CN116871140B - Method for preparing coating on nonmetallic surface by vacuum coating process - Google Patents

Method for preparing coating on nonmetallic surface by vacuum coating process Download PDF

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Publication number
CN116871140B
CN116871140B CN202310854804.7A CN202310854804A CN116871140B CN 116871140 B CN116871140 B CN 116871140B CN 202310854804 A CN202310854804 A CN 202310854804A CN 116871140 B CN116871140 B CN 116871140B
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coating
parts
epoxy resin
intermediate layer
vacuum coating
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CN116871140A (en
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卢世义
卢鑫
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Guangzhou Xinbo Pigment Technology Co ltd
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Guangzhou Xinbo Pigment Technology Co ltd
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    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-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
    • 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
    • B05D7/587—No clear coat specified some layers being coated "wet-on-wet", the others not
    • 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
    • C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • 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
    • 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
    • B05D2504/00—Epoxy 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
    • B05D2518/00—Other type of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention relates to a method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process, belonging to the technical field of vacuum coating. The cationic auxiliary agent is used in the intermediate layer raw material provided by the invention to enhance the adsorption force, and meanwhile, the intermediate layer and the surface layer form a net-shaped cross-linked state, so that the fixation of the surface layer is enhanced; according to the modified epoxy resin provided by the invention, the acryloyloxy group and the epoxy group are connected into the resin, the surface curing effect is good under the cooperation of the photoinitiator and the triethylamine, and simultaneously, the triethylamine not only can be the auxiliary initiator of the hydrogen abstraction photoinitiator to initiate free radical polymerization, but also can be used as the thermosetting agent of the epoxy group to participate in crosslinking curing, so that the crosslinking density is improved; the invention solves the problem that the coating of the vacuum coating of the nonmetallic material is easy to fade and fall off in the prior art; the prior vacuum coating maintains good fixation effect after the middle layer and the surface layer are coated.

Description

Method for preparing coating on nonmetallic surface by vacuum coating process
Technical Field
The invention belongs to the technical field of vacuum coating, and particularly relates to a method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process.
Background
The vacuum coating technology is a technology for forming a metal film by heating and evaporating a coating material under high vacuum and sputtering or depositing the coating material on the surface of a coated product by using a physical vapor deposition method. Compared with the traditional water electroplating technology, the technology has the advantages of small pollution, low energy consumption, low cost, strong decorative effect and metallic feeling, and the like. The vacuum coating technology is rapidly developed in nearly half century, and is widely applied to the fields of automobiles, electronic 3C, household appliances, hardware, daily packaging, artistic decoration, toys and the like. The vacuum coating technology needs vacuum coating primer to seal the substrate and vacuum coating finish paint to protect the coating layer, so that the vacuum coating paint is an indispensable component of the vacuum coating technology, and the rapid development of the vacuum coating paint in China greatly promotes the development of the vacuum coating technology.
The current construction process of the vacuum coating mainly comprises coating, dip coating, air spraying and the like. Dip coating and air spraying are the earliest construction processes and are currently the main ones. The air spraying uses compressed air to atomize the paint for coating, can arbitrarily select the paint spraying condition, is easy to operate, is suitable for the workpiece with important spraying quality, but has low paint utilization rate (less than 50 percent) and serious waste. Dip coating is a coating method in which a coating film is formed on the surface of a coated article after the coated article is immersed in a paint liquid and dried by natural air drying or baking. The paint dipping equipment is simple, the operation is convenient, the work efficiency is high, the paint utilization rate is high, but the paint dipping equipment is only suitable for streamline workpieces which are simple in shape, have no pits and do not carry paint, and the thickness of a coating film on the upper part and the lower part of a coated object is uneven, the volatilization amount of a solvent is large, and the environment is polluted.
The vacuum coating is dyed by water dyeing or oil dyeing after the surface layer is dried, but the adhesion force of the water dyeing and the oil dyeing is not strong, the color is easy to fade, and the effect is seriously affected.
Disclosure of Invention
The invention relates to a method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process, belonging to the technical field of vacuum coating. The cationic auxiliary agent is used in the intermediate layer raw material provided by the invention to enhance the adsorption force, and meanwhile, the intermediate layer and the surface layer form a net-shaped cross-linked state, so that the fixation of the surface layer is enhanced; the invention solves the problem that the coating of the vacuum coating of the nonmetallic material is easy to fade and fall off in the prior art; the prior vacuum coating maintains good fixation effect after the middle layer and the surface layer are coated.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process comprises the following operation steps:
step one, surface treatment: carrying out oil removal and dust removal pretreatment on the base material;
step two, coating: coating the surface of the substrate by adopting a thermal evaporation coating method or a magnetron sputtering coating method;
step three, coating an intermediate layer: selecting a dip coating or spray coating method according to the properties of the substrate, and applying an intermediate layer on the surface of the coated substrate;
step four, baking the middle layer: drying the substrate coated with the intermediate layer;
step five, coating and curing the surface layer: and (3) carrying out surface coating on the substrate with the intermediate layer by using surface coating, and curing and drying to obtain the surface coating.
As a preferable scheme of the invention, the intermediate layer in the third step consists of the following raw materials in parts by weight:
80-100 parts of nano silicon dioxide, 0.3-0.6 part of dispersing agent, 30-40 parts of polyvinyl alcohol, 0.03-0.08 part of cross-linking agent and 8-12 parts of cation auxiliary agent.
As a preferred scheme of the invention, the cationic auxiliary comprises the following raw materials in percentage by mass:
8-12% of styrene, 11-15% of butyl acrylate, 1.0-1.5% of acrylic acid, 1.2-1.5% of hexadecyl trimethyl ammonium chloride, 0.1-0.3% of azo diisobutyl amidine hydrochloride and the balance of deionized water.
As a preferable scheme of the invention, the temperature of the drying in the step four is 60-70 ℃ and the time is 1.5-2.5h.
As a preferred embodiment of the present invention, the topcoat coating in the fifth step comprises the following raw materials in parts by weight:
30-50 parts of modified epoxy resin, 5-15 parts of polyurethane acrylic ester, 10-30 parts of trimethylolpropane triacrylate, 5-20 parts of composite photoinitiator, 0.1-0.5 part of flatting agent, 10-30 parts of ethyl acetate and 10-30 parts of butyl acetate.
As a preferred embodiment of the present invention, the topcoat coating is prepared by the following method:
taking quantitative modified epoxy resin, polyurethane acrylic ester, trimethylolpropane triacrylate, a composite photoinitiator, a leveling agent, ethyl acetate and butyl acetate, stirring for 1-2h, and filtering to obtain the surface coating.
As a preferable scheme of the invention, the modified epoxy resin is prepared from the following raw materials in parts by weight:
50-80 parts of phenolic epoxy resin, 10-20 parts of acrylic acid, 0.2-1 part of p-methylphenol, 0.5-2 parts of triphenylphosphine, 30-60 parts of isophorone diisocyanate, 15-30 parts of hydroxyethyl acrylate and 0.02-0.1 part of dibutyltin dilaurate.
As a preferable scheme of the invention, the composite photoinitiator consists of the following raw materials in parts by weight: 1841-5 parts of photoinitiator, 3-8 parts of photoinitiator I TX, and 3-8 parts of photoinitiator DMEA.
As a preferred embodiment of the present invention, the modified epoxy resin is prepared by the following method:
heating isophorone diisocyanate to 45-55 ℃, adding a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate, reacting for 2-4h under heat preservation, and cooling for later use; adding phenolic epoxy resin into a reactor, heating to 80-130 ℃, dropwise adding acrylic acid and a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate while stirring, preserving heat for 2-4h after the dropwise adding, and cooling to 55-60 ℃ when the acid value is less than 5mg KOH/g, and preserving heat for 2-4h to obtain the modified epoxy resin.
The invention has the beneficial effects that:
1. the invention provides a method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process, which comprises the steps of firstly carrying out vacuum coating on the surface of a substrate, then coating an intermediate layer, and finally coating a surface layer; the problem that a coating layer formed by vacuum plating a nonmetallic material is easy to fade and fall off in the prior art is solved; the prior vacuum coating maintains good fixation effect after the middle layer and the surface layer are coated;
2. in the intermediate layer raw material provided by the invention, the cationic auxiliary agent is used for generating electrostatic action to enhance the adsorption force, and the epoxy group is subjected to ring opening and carboxyl reaction in the baking process, so that the intermediate layer and the surface layer form a net-shaped cross-linked state, and the fixation of the surface layer is enhanced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A modified epoxy resin is prepared from the following raw materials:
phenolic epoxy resin 5kg, acrylic acid 1kg, p-methylphenol 20g, triphenylphosphine 50g, isophorone diisocyanate 3kg, hydroxyethyl acrylate 1.5kg, and dibutyltin dilaurate 2g.
The modified epoxy resin is prepared by the following method:
heating isophorone diisocyanate to 45 ℃, adding a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate, reacting for 2 hours in a heat-preserving way, and cooling for later use; adding phenolic epoxy resin into a reactor, heating to 80 ℃, dropwise adding acrylic acid and a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate while stirring, preserving heat for 2 hours after the dropwise adding, and cooling to 55 ℃ when the acid value is less than 5mg KOH/g, and preserving heat for 2 hours to obtain the modified epoxy resin.
Example 2
A modified epoxy resin is prepared from the following raw materials:
6.5kg of phenolic epoxy resin, 1.5kg of acrylic acid, 60g of p-methylphenol, 125g of triphenylphosphine, 4.5kg of isophorone diisocyanate, 2.2kg of hydroxyethyl acrylate and 6g of dibutyltin dilaurate.
The modified epoxy resin is prepared by the following method:
heating isophorone diisocyanate to 50 ℃, adding a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate, reacting for 3 hours in a heat-preserving way, and cooling for later use; adding phenolic epoxy resin into a reactor, heating to 105 ℃, dropwise adding acrylic acid and a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate while stirring, preserving heat for 3 hours after the dropwise adding, and cooling to 58 ℃ when the acid value is less than 5mg KOH/g, and preserving heat for 3 hours to obtain the modified epoxy resin.
Example 3
A modified epoxy resin is prepared from the following raw materials:
8kg of phenolic epoxy resin, 2kg of acrylic acid, 100g of p-methylphenol, 200g of triphenylphosphine, 6kg of isophorone diisocyanate, 3kg of hydroxyethyl acrylate and 10g of dibutyltin dilaurate.
The modified epoxy resin is prepared by the following method:
heating isophorone diisocyanate to 55 ℃, adding a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate, reacting for 4 hours in a heat-preserving way, and cooling for later use; adding phenolic epoxy resin into a reactor, heating to 130 ℃, dropwise adding acrylic acid and a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate while stirring, preserving heat for 4 hours after the dropwise adding, and cooling to 60 ℃ when the acid value is less than 5mg KOH/g, and preserving heat for 4 hours to obtain the modified epoxy resin.
Example 4
A topcoat coating comprising the following raw materials:
3kg of modified epoxy resin prepared in example 1, 0.5kg of polyurethane acrylate, 1kg of trimethylolpropane triacrylate, 0.5kg of composite photoinitiator, 10g of flatting agent, 1kg of ethyl acetate and 1kg of butyl acetate.
The surface coating is prepared by the following steps:
taking quantitative modified epoxy resin, polyurethane acrylic ester, trimethylolpropane triacrylate, a composite photoinitiator, a leveling agent, ethyl acetate and butyl acetate, stirring for 1h, and filtering to obtain the surface coating.
Example 5
A topcoat coating comprising the following raw materials:
4kg of modified epoxy resin prepared in example 2, 1kg of polyurethane acrylate, 2kg of trimethylolpropane triacrylate, 1.2kg of composite photoinitiator, 30g of flatting agent, 2kg of ethyl acetate and 2kg of butyl acetate.
The surface coating is prepared by the following steps:
taking quantitative modified epoxy resin, polyurethane acrylic ester, trimethylolpropane triacrylate, a composite photoinitiator, a leveling agent, ethyl acetate and butyl acetate, stirring for 1.5 hours, and filtering to obtain the surface coating.
Example 6
A topcoat coating comprising the following raw materials:
5kg of modified epoxy resin prepared in example 3, 1.5kg of polyurethane acrylate, 3kg of trimethylolpropane triacrylate, 2kg of composite photoinitiator, 50g of flatting agent, 3kg of ethyl acetate and 3kg of butyl acetate.
The surface coating is prepared by the following steps:
taking quantitative modified epoxy resin, polyurethane acrylic ester, trimethylolpropane triacrylate, a composite photoinitiator, a leveling agent, ethyl acetate and butyl acetate, stirring for 2 hours, and filtering to obtain the surface coating.
Example 7
A method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process comprises the following operation steps:
step one, surface treatment: the base material is subjected to oil removal and dust removal pretreatment to ensure the neatness and the dryness of the plating piece, and the defects of pitting and poor adhesive force of the bottom coating are avoided;
step two, coating: coating the surface of the base material by adopting a magnetron sputtering coating method;
step three, coating an intermediate layer: selecting a dip coating method according to the properties of the base material, and applying an intermediate layer on the surface of the coated base material;
the intermediate layer is composed of the following raw materials: 80g of nano silicon dioxide, 0.3g of dispersing agent, 30g of polyvinyl alcohol, 0.03g of cross-linking agent and 8g of cation auxiliary agent;
the cationic auxiliary agent comprises the following raw materials in percentage by mass: styrene 8%, butyl acrylate 11%, acrylic acid 1.0%, cetyl trimethyl ammonium chloride 1.2%, azo diisobutyl amidine hydrochloride 0.1%, and deionized water in balance;
step four, baking the middle layer: drying the substrate coated with the intermediate layer at 60 ℃ for 1.5 hours;
step five, coating and curing the surface layer: and (3) carrying out surface coating on the coated substrate by adopting the surface coating prepared in the embodiment 4, and curing and drying to prepare the surface coating.
Example 8
A method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process comprises the following operation steps:
step one, surface treatment: the base material is subjected to oil removal and dust removal pretreatment to ensure the neatness and the dryness of the plating piece, and the defects of pitting and poor adhesive force of the bottom coating are avoided;
step two, coating: coating the surface of the base material by adopting a magnetron sputtering coating method;
step three, coating an intermediate layer: selecting a dip coating method according to the properties of the base material, and applying an intermediate layer on the surface of the coated base material;
the intermediate layer is composed of the following raw materials: 90g of nano silicon dioxide, 0.46g of dispersing agent, 35g of polyvinyl alcohol, 0.05g of cross-linking agent and 10g of cation auxiliary agent;
the cationic auxiliary agent comprises the following raw materials in percentage by mass: 10% of styrene, 13% of butyl acrylate, 1.2% of acrylic acid, 1.3% of cetyl trimethyl ammonium chloride, 0.2% of azo diisobutyl amidine hydrochloride and the balance of deionized water;
step four, baking the middle layer: drying the substrate coated with the intermediate layer at 65 ℃ for 2 hours;
step five, coating and curing the surface layer: and (3) carrying out surface coating on the coated substrate by adopting the surface coating prepared in the embodiment 5, and curing and drying to prepare the surface coating.
Example 9
A method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process comprises the following operation steps:
step one, surface treatment: the base material is subjected to oil removal and dust removal pretreatment to ensure the neatness and the dryness of the plating piece, and the defects of pitting and poor adhesive force of the bottom coating are avoided;
step two, coating: coating the surface of the base material by adopting a magnetron sputtering coating method;
step three, coating an intermediate layer: selecting a dip coating method according to the properties of the base material, and applying an intermediate layer on the surface of the coated base material;
the intermediate layer is composed of the following raw materials: 100g of nano silicon dioxide, 0.6g of dispersing agent, 40g of polyvinyl alcohol, 0.08g of cross-linking agent and 12g of cation auxiliary agent;
the cationic auxiliary agent comprises the following raw materials in percentage by mass: 12% of styrene, 15% of butyl acrylate, 1.5% of acrylic acid, 1.5% of cetyltrimethylammonium chloride, 0.3% of azo diisobutyl amidine hydrochloride and the balance of deionized water;
step four, baking the middle layer: drying the substrate coated with the intermediate layer at 70 ℃ for 2.5 hours;
step five, coating and curing the surface layer: and (3) carrying out surface coating on the coated substrate by adopting the surface coating prepared in the example 6, and curing and drying to prepare the surface coating.
Comparative example 1
A method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process is compared with the method in the example 7, the modified epoxy resin is replaced by epoxy resin, and the rest is the same as the example 7.
Comparative example 2
A method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process is compared with example 7, does not contain a cationic auxiliary agent, and the rest is the same as example 7.
The surface coatings prepared in examples 7-9 and comparative examples 1-2 were tested as follows:
test example 1 adhesion test
According to the requirements of GB1320-88, a hand-held wiping tool is adopted, two layers of clean absorbent gauze are wrapped outside a rubber friction head, and the film layer is rubbed under the pressure of 4.9N. The wiping tool was perpendicular to the surface to be measured, and was wiped back and forth along the same trajectory, and the number of times of back and forth friction was recorded when the ion energy was 80ev, as shown in table 1.
TABLE 1
Test case Number of back and forth rubs
Example 7 28
Example 8 30
Example 9 29
Comparative example 1 22
Comparative example 2 24
As can be seen from Table 1, the surface coatings prepared by the methods of preparing the coatings on the nonmetallic surfaces using the vacuum coating process provided in examples 7 to 9 of the present invention have good adhesion, but the adhesion of comparative examples 1 and 2 is significantly reduced relative to the examples of the present invention.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (5)

1. A method for preparing a coating on a nonmetallic surface by adopting a vacuum coating process is characterized in that: the method comprises the following operation steps:
step one, surface treatment: carrying out oil removal and dust removal pretreatment on the base material;
step two, coating: coating the surface of the substrate by adopting a thermal evaporation coating method or a magnetron sputtering coating method;
step three, coating an intermediate layer: selecting a dip coating or spray coating method according to the properties of the substrate, and applying an intermediate layer on the surface of the coated substrate;
the intermediate layer consists of the following raw materials in parts by weight:
80-100 parts of nano silicon dioxide, 0.3-0.6 part of dispersing agent, 30-40 parts of polyvinyl alcohol, 0.03-0.08 part of cross-linking agent and 8-12 parts of cation auxiliary agent;
step four, baking the middle layer: drying the substrate coated with the intermediate layer;
step five, coating and curing the surface layer: carrying out surface coating on the substrate with the intermediate layer by using surface coating, curing and drying to obtain a surface coating;
the surface coating comprises the following raw materials in parts by weight:
30-50 parts of modified epoxy resin, 5-15 parts of polyurethane acrylic ester, 10-30 parts of trimethylolpropane triacrylate, 5-20 parts of composite photoinitiator, 0.1-0.5 part of flatting agent, 10-30 parts of ethyl acetate and 10-30 parts of butyl acetate;
the cationic auxiliary agent comprises the following raw materials in percentage by mass:
8-12% of styrene, 11-15% of butyl acrylate, 1.0-1.5% of acrylic acid, 1.2-1.5% of cetyl trimethyl ammonium chloride, 0.1-0.3% of azo diisobutyl amidine hydrochloride and the balance of deionized water;
the modified epoxy resin is prepared from the following raw materials in parts by weight:
50-80 parts of phenolic epoxy resin, 10-20 parts of acrylic acid, 0.2-1 part of p-methylphenol, 0.5-2 parts of triphenylphosphine, 30-60 parts of isophorone diisocyanate, 15-30 parts of hydroxyethyl acrylate and 0.02-0.1 part of dibutyltin dilaurate.
2. The method for preparing a coating on a nonmetallic surface by a vacuum coating process according to claim 1, characterized in that: and in the fourth step, the drying temperature is 60-70 ℃ and the drying time is 1.5-2.5h.
3. The method for preparing a coating on a nonmetallic surface by a vacuum coating process according to claim 1, characterized in that: the surface coating is prepared by the following steps:
taking quantitative modified epoxy resin, polyurethane acrylic ester, trimethylolpropane triacrylate, a composite photoinitiator, a leveling agent, ethyl acetate and butyl acetate, stirring for 1-2h, and filtering to obtain the surface coating.
4. The method for preparing a coating on a nonmetallic surface by a vacuum coating process according to claim 1, characterized in that: the composite photoinitiator consists of the following raw materials in parts by weight: 1-5 parts of photoinitiator 184, 3-8 parts of photoinitiator ITX and 3-8 parts of photoinitiator DMEA.
5. The method for preparing a coating on a nonmetallic surface by a vacuum coating process according to claim 1, characterized in that: the modified epoxy resin is prepared by the following method:
heating isophorone diisocyanate to 45-55 ℃, adding a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate, reacting for 2-4h under heat preservation, and cooling for later use; adding phenolic epoxy resin into a reactor, heating to 80-130 ℃, dropwise adding acrylic acid and a mixed solution of hydroxyethyl acrylate, p-methylphenol, triphenylphosphine and dibutyltin dilaurate while stirring, preserving heat for 2-4h after the dropwise adding, and cooling to 55-60 ℃ when the acid value is less than 5mg KOH/g, and preserving heat for 2-4h to obtain the modified epoxy resin.
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