CN116731603A - Vacuum plating laser engraving protective paint and preparation method and application thereof - Google Patents
Vacuum plating laser engraving protective paint and preparation method and application thereof Download PDFInfo
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- CN116731603A CN116731603A CN202310533618.3A CN202310533618A CN116731603A CN 116731603 A CN116731603 A CN 116731603A CN 202310533618 A CN202310533618 A CN 202310533618A CN 116731603 A CN116731603 A CN 116731603A
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- Prior art keywords
- paint
- protective paint
- laser engraving
- vacuum plating
- layer
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- 239000002519 antifouling agent Substances 0.000 title claims abstract description 88
- 238000007747 plating Methods 0.000 title claims abstract description 66
- 238000010147 laser engraving Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003973 paint Substances 0.000 claims abstract description 54
- 229920002635 polyurethane Polymers 0.000 claims abstract description 33
- 239000004814 polyurethane Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- -1 acrylic ester Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 9
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000010329 laser etching Methods 0.000 claims description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 34
- 239000000853 adhesive Substances 0.000 abstract description 16
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004132 cross linking Methods 0.000 abstract description 9
- 239000011247 coating layer Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000035515 penetration Effects 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 5
- 235000011613 Pinus brutia Nutrition 0.000 description 5
- 241000018646 Pinus brutia Species 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000009402 Dabao Substances 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241001134446 Niveas Species 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008269 hand cream Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 229940099259 vaseline Drugs 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/061—Special surface effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/586—No clear coat specified each layer being cured, at least partially, separately
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D5/002—Priming paints
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2201/00—Polymeric substrate or laminate
- B05D2201/02—Polymeric substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2503/00—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention particularly discloses a vacuum plating laser engraving protective paint and a preparation method and application thereof. The invention is based on that a large amount of hydroxyl contained in the dual-curing solvent type modified polyurethane acrylic ester can react with an added curing agent to form chemical bond crosslinking, the four-functional solvent type modified polyurethane acrylic ester can effectively enhance the adhesive force between the coating and the plating layer in the application process, the nine-functional polyurethane acrylic resin enhances the scratch resistance of the surface of the protective paint, the protective paint coating exposed at the laser carving position resists scratch, the six-functional acrylic ester monomer enhances the crosslinking curing and leveling effect, the photoinitiator plays a role of opening the double bond curing of the resin, the phosphate auxiliary agent can effectively enhance the penetration and the biting of the protective paint to the coating layer and the formation of covalent bonds or chemical bonds between the protective paint and the primer in the application process, and further enhances the adhesive force between the paint layers; therefore, the protective paint can show specular surface plating highlight effect after laser carving on the basis of meeting the adhesive force performance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a vacuum plating laser engraving protective paint and a preparation method and application thereof.
Background
At present, electronic products such as smart phone battery covers Logo are inlaid with characters on the surfaces of the products or are subjected to gold stamping technology on colored paint and then are sprayed with finish paint for protection, the inlaid characters can fall off after long-time use, and when a client produces the gold stamping technology in a mass mode, the product sprayed with the middle paint is subjected to the phenomena of grinding, bumping and the like when the product is disassembled and gold stamped due to no finish paint protection, so that the mass production yield is low and the cost is increased, and the gold stamping Logo has performance deviations such as water boiling test and adhesive force test. The technical defects of the process are that the coating is more, NCVM coating and laser etching wiping are needed, and the product is required to be subjected to laser etching within 48 hours after being put down, and the product is required to be wiped within 24 hours after the laser etching is finished.
Disclosure of Invention
In order to solve the technical problems, the invention provides a vacuum plating laser engraving protective paint, which comprises the following components in percentage by weight:
wherein the diluent is at least one of ethyl acetate, diacetone alcohol, ethylene glycol butyl ether and propylene glycol methyl ether acetate.
Preferably, the dual-curing solvent type modified polyurethane acrylic ester is DR-A821 of Taiwan Changxing chemistry, the tetrafunctional solvent type modified polyurethane acrylic ester is DY-481 of Shenzhen Luo Kete, and the nine functional aliphatic polyurethane acrylic resin is H-2013 of Dongguan-Chemicals.
Preferably, the hexafunctional acrylate monomer is M404 in eastern asia japan.
Preferably, the leveling agent is EFKA3600 of BASF, germany, and the phosphate is CD9051 of saromax.
Preferably, the photoinitiator is at least one of alpha-hydroxycyclohexyl benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
Preferably, the diluent comprises the following components by weight:
the invention also provides a preparation method of the vacuum plating laser etching protective paint, which is used for preparing the vacuum plating laser etching protective paint and at least comprises the following steps:
s1, adding dual-curing solvent type modified polyurethane acrylic ester, tetrafunctional solvent type modified polyurethane acrylic ester, nine-functional aliphatic polyurethane acrylic ester and six-functional acrylic ester monomers into a diluent with the volume of 1/3, and uniformly stirring;
s2, adding phosphate, a photoinitiator and a leveling agent, and uniformly stirring;
and S3, finally adding the rest 2/3 of the volume of the diluent, uniformly stirring, and filtering to obtain the vacuum plating laser etching protective paint.
The invention also provides an application of the vacuum plating laser etching protective paint, wherein the vacuum plating laser etching protective paint or the prepared vacuum plating laser etching protective paint is applied to electronic products, and the specific process comprises the following steps:
s100, spraying a treating agent on a substrate, wherein the thickness of the sprayed film is 10-20 mu m, and leveling for 5-8min at 50-60 ℃ to obtain a primary sprayed substrate, and the substrate is made of PC, ABS or one of 80% PC and 20% GF composite material in mass fraction;
s200, spraying the primer on the primary spraying substrate, wherein the thickness of the sprayed film is 20-30 mu m, leveling for 5-8min at 50-60 ℃, and curing with energy of 700-900mJ/cm < 2 >, so as to obtain a primer layer;
s300, performing NCVM (non-conductive metal plating) on the primer layer, wherein an electroplating target is indium, and the thickness of the electroplating film is 20-30nm;
s400, spraying the vacuum plating laser etching protective paint on an NCVM electroplated layer, wherein the sprayed film thickness is 20-30 mu m, leveling for 5-8min at 50-60 ℃ and curing with energy of 400-600mJ/cm < 2 >, so as to obtain a laser etching protective paint layer;
s500, spraying a colored paint on the laser carving protective paint layer, wherein the thickness of the sprayed paint layer is 8-12 mu m, and baking at 60-70 ℃ for 10-15min to cure the paint layer to obtain the colored paint layer;
s600, spraying electroplating finish paint on the colored paint layer, wherein the sprayed film thickness is 15-25 mu m, leveling for 5-8min at 50-60 ℃ and curing with energy of 800-1000mJ/cm < 2 >, so as to obtain the finish paint layer;
s700, carrying out logo laser engraving at a fixed position on the surface of the finish paint layer, removing the finish paint layer and the color paint layer, and reserving the laser engraving protective paint layer and the coating below the same to obtain a finished product.
Preferably, the treating agent, the primer, the color paint and the finish paint are all from new loose well materials, wherein the composition of the treating agent and the percentage thereof are as follows:
the primer consists of the following components in percentage:
the composition of the paint and the percentages thereof are as follows:
the composition and percentage of the finish paint are as follows:
wherein the mixed solvent is a mixture of ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate.
Compared with the prior art, the vacuum plating laser engraving protective paint and the preparation method and application thereof provided by the invention are characterized in that the protective paint is based on a large number of hydroxyl groups contained in dual-curing solvent modified polyurethane acrylate, so that the dual-curing solvent modified polyurethane acrylate reacts with an added curing agent in the application process and forms chemical bond crosslinking, the four-functional solvent modified polyurethane acrylate can effectively enhance the adhesive force between the application process and an electroplated layer, the nine-functional polyurethane acrylic resin enhances the scratch resistance of the surface of the protective paint, the protective paint coating exposed at the laser engraving position is scratch resistant, the six-functional acrylate monomer enhances the crosslinking curing and leveling effects, the photoinitiator plays a role of opening resin double bond curing, and the phosphate auxiliary can effectively enhance the penetration and biting of the protective paint to a coating layer and form covalent bonds or chemical bonds between the protective paint and the primer in the application process to further enhance the adhesive force between the paint layers; the laser etching protective paint provided by the invention can show a mirror surface plating highlight effect on the position or area after laser etching on the basis of meeting the adhesive force performance, so that the surface of the paint is leveled and smooth, and the microscopic angle surface has no concave-convex points.
Drawings
FIG. 1 is a flow chart of a preparation method of a vacuum plating laser engraving protective paint in the invention,
FIG. 2 is a flow chart of the application of a vacuum plating laser engraving protective paint in the invention.
Detailed Description
In order to make the technical scheme of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings.
The vacuum plating laser etching protective paint provided by the invention comprises the following components in percentage by weight:
wherein the diluent is at least one of ethyl acetate, diacetone alcohol, ethylene glycol butyl ether and propylene glycol methyl ether acetate.
In the embodiment, the dual-curing solvent type modified polyurethane acrylic ester is DR-A821 of Taiwan Changxing chemistry, the tetrafunctional solvent type modified polyurethane acrylic ester is DY-481 of Shenzhen Luo Kete, and the nine functional aliphatic polyurethane acrylic resin is H-2013 of Dongguan Hao chemical industry; the hexafunctional acrylate monomer is M404 in eastern asia japan; the leveling agent is EFKA3600 of BASF in Germany, and the phosphate is CD9051 of saromo; the photoinitiator is at least one of alpha-hydroxycyclohexyl benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
Wherein the diluent comprises the following components by weight:
in the embodiment, the vacuum plating laser etching protective paint is based on a large number of hydroxyl groups contained in dual-curing solvent type modified polyurethane acrylate, so that the protective paint can react with an added curing agent and form chemical bond crosslinking in the application process, the four-functional solvent type modified polyurethane acrylate can also effectively enhance the adhesive force between the protective paint and an electroplated layer in the application process, the nine-functional polyurethane acrylic resin can effectively enhance the scratch resistance of the protective paint, the protective paint coating exposed at the laser etching position in the application process has the characteristic of scratch resistance, the six-functional acrylate monomer improves the crosslinking curing and leveling effect, the surface of the protective paint is leveled, the microscopic angle surface has no concave-convex points, the photoinitiator plays a role in opening resin double bond curing, and the phosphate auxiliary can effectively improve the penetration and biting of the protective paint to a coating layer and the adhesive force between the protective paint and a primer in the application process or the chemical bond further improves the adhesive force between the paint layers; the laser etching protective paint provided by the invention can show specular surface plating highlight effect on the basis of meeting the adhesive force performance.
As shown in fig. 1, the invention also provides a preparation method of the vacuum plating laser engraving protective paint, which is used for preparing the vacuum plating laser engraving protective paint and at least comprises the following steps:
s1, adding dual-curing solvent type modified polyurethane acrylic ester, tetrafunctional solvent type modified polyurethane acrylic ester, nine-functional aliphatic polyurethane acrylic ester and six-functional acrylic ester monomers into a diluent with the volume of 1/3, and uniformly stirring;
s2, adding phosphate, a photoinitiator and a leveling agent, and uniformly stirring;
and S3, finally adding the rest 2/3 of the volume of the diluent, uniformly stirring, and filtering to obtain the vacuum plating laser etching protective paint.
Based on the technical effect description of the vacuum plating laser etching protective paint, the vacuum plating laser etching protective paint prepared by the preparation method has the same technical effect and is not repeated here.
As shown in fig. 2, the invention further provides an application of the vacuum plating laser etching protective paint, the vacuum plating laser etching protective paint or the prepared vacuum plating laser etching protective paint is applied to electronic products, and the specific process comprises the following steps:
s100, spraying a treating agent on a substrate, wherein the thickness of the sprayed film is 10-20 mu m, and leveling for 5-8min at 50-60 ℃ to obtain a primary sprayed substrate, and the substrate is made of one of PC (polycarbonate), ABS (acrylonitrile-butadiene-styrene) or a composite material with the mass fraction of 80% PC and the mass fraction of 20% GF (glass fiber);
in the step, the treating agent is used for covering poor base materials to improve the production yield of products, wherein the composition and the percentage of the treating agent are as follows:
wherein the mixed solvent is a mixture of ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate;
s200, spraying the primer on the primary spraying substrate, wherein the thickness of the sprayed film is 20-30 mu m, leveling for 5-8min at 50-60 ℃, and curing with energy of 700-900mJ/cm < 2 >, so as to obtain a primer layer;
in this step, the primer has the following composition and percentage thereof:
wherein the mixed solvent is a mixture of ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate;
s300, performing NCVM (non-conductive metal plating) on the primer layer, wherein an electroplating target is indium, and the thickness of the electroplating film is 20-30nm;
s400, spraying the vacuum plating laser etching protective paint on an NCVM electroplated layer, wherein the sprayed film thickness is 20-30 mu m, leveling for 5-8min at 50-60 ℃ and curing with energy of 400-600mJ/cm < 2 >, so as to obtain a laser etching protective paint layer;
s500, spraying a colored paint on the laser carving protective paint layer, wherein the thickness of the sprayed paint layer is 8-12 mu m, and baking at 60-70 ℃ for 10-15min to cure the paint layer to obtain the colored paint layer;
in this step, the composition of the paint and the percentages thereof are as follows:
wherein the mixed solvent is a mixture of ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate;
s600, spraying electroplating finish paint on the colored paint layer, wherein the sprayed film thickness is 15-25 mu m, leveling for 5-8min at 50-60 ℃ and curing with energy of 800-1000mJ/cm < 2 >, so as to obtain the finish paint layer;
in the step, the composition and the percentage of the finishing paint are as follows:
wherein the mixed solvent is a mixture of ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate;
s700, carrying out logo laser engraving at a fixed position on the surface of the finish paint layer, removing the finish paint layer and the color paint layer, and reserving the laser engraving protective paint layer and the coating below the same to obtain a finished product.
In this embodiment, by applying the vacuum plating laser etching protection paint or the vacuum plating laser etching protection paint prepared by the above to an electronic product for laser etching, on the basis of meeting the crosslinking adhesion performance, the surface of the position or area after laser etching is leveled and flat, the microscopic angle surface has no concave-convex points, and the mirror surface plating highlight effect is presented.
The treating agent, the UV vacuum plating primer, the color paint and the UV vacuum plating finishing paint are all purchased from Hunan pine well New Material Co., ltd, wherein: the model of the treating agent is pine Primer SP100-00023-1, the model of the Primer is pine SP110-10002, the model of the color paint is pine BP380-33021, and the model of the finish paint is pine PET00457A. Wherein, the ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate in the mixed solvent are mixed according to the proportion of 40:20:10:20:10.
In order to further understand the working principle and the effective technical effect of the invention, a series of specific embodiments are described based on the preparation method of the vacuum plating laser etching protective paint and the application method of the vacuum plating laser etching protective paint.
In this example, 10 examples are used to illustrate, table 1 shows the different weight ratios of the raw materials of the vacuum plating laser etching protective paint in the first 6 examples, and table 2 shows the performance test result table of the different vacuum plating laser etching protective paint applied in the middle frame of the mobile phone.
Table 1 table of different weight ratios of raw materials of vacuum plating laser engraving protective paint
Example 7
This comparative example prepared a vacuum plating laser engraving protective paint, which was different from example 3 in that: this example removes 4 parts of the dual cure solvent-based modified urethane acrylate of example 3, adding 4 parts of the tetrafunctional solvent-based modified urethane acrylate.
Example 8
The difference between the vacuum plating laser engraving protective paint prepared in this example and the vacuum plating laser engraving protective paint prepared in example 3 is that: this example removes 2 parts of the 4 parts dual cure solvent-based modified urethane acrylate of example 3, adding 2 parts of the tetrafunctional solvent-based modified urethane acrylate.
Example 9
The difference between the vacuum plating laser engraving protective paint prepared in this example and the vacuum plating laser engraving protective paint prepared in example 3 is that: in this example, 2 parts of the four-functional solvent-type modified urethane acrylate of example 3 was removed, and 2 parts of the dual-curable solvent-type modified urethane acrylate was added.
Example 10
The difference between the vacuum plating laser engraving protective paint prepared in this example and the vacuum plating laser engraving protective paint prepared in example 3 is that: this example removes 4 parts of the 20 parts tetrafunctional solvent-based modified urethane acrylate of example 3, adding 4 parts of the dual cure solvent-based modified urethane acrylate.
The application example is to coat the vacuum plating laser engraving protective paint prepared in the examples 1-10 on the surface of a mobile phone battery cover based on the application method of the vacuum plating laser engraving protective paint.
Table 2 table of results of performance test of different vacuum plating laser etching protective paint applied to cell cover surface of mobile phone
Wherein the adhesion test in Table 2 was carried out with reference to the standard document of GB 9286-1998;
the water boiling test means that the coating is placed in a water bath kettle with constant temperature of 100 ℃, after 1 hour, the coating is taken out, and after 2 hours of standing at normal temperature, the adhesive force is tested, the adhesive force of the coating is more than or equal to 4B, and the appearance is qualified without foaming, wrinkling and discoloration.
The cosmetic test is to uniformly coat the mixture of different cosmetics on the surface of a coated object, then put the coated object in a constant temperature and humidity box with the temperature of 70 ℃ and the RH of 85%, take out the coated object after 72 hours, wipe the cosmetics on the surface of the coated object clean, and test the adhesive force after the coated object is placed for 4 hours at normal temperature, wherein the adhesive force of the coating is more than or equal to 4B, and the appearance is qualified without foaming, wrinkling and discoloration.
In this example, the cosmetic test was performed according to cosmetic test standards published by millet company.
The specific experimental steps of the cosmetic test experiment are as follows:
a. dabao beauty day cream, nivea after-shave lotion, dabao refreshing moisturizing sun cream, vaseline multiple moisturizing hand cream, dabao SOD protein cream, skin-moisturizing lotion for newborn babies and skin-moisturizing oil for newborn babies are respectively taken 10g and put into a measuring cup to be uniformly mixed;
b. uniformly coating the mixture on the surface of a coated object by using a toothbrush;
c. placing the coated product coated with the cosmetics into a constant temperature and humidity box, and setting the conditions to be the temperature of 70 ℃ and the humidity of 85% for 72 hours;
d. after wiping the cosmetic on the surface of the coated article, the coated article was left at room temperature for 4 hours, and after checking the appearance of the coated article for OK, the adhesion was tested.
As can be seen from table 2, the laser engraving protective paint prepared in example 2, example 3, example 8 and example 9 has optimal performances, and the conventional adhesion 4B, the water boiling and the cosmetics have OK appearance and adhesive force 4B, so that the requirements of the optimal adhesion performance test are met; in the examples 7 and 10, the tetra-functional solvent-modified polyurethane acrylate and the dual-curing solvent-modified polyurethane acrylate are used for mutual replacement in different proportions, and the prepared laser etching protective paint has poor interlayer adhesion, water boiling and cosmetic testing performances and cannot meet the use requirements. The nine-functional urethane acrylic resin of example 1 added in 6 parts has a lower crosslinking density in a smaller proportion and has poorer poaching performance than that of examples 2, 3, 8 and 9; the nine-functional urethane acrylic resin of examples 4-6 added in 12-15 parts had a higher crosslinking density in a slightly higher proportion and had a conventional adhesion property inferior to that of examples 2, 3, 8 and 9; the proportions of the four-functional solvent-based modified polyurethane acrylate and the dual-curing solvent-based modified polyurethane acrylate in the examples 2, 3, 8 and 9 and the proportions of the six-functional acrylate monomer and the nine-functional polyurethane acrylic resin are all suitable, so that the adhesion performance of the laser etching protective paint is further improved, and the water boiling and cosmetic performances of the laser etching protective paint are further improved. Therefore, the vacuum plating laser engraving protective paint provided by the invention is particularly suitable for NCL technology, and meets the requirements of excellent adhesion and water boiling performance while meeting the appearance of high metal texture.
The vacuum plating laser etching protective paint provided by the invention and the preparation method and application thereof are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the core concepts of the invention. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (9)
1. The vacuum plating laser engraving protective paint is characterized by comprising the following components in parts by weight:
wherein the diluent is at least one of ethyl acetate, diacetone alcohol, ethylene glycol butyl ether and propylene glycol methyl ether acetate.
2. The vacuum plating laser engraving protective paint of claim 1, wherein the dual-curing solvent-modified polyurethane acrylate is DR-a821 of taiwan changxing chemistry, the tetrafunctional solvent-modified polyurethane acrylate is DY-481 of shenzhen Luo Kete, and the nine functional aliphatic polyurethane acrylic resin is H-2013 of dongguan han chemical industry.
3. The vacuum-plated laser engraving protective paint of claim 2, wherein the hexafunctional acrylate monomer is M404 of eastern japan.
4. The vacuum plating laser engraving protective paint of claim 3, wherein the leveling agent is EFKA3600 of BASF, germany, and the phosphate is CD9051 of saromo.
5. The vacuum plating laser engraving protective paint of claim 4, wherein the photoinitiator is at least one of alpha-hydroxycyclohexyl benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
6. The vacuum-plated laser engraving protective paint of claim 5, wherein the diluent comprises the following components by weight:
7. a method for preparing a vacuum plating laser engraving protective paint, which is characterized in that the method is used for preparing the vacuum plating laser engraving protective paint according to any one of claims 1 to 6, and at least comprises the following steps:
s1, adding dual-curing solvent type modified polyurethane acrylic ester, tetrafunctional solvent type modified polyurethane acrylic ester, nine-functional aliphatic polyurethane acrylic ester and six-functional acrylic ester monomers into a diluent with the volume of 1/3, and uniformly stirring;
s2, adding phosphate, a photoinitiator and a leveling agent, and uniformly stirring;
and S3, finally adding the rest 2/3 of the volume of the diluent, uniformly stirring, and filtering to obtain the vacuum plating laser etching protective paint.
8. Application of the vacuum plating laser engraving protective paint as claimed in any one of claims 1 to 6 or the vacuum plating laser engraving protective paint prepared in claim 7 in electronic products, which comprises the following specific processes:
s100, spraying a treating agent on a substrate, wherein the thickness of the sprayed film is 10-20 mu m, and leveling for 5-8min at 50-60 ℃ to obtain a primary sprayed substrate, and the substrate is made of PC, ABS or one of 80% PC and 20% GF composite material in mass fraction;
s200, spraying the primer on the primary spraying substrate, wherein the thickness of the sprayed film is 20-30 mu m, leveling for 5-8min at 50-60 ℃, and curing with energy of 700-900mJ/cm < 2 >, so as to obtain a primer layer;
s300, performing NCVM (non-conductive metal plating) on the primer layer, wherein an electroplating target is indium, and the thickness of the electroplating film is 20-30nm;
s400, spraying the vacuum plating laser etching protective paint on an NCVM electroplated layer, wherein the sprayed film thickness is 20-30 mu m, leveling for 5-8min at 50-60 ℃ and curing with energy of 400-600mJ/cm < 2 >, so as to obtain a laser etching protective paint layer;
s500, spraying a colored paint on the laser carving protective paint layer, wherein the thickness of the sprayed paint layer is 8-12 mu m, and baking at 60-70 ℃ for 10-15min to cure the paint layer to obtain the colored paint layer;
s600, spraying electroplating finish paint on the colored paint layer, wherein the sprayed film thickness is 15-25 mu m, leveling for 5-8min at 50-60 ℃ and curing with energy of 800-1000mJ/cm < 2 >, so as to obtain the finish paint layer;
s700, carrying out logo laser engraving at a fixed position on the surface of the finish paint layer, removing the finish paint layer and the color paint layer, and reserving the laser engraving protective paint layer and the coating below the same to obtain a finished product.
9. The use of a vacuum plating laser engraving protective paint according to claim 8, wherein the treating agent, the primer, the color paint and the top paint are all from new materials of a loose well, and the composition and the percentage of the treating agent are as follows:
the primer consists of the following components in percentage:
the composition of the paint and the percentages thereof are as follows:
the composition and percentage of the finish paint are as follows:
wherein the mixed solvent is a mixture of ethyl acetate, butyl acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221459A (en) * | 2016-08-31 | 2016-12-14 | 湖南松井新材料有限公司 | Imitative anodic oxidation and the coating of CNC effect, the base material having that effect and preparation method |
| CN106752860A (en) * | 2016-12-02 | 2017-05-31 | 东莞市惠尔明高分子材料科技有限公司 | A kind of 3D laser carvings optical curing of UV coating and preparation method thereof |
| CN107384180A (en) * | 2017-07-14 | 2017-11-24 | 东莞市佩琦涂料有限公司 | A kind of 3D laser carvings plating UV dope and preparation method thereof |
| CN108276900A (en) * | 2018-02-28 | 2018-07-13 | 湖南松井新材料股份有限公司 | Plate coating system and the metalwork product with imitative ceramic effect |
| CN108276898A (en) * | 2017-12-29 | 2018-07-13 | 湖南松井新材料有限公司 | Plate coating system, plastic parts and its preparation process with metal effect coating |
| CN113337201A (en) * | 2021-06-30 | 2021-09-03 | 湖南松井新材料股份有限公司 | Primer and preparation method and application thereof |
| CN113736357A (en) * | 2021-08-30 | 2021-12-03 | 湖南松井新材料股份有限公司 | Vacuum coating nano white slurry medium paint and preparation method and application thereof |
-
2023
- 2023-05-12 CN CN202310533618.3A patent/CN116731603A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221459A (en) * | 2016-08-31 | 2016-12-14 | 湖南松井新材料有限公司 | Imitative anodic oxidation and the coating of CNC effect, the base material having that effect and preparation method |
| CN106752860A (en) * | 2016-12-02 | 2017-05-31 | 东莞市惠尔明高分子材料科技有限公司 | A kind of 3D laser carvings optical curing of UV coating and preparation method thereof |
| CN107384180A (en) * | 2017-07-14 | 2017-11-24 | 东莞市佩琦涂料有限公司 | A kind of 3D laser carvings plating UV dope and preparation method thereof |
| CN108276898A (en) * | 2017-12-29 | 2018-07-13 | 湖南松井新材料有限公司 | Plate coating system, plastic parts and its preparation process with metal effect coating |
| CN108276900A (en) * | 2018-02-28 | 2018-07-13 | 湖南松井新材料股份有限公司 | Plate coating system and the metalwork product with imitative ceramic effect |
| CN113337201A (en) * | 2021-06-30 | 2021-09-03 | 湖南松井新材料股份有限公司 | Primer and preparation method and application thereof |
| CN113736357A (en) * | 2021-08-30 | 2021-12-03 | 湖南松井新材料股份有限公司 | Vacuum coating nano white slurry medium paint and preparation method and application thereof |
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