阅读说明：本技术 一种塑胶表面镀层结构及其制备方法 (Plastic surface coating structure and preparation method thereof ) 是由 胡栋明 邓迎春 贾夕满 于 2021-08-25 设计创作，主要内容包括：本申请涉及塑胶制品表面电镀技术领域,具体公开了一种塑胶表面镀层结构及其制备方法。本申请的塑胶表面镀层结构,从塑胶表面层开始依次为导电金属层、电镀镍层、PVD颜色层、透明二氧化硅薄膜层,所述塑胶经过表面处理剂处理,所述表面处理剂主要由如下原料组成：增塑剂、十二烷基硫酸钠、偶联剂、水；本申请的塑胶表面镀层结构的制备方法,包括如下步骤：(1)塑胶制品前处理：将塑胶制品经过表面处理剂进行处理,即得塑胶制品一；(2)塑胶制品预金属化：将步骤(1)得到的塑胶制品一进行镀导电金属层；(3)塑胶制品电镀镍；(4)塑胶制品电镀功能层。本申请的塑胶表面镀层结构吸镀能力较强。(The application relates to the technical field of plastic product surface electroplating, and particularly discloses a plastic surface coating structure and a preparation method thereof. The utility model provides a plastic surface coating structure begins to be conductive metal layer, electroplated nickel layer, PVD colour layer, transparent silica thin layer in proper order from the plastic superficial layer, the plastic is handled through the surface treatment agent, the surface treatment agent mainly comprises following raw materials: plasticizer, sodium dodecyl sulfate, coupling agent and water; the preparation method of the plastic surface coating structure comprises the following steps: (1) plastic product pretreatment: treating the plastic product with a surface treating agent to obtain a plastic product I; (2) pre-metallization of plastic products: plating a conductive metal layer on the plastic product I obtained in the step (1); (3) electroplating nickel on the plastic product; (4) and (4) electroplating a functional layer on the plastic product. The plastic surface coating structure has strong suction plating capability.)

1. A plastic surface coating structure is characterized in that a conductive metal layer, an electroplated nickel layer, a PVD color layer and a transparent silicon dioxide film layer are sequentially arranged from a plastic surface layer, the thickness of the transparent silicon dioxide film layer is 500-1200 mu m, the thickness of the conductive metal layer is 3-5 mu m, the thickness of the electroplated nickel layer is 5-8 mu m, the thickness of the PVD color layer is 0.5-1 mu m, the plastic is treated by a surface treating agent, and the surface treating agent mainly comprises the following raw materials in parts by weight: 5-10 parts of plasticizer, 5-10 parts of sodium dodecyl sulfate, 10-15 parts of coupling agent and 50-60 parts of water, wherein the plasticizer is at least two of acetyl tributyl citrate, cyclohexane-1, 2-diisooctyl phthalate and ethylene glycol butyl ether, and the coupling agent is at least two of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and perfluoroalkyl phenoxysulfonic vinyl ether.

2. The plastic surface coating structure of claim 1, wherein: the mass ratio of the plasticizer to the coupling agent is (7-8) to (12-13).

3. The plastic surface coating structure of claim 2, wherein: the plasticizer consists of acetyl tributyl citrate, cyclohexane-1, 2-diisooctyl phthalate and ethylene glycol butyl ether according to the mass ratio of (2-3) to (4-6) to (5-8).

4. The plastic surface coating structure of claim 3, wherein: the coupling agent is composed of at least one of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphoryl oxy) titanate and perfluoroalkyl phenoxy sulfonic vinyl ether according to the mass ratio of (4-6) to (2-3).

5. The plastic surface coating structure of claim 4, wherein: the coupling agent consists of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, isopropyl tri (dioctyl pyrophosphoryl oxy) titanate and perfluoroalkyl phenoxy sulfonic vinyl ether according to the mass ratio of (1-2) to (3-4) to (2-3).

6. The plastic surface coating structure of claim 5, wherein: the surface treating agent also comprises 7-8 parts by weight of hydrophilic agent, wherein the hydrophilic agent is at least two of 3-methoxy-2, 2-dimethylpropionic acid, fatty acid methyl ester polyoxyethylene ether and sodium dodecyl benzene sulfonate.

7. The plastic surface coating structure of claim 6, wherein: the hydrophilic agent consists of 3-methoxy-2, 2-dimethylpropionic acid, fatty acid methyl ester polyoxyethylene ether and sodium dodecyl benzene sulfonate according to the mass ratio of (2-3) to (3-5) to (4-6).

8. The plastic surface coating structure of claim 7, wherein: the thickness of the transparent silicon dioxide film layer is 800-900 mu m.

9. A method for preparing a plastic surface coating structure according to any one of claims 1 to 8, wherein: the method comprises the following steps:

(1) plastic product pretreatment: carrying out hydrocarbon vacuum oil removal and drying treatment on the plastic product, treating the plastic product by using a surface treating agent, and drying to obtain a first plastic product;

(2) pre-metallization of plastic products: plating a conductive metal layer on the first plastic product obtained in the step (1) to obtain a second plastic product;

(3) electroplating nickel on the plastic product: electroplating nickel on the plastic product II obtained in the step (2) to obtain a plastic product III;

(4) electroplating a functional layer on the plastic product: plating a PVD color layer and a transparent silicon dioxide thin film layer on the plastic product III obtained in the step (3).

10. The method for preparing a plastic surface coating structure according to claim 9, wherein the method comprises the following steps: the method for processing the plastic product by the surface treatment agent in the step (1) comprises the following steps: immersing the plastic product in the surface treating agent for 40-50min, ultrasonically cleaning in clear water for 7-8min after soaking, then placing on oxidizing flame for calcining for 1-2min, and cleaning with clear water and drying in the air.

Technical Field

The application relates to the technical field of plastic product surface electroplating, in particular to a plastic surface coating structure and a preparation method thereof.

Background

The plastic product is made of plastics, and is made up by using high-molecular compound polymerized by addition polymerization or polycondensation reaction, and can freely change its composition and form, and is formed from synthetic resin, filler, plasticizer, stabilizing agent, lubricating agent and colouring material. Plastic electroplating has been applied in large scale in the industries of automobiles, household appliances, bathrooms and the like, and the technology mainly comprises the chemical metallization and electroplating processes of the plastic surface.

With the rapid development of the industry, the application of plastic electroplating is increasingly wide, which becomes one of the important means for surface decoration in plastic products, compared with metal products, the plastic electroplated products not only can realize good metal texture, but also can reduce the weight of the products, effectively improve the appearance and the decoration of the plastic, and simultaneously improve the performances of the plastic in the aspects of electricity, heat, corrosion resistance and the like, and the plastic electroplated products have wide application range in the application field of plastics nowadays.

In the electroplating process, need use alligatoring liquid to handle plastics to make plastics become hydrophilicity from hydrophobicity, thereby improve the cohesion on plastic surface, traditional alligatoring liquid is handled plastics after, there is the inconsistent condition of hydrophilicity in the surface, thereby when leading to later stage electroplating, plastics and intermetallic cohesion are not good, and the ability of inhaling of plastics is not high.

Disclosure of Invention

In order to improve the absorbing and plating capacity of plastic products, the application provides a plastic surface plating layer structure and a preparation method thereof.

In a first aspect, the present application provides a plastic surface coating structure, which adopts the following technical scheme:

a plastic surface coating structure comprises a conductive metal layer, an electroplated nickel layer, a PVD color layer and a transparent silicon dioxide film layer in sequence from a plastic surface layer, wherein the thickness of the transparent silicon dioxide film layer is 500-1200 mu m, the thickness of the conductive metal layer is 3-5 mu m, the thickness of the electroplated nickel layer is 5-8 mu m, the thickness of the PVD color layer is 0.5-1 mu m, the plastic is treated by a surface treating agent, and the surface treating agent mainly comprises the following raw materials in parts by weight: 5-10 parts of plasticizer, 5-10 parts of sodium dodecyl sulfate, 10-15 parts of coupling agent and 50-60 parts of water, wherein the plasticizer is at least two of acetyl tributyl citrate, cyclohexane-1, 2-diisooctyl phthalate and ethylene glycol butyl ether, and the coupling agent is at least two of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and perfluoroalkyl phenoxysulfonic vinyl ether.

By adopting the technical scheme, the plastic product is sequentially plated with the conductive metal layer, the electroplated nickel layer, the PVD color layer and the transparent silicon dioxide film layer after being treated by the surface treating agent, and the transparent silicon dioxide film layer is convenient for reducing direct contact between other plating layer structures on the plastic product and the outside, so that the corrosion resistance of the plating layer structure on the plastic product is improved, and the condition that the plating layer structure is abraded is reduced; the plasticizer in the surface treatment agent can treat the surface of the plastic product, so that the surface of the plastic product has better ductility and flexibility, the addition of the coupling agent can enhance the treatment effect of the plasticizer on the plastic product, and simultaneously, the lauryl sodium sulfate can increase the wettability and the permeability of the surface of the plastic product, so that the treatment effect of the plasticizer on the surface of the plastic product is further increased, and simultaneously, the coupling agent and the plasticizer can introduce active groups and hydrophilic groups to the surface of the plastic product, so that the hydrophilic capacity of the plastic product is increased, and the binding force between the coupling agent and a coating is enhanced.

Preferably, the mass ratio of the plasticizer to the coupling agent is (7-8) to (12-13).

Through adopting above-mentioned technical scheme, optimize the proportion of plasticizer, coupling agent to make the collocation of plasticizer, coupling agent more reasonable, the addition of coupling agent is greater than the addition of plasticizer, thereby increases the plastification of plasticizer to plastics, and then improves the compliance and the ductility of plastics, and simultaneously, the coupling agent can also increase the hydrophilicity of plastics, and then makes plastics and conductive metal layer cohesion stronger, and then improves the absorption of plastics and plates the ability.

Preferably, the plasticizer consists of acetyl tributyl citrate, cyclohexane-1, 2-dioctyl phthalate and ethylene glycol butyl ether according to the mass ratio of (2-3) to (4-6) to (5-8).

By adopting the technical scheme, the proportion of each component of the plasticizer is optimized, so that the collocation of each component is more reasonable, the ethylene glycol butyl ether can increase the solubility of the acetyl tributyl citrate and the cyclohexane-1, 2-diisooctyl phthalate in water, and simultaneously increase the compatibility between the acetyl tributyl citrate, the cyclohexane-1, 2-diisooctyl phthalate and the plastic product, thereby further increasing the effect of each component of the plasticizer on the plastic product, improving the hydrophilic capacity of the plastic product, and further improving the binding force between the plastic product and other coating layers.

Preferably, the coupling agent consists of at least one of 3- (2, 3-glycidoxy) propyltrimethoxysilane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and perfluoroalkyl phenoxysulfo vinyl ether in a mass ratio of (4-6) to (2-3).

By adopting the technical scheme, the proportion of each component of the coupling agent is optimized, so that the collocation of each component is more reasonable, the affinity of the perfluoroalkyl phenoxy sulfonic vinyl ether with water is extremely high, the mutual acting force is small, the effect is obvious, when the application is less, the surface tension of the plastic product can be reduced, and after the coupling agent is matched with 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, the surface tension of the plastic product can be further reduced, so that the treatment effect of the plasticizer on the plastic product is enhanced.

Preferably, the coupling agent consists of 3- (2, 3-glycidoxy) propyltrimethoxysilane, isopropyl tri (dioctyl pyrophosphoryl oxy) titanate and perfluoroalkyl phenoxysulfonic vinyl ether in a mass ratio of (1-2) to (3-4) to (2-3).

By adopting the technical scheme, the proportion of each component of the coupling agent is further optimized, so that the collocation of each component is more reasonable, and after the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and the perfluoroalkyl phenoxy sulfonic vinyl ether are cooperatively matched together, the surface tension of the surface of the plastic product can be further reduced, so that the bonding force between the plastic product and the conductive metal layer is better during electroplating.

Preferably, the surface treating agent also comprises 7-8 parts by weight of a hydrophilic agent, wherein the hydrophilic agent is at least two of 3-methoxy-2, 2-dimethylpropionic acid, fatty acid methyl ester polyoxyethylene ether and sodium dodecyl benzene sulfonate.

Through adopting above-mentioned technical scheme, the hydrophilic performance that is used for further improving plastics of addition of hydrophilic agent, hydrophilic agent have very strong infiltration ability, with coupling agent effect back, can increase the wettability of plastic product, and then increase the hydrophilic performance of plastic product, introduce active functional group to the plastic product surface simultaneously, and then improve the cohesion between plastic product and the metal coating, and then improve the mechanical properties of plastic product cladding material structure.

Preferably, the hydrophilic agent consists of 3-methoxy-2, 2-dimethylpropionic acid, fatty acid methyl ester polyoxyethylene ether and sodium dodecyl benzene sulfonate according to the mass ratio of (2-3) to (3-5) to (4-6).

Through adopting above-mentioned technical scheme, carried out further optimization to the proportion of each component of hydrophilic agent to make the collocation of each component more reasonable, thereby increase the hydrophilic agent to the treatment effect of plastic product, improve the hydrophilic of plastic product and with other cladding materials between the cohesion, and then make the plastic surface coating corrosion resistance who makes stronger.

Preferably, the thickness of the transparent silicon dioxide thin film layer is 800-900 μm.

Through adopting above-mentioned technical scheme, optimize the thickness on transparent silica thin layer to make transparent silica thin layer and nickel plating layer cohesion better, be difficult for droing, simultaneously, the thickness on transparent silica thin layer observes the influence less to the colour layer on the plastics, does not influence the show on colour layer, simultaneously, can reduce the colour layer and appear.

In a second aspect, the present application provides a method for preparing a plastic surface coating structure, which adopts the following technical scheme: a preparation method of a plastic surface coating structure comprises the following steps:

(1) plastic product pretreatment: carrying out hydrocarbon vacuum oil removal and drying treatment on the plastic product, treating the plastic product by using a surface treating agent, and drying to obtain a first plastic product;

(2) pre-metallization of plastic products: plating a conductive metal layer on the first plastic product obtained in the step (1) to obtain a second plastic product;

(3) electroplating nickel on the plastic product: electroplating nickel on the plastic product II obtained in the step (2) to obtain a plastic product III;

(4) electroplating a functional layer on the plastic product: plating a PVD color layer and a transparent silicon dioxide thin film layer on the plastic product III obtained in the step (3).

Through adopting above-mentioned technical scheme, plastic goods can fully contact with surface treatment agent after hydrocarbon vacuum deoiling and stoving to improve the processing condition of surface treatment agent to plastic goods, make plastic goods when electroplating, more stable, inhale simultaneously and plate the ability increase, plastic goods is through surface treatment agent processing back, and hydrophilic performance increases, and then makes the cohesion increase of cladding material, and then improves the mechanical properties of cladding material.

Preferably, the method for processing the plastic product by the surface treatment agent in the step (1) comprises the following steps: immersing the plastic product in the surface treating agent for 40-50min, ultrasonically cleaning in clear water for 7-8min after soaking, then placing on oxidizing flame for calcining for 1-2min, and cleaning with clear water and drying in the air.

By adopting the technical scheme, the plastic product after being deoiled and dried is immersed in the surface treatment agent for soaking, so that the hydrophilic performance of the plastic product can be improved, and simultaneously, the surface treatment agent interacts with the surface of the plastic product, and active groups in the surface treatment agent are introduced into the surface of the plastic product, so that the viscosity of the plastic product is improved, the binding force with metal is enhanced, and the suction plating capacity of the plastic product is improved.

In summary, the present application has the following beneficial effects:

1. the binding force of the plastic surface coating structure treated by the surface treating agent and the conductive metal layer is better, the hydrophilic performance of the plastic product is obviously improved, the stability is better, the adsorption and plating capacity is enhanced, and the binding force of the coating is improved.

2. The utility model provides a plastic surface coating structure is through plating transparent silica thin layer to can increase the stability of plastic surface coating structure, isolated colour layer and external, thereby reduce the corruption and the wearing and tearing condition on colour layer, simultaneously, silica thin layer is transparent, and does not influence the ornamental performance of plastic goods.

Detailed Description

The present application will be described in further detail with reference to examples.

The plastic product is any one of acrylonitrile-butadiene-styrene (ABS), polycarbonate, nylon 66, polyphenyl ether and polybutylene terephthalate, and more preferably, the plastic product is polycarbonate.

The preparation method of the plastic surface coating structure comprises the following steps:

(1) plastic product pretreatment: carrying out hydrocarbon vacuum oil removal and drying treatment on the plastic product, then placing the dried plastic product into a conventional chromium-sulfur mixed acid washing solution for coarsening for 12min at 70 ℃, then washing with clear water, then continuously drying, treating with a surface treating agent, and drying to obtain a plastic product I;

(2) pre-metallization of plastic products: plating a conductive metal layer on the first plastic product obtained in the step (1) to obtain a second plastic product;

(3) electroplating nickel on the plastic product: electroplating nickel on the plastic product II obtained in the step (2) to obtain a plastic product III;

(4) electroplating a functional layer on the plastic product: plating a PVD color layer and a transparent silicon dioxide thin film layer on the plastic product III obtained in the step (3).

Wherein, the polycarbonate is subjected to hydrocarbon vacuum oil removal and drying treatment, the oil removal time is 3-8min, the vacuum drying time is 5-15min, and the drying temperature is 65-120 ℃. Further preferably, the oil removing time is 5min, the vacuum drying time is 10min, and the drying temperature is 100 ℃.

Wherein, the chromium-sulfur mixed acid washing liquid comprises the following raw materials in concentration: chromic anhydride 400g/L and sulfuric acid 380 g/L.

The preparation method of the surface treating agent comprises the following steps: the plasticizer, the lauryl sodium sulfate, the coupling agent and the water are mixed and stirred uniformly.

The method for treating the polycarbonate by the surface treating agent comprises the following steps: cooling the surface treating agent to 30-40 ℃, immersing the polycarbonate subjected to the hydrocarbon vacuum oil removal treatment in the surface treating agent for 40-50 min; taking out clear water to wash for 4-5min after soaking, then immersing in clear water to soak for 15-18min, and then ultrasonically cleaning for 7-8min, wherein the ultrasonic frequency is 30KHz-40 KHz; and immersing the cleaned polycarbonate in sodium dodecyl sulfate for 35-45min, taking out the polycarbonate after immersion, washing with clear water for 4-5min, then ultrasonically cleaning for 15-18min, then calcining on oxidizing flame for 1-2min, cleaning with clear water, and then drying.

Wherein, the conductive metal layer is plated by depositing a titanium metal layer with the thickness of 0.05 μm in a magnetron sputtering mode, and then sputtering and depositing a metal copper layer with the thickness of 0.45 μm.

Wherein, the electroplating nickel is divided into three parts, and the watt nickel electroplating, the bright nickel electroplating and the micropore nickel electroplating are sequentially carried out on the plastic product II, the watt nickel electroplating adopts a known watt nickel formula for electroplating, the thickness of a watt nickel layer is 1-1.5 mu m, the bright nickel electroplating adopts a known bright nickel formula for electroplating, the thickness of a bright nickel layer is 3-5 mu m, the micropore nickel electroplating adopts a known micropore nickel formula for electroplating, and the thickness of a micropore nickel layer is 1-1.5 mu m.

Wherein, the formula of the watt nickel is as follows: 350g/L of nickel sulfate, 30-35g/L of nickel chloride and 30-35g/L of boric acid.

Wherein, bright nickel formula is: 280g/L of nickel chloride, 40g/L of boric acid, 36g/L of magnesium chloride, 0.48g/L of saccharin and 1g/L of sodium dodecyl sulfate.

Wherein, the formula of the microporous nickel is as follows: 400g/L of nickel sulfate 300-400g/L, 50-60g/L of nickel chloride, 40-45g/L of boric acid, 0.4-0.5g/L of 1, 4-butynediol, 2.5-3g/L of saccharin, 0.15-0.2g/L of polyethylene glycol and 10-25g/L of aluminum oxide.

Wherein, the PVD color layer is plated by a magnetron sputtering method.

The transparent silicon dioxide film is obtained through a sol-gel method, tetraethoxysilane, water, ethanol and hydrochloric acid are uniformly mixed at 70 ℃, the mixture is continuously stirred until the viscosity of the solution is increased to form gel, wherein the volume ratio of the tetraethoxysilane to the water to the ethanol to the hydrochloric acid is 15:5:40:0.07, the plastic product plated with the PVD color layer is put into the gel solution, immersed for 4min and then taken out, and the gel is dried.

The surface treating agent also comprises 5-6 parts by weight of an auxiliary agent, wherein the auxiliary agent is at least two of 2,2 '-methylene bis (4, 6-di-tert-butylphenol), maleic anhydride grafted polypropylene and silver-plated copper powder, and the auxiliary agent is further preferably composed of 2, 2' -methylene bis (4, 6-di-tert-butylphenol), maleic anhydride grafted polypropylene and silver-plated copper powder according to the mass ratio of (1-3) to (2-4) to (4-6).

Preferably, the solid content of the perfluoroalkyl phenoxysulfonic vinyl ether is (98 +/-2)%, the foaming force is 120mm, the viscosity is 200-³。

Preferably, the content of the effective substance of the acetyl tributyl citrate is 99 percent, and the CAS number is 77-90-7.

Preferably, the cyclohexane-1, 2-dicarboxylic acid diisooctyl ester has a CAS number of 84-71-9.

Preferably, ethylene glycol butyl ether has a CAS number of 111-76-2.

Preferably, the sodium lauryl sulfate has a purity of 99.0% and a CAS number of 151-21-3.

Preferably, 3- (2, 3-glycidoxy) propyltrimethoxysilane has a CAS number of 2530-83-8.

Preferably, isopropyl tris (dioctyl pyrophosphato acyloxy) titanate has a CAS number of 67691-13-8.

Preferably, 3-methoxy-2, 2-dimethylpropionic acid has a CAS number of 64241-78-7.

Preferably, the purity of the fatty acid methyl ester polyoxyethylene ether is 98 percent, and the CAS number is 65218-33-7.

Preferably, sodium dodecylbenzenesulfonate has a CAS number of 25155-30-0.

Preferably, the grafting rate of the maleic anhydride grafted polypropylene is 1-1.2%, and the melt index is 100g/10 min.

Preferably, the 2, 2' -methylenebis (4, 6-di-tert-butylphenol) has an active substance content of 99.5% and a CAS number of 14362-12-0.

Preferably, the granularity of the silver-plated copper powder is 800 meshes, and the copper content is more than or equal to 3 percent.

TABLE 1 raw material specification, type and manufacturer

Raw materials	Specification and model	Manufacturer of the product
			Acetyl tributyl citrate	ATBC	Foshan Jinjia New Material Technology Co.,Ltd.
Cyclohexane-1, 2-dicarboxylic acid diisooctyl ester	99％	Wuhanpeng base Biotech Co Ltd
			Ethylene glycol butyl ether	99.0％	Shanghai Jizhi Biochemical Technology Co.,Ltd.
Sodium dodecyl sulfate	74255	Merck official flagship store
			3- (2, 3-glycidoxy) propyltrimethoxysilane	98.5％	HUANGSHAN VIOLET BIOTECHNOLOGY Co.,Ltd.
Isopropyl tris (dioctyl pyrophosphate acyloxy) titanate	98％	Hubei Longxin chemical industry Co Ltd
			Perfluoroalkyl phenoxysulfonic vinyl ethers	FCF-204	GUANGZHOU SHUNRUN NEW MATERIAL TECHNOLOGY Co.,Ltd.
3-methoxy-2, 2-dimethylpropionic acid	98％	Shanghai Jinjinle industry Co Ltd
			Fatty acid methyl ester polyoxyethylene ether	S12707315	Shandong Youso chemical technology Co Ltd
Sodium dodecyl benzene sulfonate	2021010	Jinan Hongde chemical industries, Ltd
			2, 2' -methylenebis (4, 6-di-tert-butylphenol)	pwf2246a	Flower climbing chemical strength store
Maleic anhydride grafted polypropylene	332K	Shenzhen Haian plastics chemical Co Ltd
			Silver-plated copper powder	1	Tenghuake official flagship store

Examples

Example 1

The plastic surface coating structure of this embodiment is conductive metal layer, electroplated nickel layer, PVD colour layer, transparent silica thin film layer in proper order from the plastic surface layer, and the plastic goods is handled through surface treatment agent, and surface treatment agent comprises the raw materials of following weight: 5kg of plasticizer, 5kg of lauryl sodium sulfate, 10kg of coupling agent and 50kg of water, wherein the plasticizer comprises tributyl acetylcitrate and cyclohexane-1, 2-diisooctyl diformate in a mass ratio of 2:3, the coupling agent comprises 3- (2, 3-glycidoxy) propyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate in a mass ratio of 4:2, the thickness of the conductive metal layer is 3 microns, the thickness of the transparent silicon dioxide film layer is 500 microns, the thickness of the nickel layer is 5 microns, and the thickness of the PVD color layer is 0.5 microns.

The preparation method of the plastic surface coating structure of the embodiment includes the following steps:

(1) plastic product pretreatment: carrying out hydrocarbon vacuum oil removal and drying treatment on the plastic product, wherein the oil removal time is 5min, the vacuum drying time is 10min, the drying temperature is 100 ℃, then placing the dried plastic product into a conventional chromium-sulfur mixed acid washing solution, coarsening for 12min at 70 ℃, then washing with clear water, continuing drying, then treating with a surface treating agent, and drying to obtain a plastic product I;

(2) pre-metallization of plastic products: depositing a 0.05 mu m thick titanium metal layer on the plastic product I obtained in the step (1) by adopting a magnetron sputtering mode, and then sputtering and depositing a 0.45 mu m thick metal copper layer, thereby plating a conductive metal layer on the plastic product I to obtain a plastic product II;

(3) electroplating nickel on the plastic product: electroplating nickel on the plastic product II obtained in the step (2), performing watt nickel electroplating to obtain a watt nickel layer with the thickness of 1 mu m, performing bright nickel electroplating on the watt nickel layer to obtain a bright nickel layer with the thickness of 3 mu m, performing microporous nickel electroplating on the bright nickel layer to obtain a microporous nickel layer with the thickness of 1 mu m, and thus obtaining a plastic product III;

(4) electroplating a functional layer on the plastic product: plating a PVD color layer and a transparent silicon dioxide thin film layer on the plastic product III obtained in the step (3), plating the PVD color layer on the plastic product III by a magnetron sputtering method, and plating the color layer by a solution gel method to obtain the transparent silicon dioxide thin film layer.

The preparation method of the surface treating agent of the embodiment comprises the following steps: and mixing and stirring the plasticizer, the lauryl sodium sulfate, the coupling agent and the water uniformly according to the proportion.

The method for processing the plastic product by the surface treatment agent comprises the following steps: cooling the surface treating agent to 35 ℃, immersing the polycarbonate subjected to the hydrocarbon vacuum oil removal treatment in the surface treating agent, and soaking for 45 min; taking out clear water to wash for 5min after soaking, then immersing in clear water to soak for 16min, and then ultrasonically cleaning for 8min, wherein the ultrasonic frequency is 40 KHz; and (3) immersing the cleaned polycarbonate in sodium dodecyl sulfate for 45min, taking out the polycarbonate after immersion, washing with clear water for 5min, then performing ultrasonic cleaning for 18min, placing on oxidizing flame for calcining for 2min after washing, and drying after cleaning with clear water.

Example 2

The plastic surface coating structure of this embodiment is conductive metal layer, electroplated nickel layer, PVD colour layer, transparent silica thin film layer in proper order from the plastic surface layer, and the plastic goods is handled through surface treatment agent, and surface treatment agent comprises the raw materials of following weight: 10kg of plasticizer, 10kg of sodium dodecyl sulfate, 15kg of coupling agent and 60kg of water, wherein the plasticizer comprises tributyl acetylcitrate and cyclohexane-1, 2-diisooctyl phthalate according to the mass ratio of 2:3, the coupling agent comprises 3- (2, 3-glycidoxy) propyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of 4:2, the thickness of the conductive metal layer is 5 microns, the thickness of the transparent silicon dioxide film layer is 1200 microns, the thickness of the nickel layer is 8 microns, and the thickness of the PVD color layer is 1 micron.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 1.

The preparation method of the surface treating agent of this example is exactly the same as that of example 1.

The method for processing the plastic product of this embodiment by the surface treatment agent is exactly the same as that of embodiment 1.

Example 3

The plastic surface coating structure of this embodiment is conductive metal layer, electroplated nickel layer, PVD colour layer, transparent silica thin film layer in proper order from the plastic surface layer, and the plastic goods is handled through surface treatment agent, and surface treatment agent comprises the raw materials of following weight: 7kg of plasticizer, 7kg of lauryl sodium sulfate, 12kg of coupling agent, 7kg of hydrophilic agent, 5kg of auxiliary agent and 60kg of water, wherein the plasticizer comprises acetyl tributyl citrate and cyclohexane-1, 2-diisooctyl phthalate according to the mass ratio of 2:3, the coupling agent comprises 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of 4:2, the hydrophilic agent comprises 3-methoxy-2, 2-dimethyl propionic acid and fatty acid methyl ester polyoxyethylene ether according to the mass ratio of 1:2, the auxiliary agent comprises 2, 2' -methylene bis (4, 6-di-tert-butylphenol), maleic anhydride grafted polypropylene and silver-plated copper powder according to the mass ratio of 1:2:4, the thickness of the conductive metal layer is 4 mu m, the thickness of the transparent silicon dioxide film layer is 800 mu m, the thickness of the nickel layer is 6 μm, and the thickness of the PVD color layer is 0.7 μm.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 2.

The preparation method of the surface treating agent of the embodiment comprises the following steps: the plasticizer, the lauryl sodium sulfate, the coupling agent, the hydrophilic agent, the auxiliary agent and the water are mixed and stirred uniformly according to the proportion.

The method for processing the plastic product with the surface treating agent in this embodiment is completely the same as that in embodiment 2.

Example 4

The plastic surface coating structure of this embodiment is conductive metal layer, electroplated nickel layer, PVD colour layer, transparent silica thin film layer in proper order from the plastic surface layer, and the plastic goods is handled through surface treatment agent, and surface treatment agent comprises the raw materials of following weight: 8kg of plasticizer, 7kg of lauryl sodium sulfate, 13kg of coupling agent, 8kg of hydrophilic agent, 6kg of auxiliary agent and 60kg of water, wherein the plasticizer comprises acetyl tributyl citrate and cyclohexane-1, 2-diisooctyl phthalate according to the mass ratio of 2:3, the coupling agent comprises 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate according to the mass ratio of 4:6, the hydrophilic agent comprises 3-methoxy-2, 2-dimethyl propionic acid, fatty acid methyl polyoxyethylene ether and sodium dodecyl benzene sulfonate according to the mass ratio of 2:3:4, the auxiliary layer comprises 2, 2' -methylene bis (4, 6-di-tert-butylphenol), maleic anhydride grafted polypropylene and silver-plated copper powder according to the mass ratio of 1:2:4, and the thickness of the conductive metal layer is 4 mu m, the thickness of the transparent silicon dioxide film layer is 900 micrometers, the thickness of the nickel layer is 7 micrometers, and the thickness of the PVD color layer is 0.7 micrometers.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 3.

The preparation method of the surface treating agent of this example is exactly the same as that of example 3.

The method for processing the plastic product with the surface treating agent is exactly the same as that of the embodiment 3.

Example 5

This embodiment is different from embodiment 4 in that: the plasticizer consists of acetyl tributyl citrate, cyclohexane-1, 2-dioctyl phthalate and ethylene glycol butyl ether according to the mass ratio of 2:4:5, and the rest is completely the same as the plasticizer in the embodiment 4.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 4.

The preparation method of the surface treating agent of this example is exactly the same as that of example 4.

The method for processing the plastic product of this embodiment by the surface treatment agent is exactly the same as that of embodiment 4.

Example 6

This embodiment is different from embodiment 4 in that: the plasticizer consists of acetyl tributyl citrate, cyclohexane-1, 2-dioctyl phthalate and ethylene glycol butyl ether according to the mass ratio of 3:6:8, and the rest is completely the same as the plasticizer in the embodiment 4.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 4.

The preparation method of the surface treating agent of this example is exactly the same as that of example 4.

The method for processing the plastic product of this embodiment by the surface treatment agent is exactly the same as that of embodiment 4.

Example 7

This embodiment is different from embodiment 4 in that: the plasticizer consists of acetyl tributyl citrate, cyclohexane-1, 2-dioctyl phthalate and ethylene glycol butyl ether according to the mass ratio of 3:5:6, and the rest is completely the same as the plasticizer in the embodiment 4.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 4.

The preparation method of the surface treating agent of this example is exactly the same as that of example 4.

The method for processing the plastic product of this embodiment by the surface treatment agent is exactly the same as that of embodiment 4.

Example 8

This embodiment is different from embodiment 7 in that: the coupling agent consists of 3- (2, 3-glycidoxy) propyl trimethoxy silane and perfluoroalkyl phenoxy sulfonic vinyl ether according to the mass ratio of 4:2, and the rest is completely the same as the embodiment 7.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 7.

The preparation method of the surface treating agent of this example was exactly the same as that of example 7.

The method of treating the plastic product with the surface treating agent is exactly the same as that of example 7.

Example 9

This embodiment is different from embodiment 7 in that: the coupling agent consists of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and perfluoroalkyl phenoxysulfonic vinyl ether according to the mass ratio of 6:3, and the rest is completely the same as the embodiment 7.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 7.

The preparation method of the surface treating agent of this example was exactly the same as that of example 7.

The method of treating the plastic product with the surface treating agent is exactly the same as that of example 7.

Example 10

This embodiment is different from embodiment 7 in that: the coupling agent consists of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and perfluoroalkyl phenoxy sulfonic vinyl ether according to the mass ratio of 1:3:2, and the rest is completely the same as that in the embodiment 7.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 7.

The preparation method of the surface treating agent of this example was exactly the same as that of example 7.

The method of treating the plastic product with the surface treating agent is exactly the same as that of example 7.

Example 11

This embodiment is different from embodiment 7 in that: the coupling agent consists of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and perfluoroalkyl phenoxy sulfonic vinyl ether according to the mass ratio of 2:4:3, and the rest is completely the same as that in the embodiment 7.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 7.

The preparation method of the surface treating agent of this example was exactly the same as that of example 7.

The method of treating the plastic product with the surface treating agent is exactly the same as that of example 7.

Example 12

This embodiment is different from embodiment 11 in that: the hydrophilic agent consists of 3-methoxy-2, 2-dimethylpropionic acid, fatty acid methyl ester polyoxyethylene ether and sodium dodecyl benzene sulfonate according to the mass ratio of 3:5:6, and the rest is completely the same as that in the embodiment 11.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 11.

The preparation method of the surface treating agent of this example was exactly the same as that of example 11.

The method of treating the plastic product with the surface treating agent is exactly the same as that of example 11.

Example 13

The present embodiment is different from embodiment 12 in that: the auxiliary agent consists of 2, 2' -methylene bis (4, 6-di-tert-butylphenol), maleic anhydride grafted polypropylene and silver-plated copper powder according to the mass ratio of 3:4:6, and the rest is completely the same as that in the example 12.

The preparation method of the plastic surface plating structure of this embodiment is completely the same as that of embodiment 12.

The preparation method of the surface treating agent of this example was exactly the same as that of example 12.

The method for processing the plastic product with the surface treating agent in this embodiment is exactly the same as that in embodiment 12.

Comparative example

The plastic surface coating structure of the comparative example comprises a conductive metal layer, an electroplated nickel layer and a PVD color layer in sequence from a plastic surface layer, wherein the thickness of the nickel layer is 5 mu m, the thickness of the PVD color layer is 0.5 mu m, and the thickness of the conductive metal layer is 3 mu m.

The preparation method of the plastic surface coating structure of the comparative example comprises the following steps:

(1) plastic product pretreatment: carrying out hydrocarbon vacuum oil removal and drying treatment on the plastic product, wherein the oil removal time is 5min, the vacuum drying time is 10min, the drying temperature is 100 ℃, after drying, coarsening the plastic product for 12min at 70 ℃ in a conventional chromium-sulfur mixed acid washing solution, then washing with clean water and drying to obtain a first plastic product;

(2) pre-metallization of plastic products: depositing a 0.05 mu m thick titanium metal layer on the plastic product I obtained in the step (1) by adopting a magnetron sputtering mode, and then sputtering and depositing a 0.45 mu m thick metal copper layer, thereby plating a conductive metal layer on the plastic product I to obtain a plastic product II;

(3) electroplating nickel on the plastic product: electroplating nickel on the plastic product II obtained in the step (2), performing watt nickel electroplating to obtain a watt nickel layer with the thickness of 1 mu m, performing bright nickel electroplating on the watt nickel layer to obtain a bright nickel layer with the thickness of 4 mu m, performing microporous nickel electroplating on the bright nickel layer to obtain a microporous nickel layer with the thickness of 1 mu m, and thus obtaining a plastic product III;

(4) electroplating a functional layer on the plastic product: plating a PVD color layer on the plastic product III obtained in the step (3), and plating the PVD color layer on the plastic product III by a magnetron sputtering method to obtain the product.

Performance test

Detection method brittleness test: the plastic surface coating structures of examples 1 to 13 and comparative example were heated in a muffle furnace at 200 ℃ for 2 hours, then quenched in room temperature water, and observed for the presence of peeling of the coating structure. Apparent state of the plating layer: the apparent state of the coating is judged by observing whether the surface of the coating is complete or not, and whether the surface of the coating has bubbles, burns, pinholes and the like, and the test results are shown in Table 2.

And (3) detecting the binding force: the plastic surface coating structures of examples 1 to 13 and comparative examples were taken, a smooth metal block was repeatedly rubbed against the coating structure for 15 to 50 seconds at an appropriate pressure, and then whether the coating structure was peeled off was observed with a 5-fold magnifying glass, and the test results are shown in table 2.

TABLE 2 Properties of the plastic surface coating structures of examples 1-13 and comparative examples

The coating condition was rated on a scale of 1 to 5 in conjunction with the adhesion test, 1 for poor, 2 for slightly poor, 3 for medium, 4 for good, and 5 for excellent.

By combining the example 1 and the comparative example and combining the table 2, it can be seen that the plating layer prepared by the comparative example is easy to fall off, and the plating absorbing capacity of the plastic product is not good, compared with the comparative example, after the plastic product of the example 1 is treated by the surface treating agent, the plating absorbing capacity of the plastic product is increased, so that the bonding force with the plating layer is good, and the falling off is not caused.

In combination with examples 1 to 4 and table 2, it can be seen that the ratio of each component in the surface treatment agent is changed and optimized, so that the falling off of the coating on the plastic product can be reduced, and the bonding force between the plastic product and the coating is improved.

In combination with examples 4-13 and Table 2, it can be seen that changing the components in the coupling agent has a greater effect on the bonding force between the plastic product and the coating, and that changing the finished product in the plasticizer also has an effect on the bonding force between the plastic product and the coating.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.