CN110424014B

CN110424014B - Plastic product and method for selectively metallizing surface of plastic substrate

Info

Publication number: CN110424014B
Application number: CN201910696729.XA
Authority: CN
Inventors: 曾庆明; 孙宇曦; 宋亦健; 李友
Original assignee: Guangdong Shuocheng Technology Co ltd
Current assignee: Guangdong Shuocheng Technology Co ltd
Priority date: 2019-07-30
Filing date: 2019-07-30
Publication date: 2022-03-15
Anticipated expiration: 2039-07-30
Also published as: CN110424014A

Abstract

The invention provides a plastic film product, wherein at least three layers of metal films are deposited on the plastic film product and respectively comprise a bonding layer, a chemical layer and a protective layer; the bonding layer consists of a bonding plastic layer and a bonding metal layer; the bonding layer has a thickness of 2-500 nm.

Description

Plastic product and method for selectively metallizing surface of plastic substrate

Technical Field

The invention relates to a plastic surface treatment method, in particular to a plastic film product and a plastic substrate surface selective metallization method.

Background

The common methods for carrying out metallization modification on the surface of plastic comprise: chemical treatment, vacuum plating, spraying, and doping metal powder or metal salt into the material. The metal film coating obtained by vacuum plating and spray plating is extremely thin, and the conductivity, shielding performance and wear resistance are poor; the method for doping metal powder or metal salt into the high polymer material has the disadvantages of troublesome operation, high cost, poor decorative performance and few applications; the chemical treatment method is a common method, has wide application range, and has the advantages of strong decoration, good binding force, excellent conductivity, controllable thickness of the metal layer and the like.

Articles made from nonconductive plastic can be metallized by electroless metallization processes. In this method, the article is first cleaned and etched, then treated with a noble metal and finally metallized. The etching is typically performed by chromic sulfuric acid. Etching is used to make the surface of the article receptive to subsequent metallization, so that the surface of the article is well wetted with the corresponding solution in subsequent processing steps, and the deposited metal eventually has a sufficiently strong adhesion on the surface.

Chemical nickel belongs to an autocatalysis system, is particularly sensitive to metal palladium and is easy to self-decompose, and metal palladium is used as a catalyst in the mature process of plastic surface metallization at the present stage, so that the requirement on the stability of the process for chemical nickel deposition is high, and solution decomposition can be caused by carelessness, so that a chemical nickel stabilizer must be added in the using process. The conventional chemical nickel stabilizer adopts high-pollution heavy metals such as lead, cadmium, mercury, thallium and the like, which does not meet the environmental protection requirement of the current society.

The practical application of the metallizable plastic in the prior art has great limitation, most of the non-electroplating-grade conventional plastics cannot be metallized, and the metallizable electroplating-grade plastic can only be metallized completely, so that the metallization selectivity is difficult to realize, and the technical problem of influencing the industry development is solved. For example, plastics such as PC, PET, PMMA, etc. are difficult to be metallized, and for conventional electroplating grade plastics, only the whole surface of the plastics can be metallized, and the selectivity of metallization is difficult to be realized.

Disclosure of Invention

The invention provides a plastic film product, wherein at least three layers of metal films are deposited on the plastic film product and respectively comprise a bonding layer, a chemical layer and a protective layer; the bonding layer consists of a bonding plastic layer and a bonding metal layer;

the bonding layer has a thickness of 2-500 nm.

As an embodiment of the present invention, the bonding layer has a thickness of 2 to 50 nm.

In one embodiment of the present invention, the thickness of the plastic film is 2 to 1000. mu.m.

In one embodiment of the present invention, the thickness of the plastic film is 2 to 100. mu.m.

The second aspect of the present invention provides a method for preparing the above plastic film product, comprising the steps of:

s01, metallizing the surface of the non-metal layer by a vacuum plating method to form a bonding layer;

s02, forming a chemical layer on the surface of the bonding layer by adopting a chemical plating mode;

and S03, forming a protective layer on the surface of the chemical layer by adopting an electroplating film plating mode.

As an embodiment of the invention, the coating step of the electroless plating at least comprises one or more of copper plating and the following steps in combination;

the combination of steps comprises:

bulking, degumming, neutralizing, adjusting, activating and pretreating, activating and reducing.

the combination of steps comprises: and (4) activating and reducing.

In one embodiment of the present invention, the raw material for preparing the metal thin film is selected from one or more of Ni, Co, Cr, Mn, and Cu.

As an embodiment of the present invention, the raw material for preparing the bonding layer is selected from one or more of Ni, Co, Cr, and Mn.

The third aspect of the invention provides the plastic film product, which is applied to the field of electromagnetic signal conduction.

Has the advantages that: according to the plastic product, the surface of the plastic film bottom layer, which is used for contacting the metal coating, is treated, so that the bonding strength between the plastic film bottom layer and metal is improved, good adhesion between the metal layer and the plastic film bottom layer is realized, a two-layer coating structure is adopted, the production efficiency is improved, and the production cost is reduced.

Detailed Description

The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

The invention provides in a first aspect a plastic film article having deposited thereon at least three layers of metal film, respectively a bonding layer, a chemical layer and a protective layer; the bonding layer consists of a bonding plastic layer and a bonding metal layer;

the bonding layer has a thickness of 2-500 nm.

Plastic film

As an embodiment of the present invention, the plastic is selected from one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polymethacrylate, polyethylene terephthalate, polybutylene terephthalate, or polyurethane.

From the viewpoint of improving the bonding force between the non-metal layer and the metal layer, the plastic is selected from one of polypropylene, polyethylene and polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate and polyurethane.

From the perspective of reducing the light transmittance of the metalized product, the non-metal layer is made of a plastic film, and the thickness of the plastic film is 2-1000 microns; more preferably 2 to 100 μm.

The second aspect of the present invention provides a method for preparing the above plastic film product, which is characterized by comprising the following steps:

Vacuum plating

Vacuum plating mainly comprises several types of vacuum evaporation, sputtering plating and ion plating, and all of them adopt the mode of depositing various metal and non-metal films on the surface of plastic parts by distillation or sputtering under the vacuum condition, so that it can obtain very thin surface coating.

The invention mainly adopts a sputtering coating mode to carry out metallization to form a bonding layer.

Sputter coating

Common sputtering coating methods mainly include direct current sputtering, radio frequency sputtering, magnetron sputtering, and reactive sputtering.

In the present invention, the sputter coating may be any sputter coating known to those skilled in the art, and by way of example, magnetron sputtering, in the present invention, the specific operation steps of magnetron sputtering are as follows:

in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, the non-metallic material is coated, the voltage of the bias power supply is set to be 80-180V, the duty ratio of the bias power supply is set to be 30-50%, the current of the medium-frequency power supply is set to be 15A-25A, the argon flow is set to be 150 plus one 180Sccm, the reaction gas flow is gradually added according to the requirement of a film system, the film coating time is set according to the requirements of the film system and the film thickness, the vacuum degree is reduced to be 2.3 multiplied by 10^-1Pa；

After the film coating is finished, various pump valves are closed in sequence according to the operation specifications of the magnetron sputtering film coating machine, and the product is taken out after the gas is discharged and the door is opened.

In the invention, a metal layer formed by sputtering coating is used as a bonding layer; the bonding layer is composed of a bonding plastic layer and a bonding metal layer.

The preparation raw material of the bonding layer is selected from one or more of Ni, Co, Cr and Mn.

Chemical plating

Electroless plating, also known as electroless plating or autocatalytic plating, is a plating method in which metal ions in a plating solution are reduced to metal by means of a suitable reducing agent in the absence of an applied current and deposited onto the surface of a part.

Electroless plating is a deposition process that produces metal by a controlled redox reaction under the catalytic action of the metal. Compared with electroplating, the chemical plating technology has the characteristics of uniform plating layer, small pin holes, no need of direct-current power supply equipment, capability of depositing on a non-conductor, certain special properties and the like.

In one embodiment of the present invention, the chemical layer formed by the electroless plating is a copper film.

the combination of steps comprises:

the combination of steps comprises: and (4) activating and reducing.

Bulkiness

Lofting is a prerequisite to provide a uniform, desirable cell wall for subsequent steps.

The leavening agent used in the invention consists of water, leavening additive and pH correction agent; and each liter of leavening agent contains 849ml of water, 150ml of leavening additive and 1ml of pH correction agent.

The leavening additive consists of 30-100g/L of N-methyl pyrrolidone, 40-60g/L of sodium hydroxide and 30-100g/L of DMF.

The pH correction agent is a 32 wt% sodium hydroxide solution.

The bulking treatment steps are as follows:

placing the object to be treated in the leavening solution for 45-110s, wherein the temperature of the leavening solution is 70-80 ℃.

The leavening solution is a mixture of leavening agent and water, and 150ml of leavening additive is contained in 1 liter of leavening solution.

The pH value of the leavening solution is 10-12.

Degumming

The glue removal is mainly used for efficiently cleaning hole walls and drilling residues and effectively preventing the separation of the hole walls; meanwhile, the bonding force between the hole wall and the base material can be effectively increased, and the separation risk is reduced.

The degumming agent used in the invention consists of water, a degumming additive and a pH regulator; and each liter of leavening agent contains 770ml of water, 125ml of degumming additive and 105ml of pH adjusting agent.

The degumming additive is permanganate, and sodium permanganate is preferred.

The pH regulator is 32% sodium hydroxide solution, and the 32% sodium hydroxide solution is 432g/L NaOH.

The glue removing treatment steps are as follows:

and placing the object to be treated in the degumming solution for 90-300s, wherein the temperature of the degumming solution is 75-85 ℃.

The degumming solution is a mixture of degumming agent and water, and 50g of degumming additive is contained in 1 liter of degumming solution; 1 liter of the degumming solution contained 45g of NaOH.

Neutralization

In the invention, the neutralization is to neutralize the acidic substances in the degumming process, so that the binding force is improved.

The neutralizer used in the invention consists of water, sulfuric acid, hydrogen peroxide and a neutralizing additive; and contains 860ml of water, 100ml of 50 wt.% sulfuric acid and 15ml of 35 wt.% H per liter of neutralizing agent₂O₂。

The neutralization treatment steps are as follows:

and placing the object to be treated in the neutralizing solution for 35-60s, wherein the temperature of the neutralizing solution is 25-35 ℃.

The neutralization solution is a mixture of a neutralizing agent and water, and 100ml of 50 wt% sulfuric acid is contained in 1 liter of the neutralization solution; 15ml of 35 wt% H₂O₂。

Adjustment of

The adjustment is to effectively remove residues of the degumming residue in the hole and adjust the charge of the hole wall, so that the hole wall becomes a surface with extremely strong adsorption capacity, and an ideal hole wall treatment effect is provided for subsequent copper plating.

The regulator used in the invention consists of water and a regulating additive; and each liter of conditioning agent contains 960ml of water, 40ml of conditioning additive.

The adjusting additive is selected from one of dopamine, dopamine hydrochloride, pyrrole, alcohol amine or nitrate.

The adjusting processing steps are as follows:

and placing the object to be treated in the adjusting solution for 60s, wherein the temperature of the adjusting solution is 50 ℃.

Activation pretreatment

In the invention, the activation pretreatment is mainly used for treating pollutants in the holes before activation and adjusting electric charge to prepare for subsequent activation.

In the invention, the activation pretreatment agent is a sodium chloride solution, and each 1 liter of the activation pretreatment agent contains 980ml of water, 10ml of sodium chloride and 10ml of activation pretreatment additive.

The activating pretreatment additive is one of tartrate, citrate, ethylene diamine tetraacetic acid salt, nitrilotriacetate and triethanolamine.

The treatment steps of the activation pretreatment are as follows:

and (3) placing the object to be treated in the activation pretreatment agent for 20s, wherein the temperature of the neutralization solution is 25 ℃.

Activation of

The activation treatment in the invention is to activate the hole wall with adjusted charge so as to provide the best condition for good coverage of the subsequent copper plating.

The activating agent used in the invention consists of water, an activating additive and an alkaline substance; and each liter of activator contains 774ml of water, 225ml of activating additive and 1ml of sodium hydroxide solution.

The concentration of the sodium hydroxide solution was 32 wt%.

As an embodiment of the present invention:

the activating additive is a main component and an auxiliary agent; the weight ratio of the two is 10: 1.

the main component is palladium sulfate, and the auxiliary agent is ethylenediamine tetraacetic acid or ethylenediamine.

The process steps for the activation are now as follows:

placing the object to be treated in an activating solution for 45s, wherein the temperature of the activating solution is 45 ℃; the pH was 10.0.

As another embodiment of the present invention:

the main component is silver nitrate, and the auxiliary agent is sodium hypophosphite or EDTA disodium.

The process steps for the activation are now as follows:

placing the object to be treated in an activating solution for 45s, wherein the temperature of the activating solution is 45 ℃; the pH value is 3-6.

Activation reduction

The activation reduction is mainly used for catalyzing and accelerating the later copper plating process.

The activating and reducing agent used in the invention consists of water, boric acid and an activating and reducing additive; and 990ml of water, 25g of boric acid, 10mg of the reducing-activating additive per liter of reducing-activating agent.

The activating and reducing additive is potassium borohydride.

The treatment steps of the activation reduction are as follows:

placing the object to be treated in an activated reducing agent for 35s, wherein the temperature of the activated reducing solution is 35 ℃; the pH value is about 6.

Electroless copper plating

In the invention, every 1 liter of the chemical copper deposition solution contains 852.5ml of water, 85ml of copper base material, 2.5ml of copper stabilizer, 45ml of copper additive, 15ml of copper reducing agent and 9g of sodium hydroxide.

The copper base is a complexing agent selected from amino acids preferably having at least 2 or up to 10 carbon atoms, the acids of polycarboxylic acids, typically aminoacetic acids such as nitrilotriacetic acid, or, typically, alkylenepolyamine polyacetic acids including ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetetraacetic acid, 1, 3-diamino-2-propanol-N, N, N ', N ' -tetraacetic acid, dihydroxyphenylenediaminediaminediacetic acid, diaminocyclohexanetetraacetic acid or ethyleneglycol-bis [ (beta-aminoethyl ether) -N, N ' -tetraacetic acid ] and N, N, N ', N ' -tetrakis- (2-hydroxypropyl) ethylenediamine, citrate, tartrate, N, N-2- (hydroxyethyl) glycine, N-bis- (2-hydroxypropyl) ethylenediamine, citrate, tartrate, Gluconate, lactate, citrate, tartrate, crown ether and/or a mixture of acupuncture points.

The copper additive is copper sulfate.

The copper reducing agent is selected from vanillin and one or more of formaldehyde, glyoxylic acid, sodium hypophosphite or methyl citral.

The electroless copper plating method comprises the following processing steps:

the object to be treated is placed in the chemical copper deposition solution for 240-450s, and the temperature of the chemical copper deposition solution is 35 ℃.

The service life of the liquid medicine is as follows: production area of bath solution is 100m²The specific gravity of/L or bath solution exceeds 1.09g/cm³。

The thickness of the third metal is 0.05-3 μm.

Plating film

Electroplating is a process of plating a thin layer of other metals or alloys on the surface of some metals by using the principle of electrolysis, and is a process of attaching a layer of metal film on the surface of a metal or other material product by using the action of electrolysis, thereby having the effects of preventing metal oxidation (such as corrosion), improving wear resistance, conductivity, light reflection, corrosion resistance (such as copper sulfate and the like), enhancing the appearance and the like.

The electroplating solution used in the invention comprises 60-90g/L of blue vitriod; 180-220g/L sulfuric acid; 40-80ppm chloride ion; 8-12ml/L of a jar opening agent; 3-5ml/L of brightener and 0.1-0.5ml/L of regulator.

The cylinder opener is sulfonate, nitrogen heterocyclic copolymer and surfactant.

The sulfonate is selected from one or more of sodium dodecyl sulfonate, sodium acyl methylamine alkane sulfonate or sodium p-toluenesulfonate; the nitrogen heterocyclic copolymer is poly (vinyl imidazole-2-acrylamide-2-methylpropanesulfonic acid-stearyl methacrylate). The surfactant is selected from one of sodium isethionate, dihexyl sodium sulfosuccinate and sodium dodecyl sulfate.

The brightener is sodium mercaptopropane sulfonate and sodium N, N-dimethyl-dithioformamide propane sulfonate, and the ratio of the brightener to the sodium N, N-dimethyl-dithioformamide propane sulfonate is 2: 1.

the regulator is polyethylene glycol with a hydroxyl value of 8-14 mg KOH/g.

The electroplating steps are as follows:

01. plating solution jar

1. Cylinder cleaning

A) Cleaning the cylinder body and each pipeline by water;

B) soaking the cylinder body and the filtering system for 2-4 hours by using 5 wt% of NaOH;

C) cleaning the cylinder body and each pipeline by clean water and then using 5 wt% of H₂Soaking in SO4 for 2-4 hr;

D) cleaning the cylinder body and each pipeline by water and opening the cylinder;

2. step of opening cylinder

A) Adding water with the volume of 2/3 cylinders, and starting filtering and inflating;

B) slowly adding 200g/L of AR-grade sulfuric acid;

C) adding 75g/L of copper sulfate;

D) hanging a cleaned copper anode, filtering for 4 hours by using a carbon core, and then replacing a cotton core for filtering;

E) when the temperature is cooled to below 30 ℃, 10ml/L of jar opening agent, 5ml/L of brightening agent and 0.5ml/L of regulator are added;

F) electrolyzing for 4-8 hours by using 0.5-2.0 ASD current density;

G) and the trial and chemical analysis can be carried out after adjusting each component to the normal range.

02 electroplating conditions were as follows:

working temperature: 20-30 ℃; the cathode current density is 1-6A/dm²The voltage is 1-3.5V; the anode is a phosphor-copper ball or a phosphor-copper corner (containing 0.03-0.06 wt% of phosphor) containing 99.9% of copper. The area ratio of the cathode to the anode is 1 (1.5-2.5); the stirring mode is air stirring (a low-pressure oil-free blower is adopted and passes through an oil-water separation device and a filtering device) and cathode movement; the filtration mode is continuous filtration with 5-10 μm cotton core or carbon core.

03, plating solution maintenance:

1. the plating solution lost due to evaporation can be supplemented by deionized water;

2. periodically analyzing the copper sulfate content, the sulfuric acid content and the chloride content;

3. adjusting the additive according to the hercules test;

4. 200ml of brightener is added for every 1000AH in normal production.

The thickness of the protective layer is 100-50000 nm.

A third aspect of the present invention provides the above plastic film article, which is applied in the field of electromagnetic signal conduction.

The technique of the present invention will be described in detail with reference to specific examples.

Example 1:

the embodiment provides a plastic film product, wherein three layers of metal films are deposited on the plastic film product and respectively comprise a bonding layer, a chemical layer and a protective layer; the bonding layer consists of a bonding plastic layer and a bonding metal layer; the thickness of the plastic film was 50 μm.

The bonding layer is coated in a sputtering mode, and the chemical layer is coated in a chemical plating mode; the protective layer is plated in an electroplating mode.

The combination plastic layer is formed by Ni metal, the combination metal layer is formed by Cr metal, and the chemical layer and the protective layer are both formed by copper metal.

The sputtering mode is as follows:

s01, in an argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, coating a non-metal material, setting the voltage of the bias power supply to 110V, the duty ratio of the bias power supply to 35%, the current of the medium-frequency power supply to 20A, setting the flow of argon to 165Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the film coating time to 15min, and reducing the vacuum degree to 2.3 x 10^-1Pa；

And after the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating, opening the door and taking out the product to obtain the product coated with the bonding plastic layer.

S02, according to the step S01, the product plated with the bonding plastic layer is subjected to a metal layer bonding metallization operation.

The metallization operation parameters of the bonding metal layer are as follows:

in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 150V, the duty ratio of the bias power supply is set to be 25%, the current of the medium-frequency power supply is set to be 20A, the flow of argon is set to be 150Sccm, the flow of reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 10min, the vacuum degree is reduced to be 2.3 multiplied by 10^-1Pa。

Chemical plating:

in the invention, the chemical plating comprises the following steps:

S001：

bulking: placing the sputtering coated product in a swelling solution for 62s, wherein the temperature of the swelling solution is 75 ℃;

S002：

removing glue: placing the bulked product in a degumming solution, wherein the standing time is 125s, and the temperature of the degumming solution is 80 ℃;

S003

neutralizing: placing the product subjected to the degumming treatment in a neutralization solution for 42s at the temperature of 30 ℃;

S004：

adjusting: the neutralized product was placed in a conditioner for 61s, and the temperature of the solution was adjusted to 50 ℃.

S005：

Activation pretreatment: the conditioned article was placed in an activating pretreatment for 22 seconds and the neutralizing solution temperature was 25 degrees celsius.

S006：

And (3) activation: the activated pre-treated article was placed in an activating agent for 46s at a 45 degree c activating solution temperature.

S007：

Activation and reduction: and (3) placing the activated product in an activated reducing agent for 36s, wherein the temperature of the activated reducing agent is 35 ℃.

S008：

Copper plating: and (3) placing the product subjected to the activation reduction treatment in chemical copper deposition liquid for 299s, wherein the temperature of the chemical copper deposition liquid is 35 ℃.

The swelling agent consists of water, a swelling additive and a pH correction agent; and each liter of leavening agent contains 849ml of water, 150ml of leavening additive and 1ml of pH correction agent. The pH correction agent is a 32 wt% sodium hydroxide solution.

The 150ml leavening additive consisted of 60g/L N-methyl pyrrolidone, 50g/L sodium hydroxide and 70g/L DMF.

The degumming agent consists of water, a degumming additive and a pH regulator; and each liter of degumming agent contains 770ml of water, 125ml of degumming additive and 105ml of pH regulator. The glue removing additive is sodium permanganate; the pH regulator is 32% sodium hydroxide solution, and the 32% sodium hydroxide solution is 432g/L NaOH.

The neutralizing agent consists of water, sulfuric acid, hydrogen peroxide and a neutralizing additive; and contains 885ml of water, 100ml of 50 wt.% sulfuric acid and 15ml of 35 wt.% H per liter of neutralizing agent₂O₂。

The regulator consists of water and a regulating additive; and each liter of the conditioner contains 960ml of water, 40mg of conditioning additive. The adjustment additive is dopamine.

The activating pretreatment agent is sodium chloride solution, and each 1 liter of the activating pretreatment agent contains 980ml of water, 10ml of sodium chloride and 10ml of triethanolamine.

The activating agent consists of water, an activating additive and an alkaline substance; and each liter of activator contains 774ml of water, 225ml of activating additive and 1ml of sodium hydroxide solution. The concentration of the sodium hydroxide solution was 32 wt%. The activating additive is a main component and an auxiliary agent; the weight ratio of the two is 10: 1.

the main component is palladium sulfate, and the auxiliary agent is ethylene diamine tetraacetic acid.

The activated reducing agent consists of water, boric acid and potassium borohydride; and 990ml of water, 25g of boric acid and 10mg of potassium borohydride per liter of activating-reducing agent.

The chemical copper deposition solution comprises 852.5ml of water, 85ml of copper base material, 2.5ml of copper stabilizer, 45ml of copper additive, 15ml of copper reducing agent and 9g of sodium hydroxide per 1 liter of chemical copper deposition solution. The copper base, copper stabilizer, copper additive and copper reducing agent were purchased from Guangdong Shuichi technologies, Inc.

The copper base agent is N-hydroxyethyl ethylene diamine tetraacetic acid; the copper additive is copper sulfate; the copper reducing agent is methyl citral.

Electroplating of

The electroplating steps are as follows:

01. plating solution jar

1. Cylinder cleaning

A) Cleaning the cylinder body and each pipeline by water;

B) soaking the cylinder body and the filtering system for 3 hours by using 5 wt% of NaOH;

C) medicine for curing diabetesAfter the cylinder body and each pipeline are cleaned by water, 5 wt% of H is used₂Soaking in SO4 for 2 hours;

2. step of opening cylinder

B) slowly adding 200g/L of AR-grade sulfuric acid;

C) adding 75g/L of copper sulfate;

F) electrolyzing for 6 hours by using 1.5 ASD current density;

02 electroplating conditions were as follows:

working temperature: 25 ℃; the cathode current density is 4A/dm²The voltage is 1.8V; the anode is a phosphor-copper ball or a phosphor-copper corner (containing 0.03-0.06 wt% of phosphor) containing 99.9% of copper. The area ratio of the cathode to the anode is 1: 2; the stirring mode is air stirring (a low-pressure oil-free blower is adopted and passes through an oil-water separation device and a filtering device) and cathode movement; the filtration mode is continuous filtration with 5-10 μm cotton core.

03, plating solution maintenance:

3. adjusting the additive according to the hercules test;

4. 200ml of brightener is added for every 1000AH in normal production.

The plating solution used in this example contained 80g/L of copper sulfate pentahydrate; 190g/L sulfuric acid; 60ppm chloride ion; 9ml/L of a jar opening agent; 4ml/L of brightener and 0.3ml/L of regulator. Hydrochloric acid is the source of chloride ions in this example.

The cylinder opener is sodium dodecyl sulfate, poly (vinyl imidazole-2-acrylamide-2-methylpropanesulfonic acid-stearyl methacrylate) and sodium hydroxyethyl sulfonate in a ratio of 5: 1: 1.

the regulator is polyethylene glycol with a hydroxyl value of 10mg KOH/g.

Example 1-1:

the present example differs from example 1 as follows:

and potassium borohydride in the activated reducing agent is replaced by sodium borohydride.

Example 2:

the present embodiment is different from embodiment 1 in that the metal of the bonding metal layer is Mn; and the specific operating parameters are as follows:

the sputtering mode is as follows:

s01, in the environment of argon and reaction gas, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, coating the non-metal material, setting the voltage of the bias power supply to be 95V, the duty ratio of the bias power supply to be 35%, the current of the medium-frequency power supply to be 18A, setting the flow of argon to be 160Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the film coating time to be 15min, and reducing the vacuum degree to 2.3 multiplied by 10^-1Pa；

in the argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, starting film coating, setting the voltage of the bias power supply to be 150V, the duty ratio of the bias power supply to be 35 percent, setting the current of the medium-frequency power supply to be 24A, setting the flow of argon to be 160Sccm, gradually adding the flow of the reaction gas according to the requirements of a film system,the time for starting coating is set to 11min, and the vacuum degree is reduced to 2.3 multiplied by 10^-1Pa。

The bulking treatment steps are as follows:

placing the object to be treated in the leavening solution for 75s, wherein the temperature of the leavening solution is 75 ℃.

Example 3:

the present embodiment is different from embodiment 1 in that the metal of the bonding plastic layer is Cr metal, and the metal of the bonding metal layer is Mn metal.

The operating parameters were the same as in example 1, with the following operating parameters:

the sputtering mode is as follows:

s01, in the argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by coating, coating the non-metal material, setting the voltage of the bias power supply to be 115V, the duty ratio of the bias power supply to be 32%, the current of the medium-frequency power supply to be 17A, setting the flow of argon to be 160Sccm, gradually adding the reaction gas according to the requirement of a film system, setting the coating time to be 12min, and reducing the vacuum degree to be 2.3 multiplied by 10^-1Pa；

in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 100V, the duty ratio of the bias power supply is set to be 40%, the current of the medium-frequency power supply is set to be 21A, the flow of argon is set to be 160Sccm, the flow of the reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 10min, the vacuum degree is reduced to be 2.3 multiplied by 10, and the target material is subjected to film coating^-1Pa。

Example 4:

this embodiment is different from embodiment 3 in that the metal of the bonding metal layer is Ni metal.

The operating parameters were the same as in example 3, with the following operating parameters:

the sputtering mode is as follows:

s01, in the environment of argon and reaction gas, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, coating the non-metal material, setting the voltage of the bias power supply to 80V, the duty ratio of the bias power supply to 50%, the current of the medium-frequency power supply to 20A, setting the flow of argon to 150Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the film coating time to 13min, and reducing the vacuum degree to 2.3 multiplied by 10^-1Pa；

in the argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, starting film coating, setting the voltage of the bias power supply to 160V, the duty ratio of the bias power supply to 45 percent, setting the current of the medium-frequency power supply to 25A, setting the flow of argon to 155Sccm, gradually adding the flow of the reaction gas according to the requirements of a film system, setting the film coating starting time to 5min, and reducing the vacuum degree to 2.3 multiplied by 10^-1Pa。

Example 5:

the difference between this embodiment and embodiment 4 is that the metal of the bonding plastic layer is Mn metal; the metal of the bonding metal layer is Ni metal.

The operating parameters were the same as in example 4, with the following operating parameters:

the sputtering mode is as follows:

s01, in the argon and reaction gas environment, turning on a bias power supply, turning on an intermediate frequency power supply of a target material required by film coating, and coating the non-metal material, wherein the voltage of the bias power supply is set to be 110V, the duty ratio of the bias power supply is set to be 45%, the current of the intermediate frequency power supply is set to be 20A, and the flow of argon is setThe flow rate of the reaction gas is gradually added according to the requirements of the film system, the film coating time is set for 15min, and the vacuum degree is reduced to 2.3 multiplied by 10^-1Pa；

in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by coating is turned on, coating is started, the voltage of the bias power supply is set to be 122V, the duty ratio of the bias power supply is set to be 40%, the current of the medium-frequency power supply is set to be 18A, the argon flow is set to be 165Sccm, the reaction gas flow is gradually added according to the requirement of a film system, the coating starting time is set to be 10min, the vacuum degree is reduced to 2.3 multiplied by 10, and the vacuum degree is reduced to be 2.3 multiplied by 10^-1Pa。

Example 6:

this embodiment is different from embodiment 5 in that the metal of the bonding metal layer is Cr.

The operating parameters were the same as in example 5, with the following operating parameters:

the sputtering mode is as follows:

s01, in an argon and reaction gas environment, turning on a bias power supply, turning on a medium-frequency power supply of a target material required by film coating, coating a non-metal material, setting the voltage of the bias power supply to be 120V, the duty ratio of the bias power supply to be 30%, the current of the medium-frequency power supply to be 20A, setting the flow of argon to be 160Sccm, gradually adding the reaction gas according to the requirements of a film system, setting the film coating time to be 11min, and reducing the vacuum degree to be 2.3 multiplied by 10^-1Pa；

in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to 130V, the duty ratio of the bias power supply is set to 45 percent, the current of the medium-frequency power supply is set to 22A, the flow of argon is set to 150Sccm, the flow of the reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to 12min, the vacuum degree is reduced to 2.3 multiplied by 10, and the vacuum degree is reduced to 2.3 multiplied by 10^-1Pa。

Example 7:

this example is different from example 1 in that the sputter coating is plated with only one metal layer, i.e., a Ni metal layer.

Example 8:

the difference between this embodiment and embodiment 1 is that this embodiment provides a non-metallic material surface metalized product that does not contain a chemical layer, i.e. has no electroless plating, and only has two metal layers formed by sputtering and one metal layer formed by electroplating.

Example 9:

this example is different from example 1 in that the electroless plating does not include four steps of conditioning, pre-activation, activation and reduction-activation, and includes only the steps of bulking, degumming, neutralizing and copper plating.

Example 10:

this example differs from example 1 in that the non-metallic material is polypropylene and has a weight average molecular weight of 30000.

The remaining operating parameters were in accordance with example 1.

Example 11:

this example differs from example 1 in that the copper reducing agent is formaldehyde.

Example 12:

this example differs from example 1 in that the brightener is sodium N, N-dimethyldithioformamide propane sulfonate.

And (3) performance testing:

1. elongation of stretching

The test method comprises the following steps: a sample 10cm long by 10cm wide was taken and pulled horizontally with a constant force of 30N until breaking, and the elongation was recorded.

The elongation (length at break-10)/10 × 100%.

2. Binding force

The test method comprises the following steps: taking a sample with the length of 10cm multiplied by the width of 10cm, adhering the sample by using a 3M adhesive tape, removing the adhesive tape, observing whether the metal on the surface of the sample is removed or not, and replacing the adhesive tape with different viscosity until the metal layer on the surface of the sample is damaged. And recording the adhesive specification of the adhesive tape, wherein the adhesive specification is related to the force, and converting to obtain the corresponding force.

3. Light transmittance

And observing the sample by using an optical microscope to observe whether the surface of the sample has light spots. No light spot was found to be acceptable.

And (3) testing results:

examples	Elongation of stretching	Binding force	Light transmittance
				Example 1	30.2％	0.62N	Qualified
Examples 1 to 1	28.6％	0.42N	Fail to be qualified
				Example 2	29.9％	0.59N	Qualified
Example 3	29.2％	0.57N	Qualified
				Example 3-1	28.0％	0.47N	Qualified
Example 4	29.3％	0.58N	Qualified
				Example 5	29.1％	0.55N	Qualified
Example 6	30.0％	0.56N	Qualified
				Example 7	28.3％	0.58N	Qualified
Example 8	29.2％	0.59N	Qualified
				Example 9	29.0％	0.59N	Qualified
Example 10	29.6％	0.60N	Qualified
				Example 11	27.2％	0.37N	Fail to be qualified
Example 12	27.2％	0.34N	Fail to be qualified

Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The plastic film product is characterized in that at least three layers of metal films are deposited on the plastic film product and respectively comprise a bonding layer, a chemical layer and a protective layer; the bonding layer consists of a bonding plastic layer and a bonding metal layer;

the thickness of the plastic film is 50 μm; the thickness of the bonding layer is 2-50 nm.

The bonding layer is coated in a sputtering mode, and the chemical layer is coated in a chemical plating mode; coating the protective layer in an electroplating mode;

the combination plastic layer is formed by Ni metal, the combination metal layer is formed by Cr metal, and the chemical layer and the protective layer are both formed by copper metal;

the sputtering mode is as follows:

After the coating is finished, closing various pump valves in sequence according to the operation rules of the magnetron sputtering coating machine, deflating and opening the door to take out the product, and obtaining the product plated with the bonding plastic layer;

s02, according to the step S01, carrying out metallization operation of a bonding metal layer on the product plated with the bonding plastic layer;

in the argon and reaction gas environment, a bias power supply is turned on, a medium-frequency power supply of a target material required by film coating is turned on, film coating is started, the voltage of the bias power supply is set to be 150V, the duty ratio of the bias power supply is set to be 25%, the current of the medium-frequency power supply is set to be 20A, the flow of argon is set to be 150Sccm, the flow of reaction gas is gradually added according to the requirements of a film system, the film coating starting time is set to be 10min, the vacuum degree is reduced to be 2.3 multiplied by 10^-1Pa；

The film coating step of the chemical plating at least comprises one or more of copper plating and the following steps of combination, wherein the combination of the steps comprises bulking, degumming, neutralization, adjustment, activation pretreatment, activation and reduction; the activating and reducing agent used for activating and reducing consists of water, boric acid and an activating and reducing additive, wherein the activating and reducing additive is potassium borohydride;

every 1 liter of chemical copper deposition solution used in the copper plating comprises 852.5ml of water, 85ml of copper base material, 2.5ml of copper stabilizer, 45ml of copper additive, 15ml of copper reducing agent and 9g of sodium hydroxide, wherein the copper reducing agent is methyl citral;

the electroplating solution used for electroplating the film comprises 80g/L of copper sulfate pentahydrate; 190g/L sulfuric acid; 60ppm chloride ion; 9ml/L of a jar opening agent; 4ml/L of brightening agent and 0.3ml/L of regulating agent, wherein the source of the chloride ions is hydrochloric acid, the brightening agent is sodium mercaptopropane sulfonate and sodium N, N-dimethyl dithioformamide propane sulfonate, and the ratio is 2: 1, the regulator is polyethylene glycol with a hydroxyl value of 10mg KOH/g.

2. The plastic film article of claim 1, which is used in the field of electromagnetic signal transmission.