversible microcapsules in the color layer less likely to precipitate and enabling the color layer to maintain structural stability in high and low temperature environments.
By comparing the combination of example 1 with comparative examples 4-5, it can be seen that the water-based acrylic emulsion is connected with N- (hydroxymethyl) acrylamide and fluorine-containing acrylic ester monomer, which has positive effects on the high temperature and low temperature resistance of the color layer, and further affects the adhesion and wear resistance of the color layer against external effects.
By combining example 1 with examples 6-7, it can be seen that after the aqueous polyurethane dispersion is inoculated with hydroxyethyl acrylate, the aqueous acrylic emulsion prepared by the method has good stabilizing effect, and the stability of the whole system and the stability of the temperature-sensitive reversible microcapsule are further improved, so that the wear resistance of the color layer is obviously improved.
The present embodiment is merely illustrative of the present application and not limiting, and one skilled in the art, after having read the present specification, may make modifications to the embodiment without creative contribution as required, but is protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum is characterized in that: comprises the following components in percentage by weight:
8-15% of a closed isocyanate curing agent;
25-40% of aqueous hydroxyl-containing polyurethane emulsion;
10-30% of aqueous acrylic emulsion;
5-15% of a temperature-sensitive color-changing material;
0.5-2% of a leveling agent;
0.1-1% of a defoaming agent;
The balance being water;
the aqueous acrylic emulsion comprises the following preparation raw materials in parts by weight:
80-100 parts of aqueous polyurethane dispersion;
Acrylic acid 1.2-1.8 parts;
5-8 parts of fluorine-containing acrylic ester monomer;
16-22 parts of fluorine-free acrylic ester monomer;
1-1.5 parts of N-methylol acrylamide;
0.3-0.6 parts of an initiator;
1.5-3 parts of an emulsifier;
60-120 parts of water;
the aqueous acrylic emulsion takes aqueous polyurethane dispersoid as a core and has a core-shell structure;
the temperature-sensitive color-changing material is a temperature-sensitive reversible microcapsule, and the average grain diameter of the temperature-sensitive reversible microcapsule is 0.5-5 mu m.
2. The temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum according to claim 1, which is characterized in that: the fluorine-containing acrylic ester monomer is one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate and dodecafluoroheptyl methacrylate.
3. The temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum according to claim 1, which is characterized in that: the fluorine-free acrylic ester monomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate.
4. The temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum according to claim 1, which is characterized in that: the preparation raw materials of the aqueous polyurethane dispersoid comprise diisocyanate, polyether polyol, a chain extender, hydroxyethyl acrylate and water, wherein the chain extender is sulfamic acid type chain extender, and the molar ratio of the diisocyanate to the polyether polyol to the chain extender to the hydroxyethyl acrylate is 1 (0.8-0.9) (0.15-0.25) (0.05-0.15).
5. The temperature-sensitive color-changing aqueous color layer coating for electrochemical aluminum according to claim 1, which is characterized in that: the preparation raw materials of the aqueous hydroxyl-containing polyurethane emulsion comprise diisocyanate, polyether polyol, a chain extender and water, wherein the chain extender is a hydroxycarboxylic acid type chain extender, and the molar ratio of the diisocyanate to the polyether polyol to the chain extender is 1 (1.2-1.4) (0.7-0.8).
6. A temperature-sensitive color-changing aqueous color layer coating for electric aluminum according to any one of claims 1-5, characterized in that: the leveling agent is one or two selected from water-based organic silicon leveling agents and acetylenic diol leveling agents; and/or the defoamer is selected from one or two of aqueous mineral oil defoamer and aqueous molecular-grade defoamer.
7. A method for preparing a temperature-sensitive color-changing electrochemical aluminum aqueous color layer coating based on any one of claims 1-6, which is characterized in that: the method comprises the following steps:
Preparation of aqueous acrylic emulsion:
Mixing and stirring acrylic acid, fluorine-containing acrylic ester monomer, fluorine-free acrylic ester monomer, N-methylolacrylamide, partial emulsifier and partial water to obtain shell emulsion;
Mixing and stirring 10-25 wt% of aqueous polyurethane dispersion, residual emulsifying agent and residual water, heating to 70-80 ℃, adding the residual aqueous polyurethane dispersion, then dropwise adding shell emulsion and initiator, continuing to perform heat preservation reaction for 80-120 min after the dropwise adding is finished, cooling, filtering and discharging to obtain aqueous acrylic emulsion;
Preparing an electrochemical aluminum water-based color layer coating:
mixing and stirring the aqueous hydroxyl-containing polyurethane emulsion, the aqueous acrylic emulsion and water, then adding the leveling agent, the temperature-sensitive color-changing material and part of the defoaming agent, mixing and stirring, then adding the closed isocyanate curing agent and the rest of the defoaming agent, mixing and stirring, filtering and discharging to obtain the electrochemical aluminum aqueous color layer coating.
8. The method for preparing the temperature-sensitive color-changing electrochemical aluminum aqueous color layer coating according to claim 7, which is characterized in that: the preparation method of the aqueous polyurethane dispersion comprises the following steps:
Mixing diisocyanate and polyether polyol, heating to 75-85 ℃ for reaction for 1-2 hours, then adding a chain extender, monitoring the NCO content in the reaction process, and adding hydroxyethyl acrylate until the NCO content is lower than 0.1wt% when the NCO content is 1.5-2.5 wt%, and stopping the reaction to obtain polyurethane prepolymer;
and then adding the polyurethane prepolymer into water for dispersion to obtain the aqueous polyurethane dispersion.
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