CN105839159B - A kind of vinyon electroplating technology - Google Patents
A kind of vinyon electroplating technology Download PDFInfo
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- CN105839159B CN105839159B CN201610343165.8A CN201610343165A CN105839159B CN 105839159 B CN105839159 B CN 105839159B CN 201610343165 A CN201610343165 A CN 201610343165A CN 105839159 B CN105839159 B CN 105839159B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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Abstract
The invention discloses a kind of vinyon electroplating technologies, include the following steps：1) vinyon powder, adhesive, accelerating agent and plasticizer are stirred according to the ratio, said mixture is then put into calendering formation in calender；2) it is impregnated using activator, is cleaned using the mixed solution of water and ethyl alcohol after taking-up, then the plastics after cleaning are punched into the finished product of required specification, the activator includes water, Water-soluble Ru salt, hydrochloric acid, boric acid and sodium metaphosphate；3) it is passed through supercritical fluid on plastic injection equipment, prepares the plastic products of surface layer microporous foam solid core；The plastic products are electroplated by electroplating technology, form the coat of metal.The present invention not only increases the binding force of workpiece and subsequent plating layer, and foaming phenomena is not present in coating, and the solderability with coated product is good.
Description
Technical field
The present invention relates to field of electroplating, specifically, being related specifically to a kind of vinyon electroplating technology.
Background technology
It is exactly to plate the other gold of a thin layer on certain metal surfaces using electrolysis principle that (Electroplating), which is electroplated,
Belong to or alloy process, be using electrolysis make the surface of metal or other materials product adhere to layer of metal film technique from
And playing prevents metal from aoxidizing (such as corrosion), improves wearability, electric conductivity, reflective, corrosion resistance (copper sulphate etc.) and promotes
The effects that beautiful.The outer layer of many coins is also plating.
The application of plastic products is more and more extensive, and since its glossiness is not so good as metal, decoration function is relatively poor, so people
Try by plastic surface galvanizing, make metallization of plastic surface, have metallic luster and aesthetics.In recent years, with vapour
The fast development of turner industry, electrical industry and household electrical appliance, ornaments industry, plastic surface galvanizing alloying technology also continue to develop.Through
Plastic products after plating integrate the characteristic of plastics, metal, and not only appearance is able to beautiful decoration, and the physics of product,
Mechanical performance all has significant improvement, and assigns the new features such as conduction, magnetic conduction, welding.So present plastic electroplating has become
For a kind of important process of decorative plastic.If in plastic surface galvanizing metal, it is necessary to first make the conductive film of frosting
One metallization of plastic surface needs to pre-process frosting --- activation.In order to ensure coating and plastic substrate
Good combination, plastic-substrates must activate.Plastic-substrates activation, surface metalization techniques are to plastic surface galvanizing metallic diaphragm
Adhesion, stability and aesthetics will generate great influence, also contribute to the electric conductivity of metallization of plastic surface layer, sink
The coating property such as lamination service life.If plastic-substrates activation is insufficient, metallization of plastic surface technology is extremely difficult to require, and is easy
Cause plating after coating it is loose, be bubbled, decortication, it is coarse phenomena such as.
At present in frosting activating pretreatment technology and technique, often use frosting coating conductive coating, go from
Ultrasonic coarsing in sub- water, containing chromate (or CrO3) immersion, frosting pickling etc. in solution.But the obtained work of these methods
Change preconditioning technique as a result, the adhesive force of its frosting matrix and coating is not strong, loose, drum still occurs often for coating after plating
Phenomena such as bubble and decortication.
104451803 A of CN disclose a kind of plastic electroplating technique, include the following steps：(1) by plastic powders, bonding
Agent, accelerating agent and nucleating agent are stirred according to the ratio, and said mixture is then put into calendering formation in calender；(2) it uses
Gasoline impregnate 2-3 hours, and cleaning of deoiling is carried out using degreaser after taking-up, is then punched into the rubber after cleaning required
The finished product of specification；(3) it is passed through supercritical fluid on plastic injection equipment, prepares the plastics system of surface layer microporous foam solid core
The plastic products are electroplated by electroplating technology for product, form the coat of metal.The binding force of obtained workpiece and coating compared with
Height, still, however it remains foaming phenomena, moreover, the solderability of the plastic products after plating is very poor, in practical applications by very
Big limitation.
Invention content
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of plastic electroplating technique, with
It solves the above problems.
Following technical scheme may be used to realize in technical problem solved by the invention：
A kind of vinyon electroplating technology, includes the following steps：
1) vinyon powder, adhesive, accelerating agent and plasticizer are stirred according to the ratio, then by above-mentioned mixing
Object is put into calendering formation in calender；
2) it is impregnated using activator, is cleaned using the mixed solution of water and ethyl alcohol after taking-up, it then will cleaning
Plastics afterwards are punched into the blank of required specification, and the activator includes water, Water-soluble Ru salt, hydrochloric acid, boric acid and sodium metaphosphate；
3) it is passed through supercritical fluid on plastic injection equipment, and passes through the injection of the quantitative control supercritical fluid, system
The plastic products of standby surface layer microporous foam solid core；The plastic products are electroplated by electroplating technology, form metal
Coating.
The present invention is by using the mixed solution comprising water, Water-soluble Ru salt, hydrochloric acid, boric acid and sodium metaphosphate as activation
Agent activates the vinyon of calendering formation, can improve the combination of the coating subsequently obtained in plastic surface galvanizing
Power, moreover, the solderability of the product after obtained plating is fine.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
Preferably, it is in terms of 100 parts by the amount of water, the dosage of the Water-soluble Ru salt is 0.05-0.2 in the activator
Part, 0.05 part, 0.08 part, 0.1 part, 0.15 part or 0.2 part is may be, for example, the dosage of the hydrochloric acid is preferably 0.5-1 parts, such as
Can be 0.5 part, 0.6 part, 0.8 part or 1 part etc., the dosage of the boric acid is preferably 20-25 parts, may be, for example, 20 parts, 22 parts, 23
Part, 24 parts or 25 parts etc., the dosage of the sodium metaphosphate is preferably 1-3 parts, may be, for example, 1 part, 1.5 parts, 2 parts or 3 parts etc..
It is the use of the Water-soluble Ru salt in terms of 100 parts by the amount of water as a preferred technical solution, in the activator
Amount is 0.1 part, and the dosage of the hydrochloric acid is 1 part, and the dosage of the boric acid is 22 parts, and the dosage of the sodium metaphosphate is 2 parts.
Preferably, the soluble ruthenium salt is ruthenium trichloride.
Preferably, the temperature of step (2) described immersion be 40-65 DEG C, may be, for example, 45 DEG C, 50 DEG C, 52 DEG C, 55 DEG C, 60
DEG C or 65 DEG C etc., preferably 45 DEG C.
Preferably, the time of step (2) described immersion be 30-100min, may be, for example, 30min, 40min, 50min,
60min, 70min, 80min or 100min etc., preferably 60min.
The electrolyte used in the electroplating technology as a preferred technical solution, contain water, soluble nickel salt, boric acid,
Hypophosphorous acid, soluble rare earth metal salt and rare earth metal complexing agent.Pass through the composition for adjusting electrolyte and above-mentioned activator
Composition, can improve the binding force that obtained coating is subsequently electroplated.
Preferably, it is in terms of 100 parts by the amount of water, the dosage of the soluble nickel salt is preferably 30-40 in the electrolyte
Part, may be, for example, 30 parts, 32 parts, 34 parts, 36 parts or 40 parts etc., the dosage of the boric acid is preferably 3-4 parts, may be, for example, 3 parts,
3.3 parts, 3.5 parts or 4 parts etc., the dosage of the hypophosphorous acid is preferably 3-6 parts, may be, for example, 3 parts, 4 parts, 5.5 parts or 6 parts etc.,
The dosage of the solubility rare earth metal salt is preferably 0.05-0.1 parts, may be, for example, 0.05 part, 0.06 part, 0.08 part or 0.1
Part etc., the dosage of the rare earth metal complexing agent is preferably 0.05-0.5 parts, may be, for example, 0.05 part, 0.08 part, 0.1 part, 0.2
Part, 0.3 part, 0.4 part or 0.5 part etc..
Preferably, soluble nickel salt in nickel chloride, nickel nitrate or nickel sulfate any one or at least two it is mixed
Close object.
Preferably, soluble rare earth metal salt in lanthanum chloride, cerium chloride, gadolinium chloride and ytterbium chloride any one or
At least two mixture.
Preferably, the rare earth metal complexing agent is selected from malic acid and/or citric acid.
Described adhesive is grouped as by each group of following parts by weight as a preferred technical solution,：Vinyl acetate resin 20-
30 parts, 5-7 parts of stearic acid, 1-3 parts of chloroform, 0.5-1 parts of carbon tetrachloride, 0.05-0.5 parts of calcium chloride, dimethylbenzene 0.5-1
Part, 1-3 parts of polymethyl acrylate, 8 parts of linear low density polyethylene.The present invention uses the adhesive of specific components, cooperation activation
The use of agent and electrolyte, the surface plating that can improve the binding force for the coating that plating obtains jointly and obtain are coated poly-
The solderability of vinyl plastics product.
Preferably, described adhesive is grouped as by each group of following parts by weight：30 parts of vinyl acetate resin, 6 parts of stearic acid,
It is 1 part of chloroform, 0.8 part of carbon tetrachloride, 0.5 part of calcium chloride, 0.5 part of dimethylbenzene, 1.5 parts of polymethyl acrylate, linear low close
Spend 8 parts of polyethylene.
Preferably, the accelerating agent be selected from glyoxaline compound, preferably be selected from 2-methylimidazole, 2-ethyl-4-methylimidazole,
In 2- phenylimidazoles or 2- undecyl imidazoles any one or at least two mixture.
Preferably, the plasticizer is selected from trioctyl trimellitate (TOTM) and/or trimellitic acid glyceryl ester.
As the preferred technical solution of the present invention, the electroplating temperature in the step 3) electroplating technology is 55-60 DEG C, example
It such as can be 55 DEG C, 58 DEG C, 59 DEG C or 60 DEG C.
Preferably, the cathode-current density in step (3) described electroplating technology is 3-5A/dm2, may be, for example, 3A/dm2、
3.5A/dm2、4A/dm2Or 5A/dm2Deng.
Compared with prior art, beneficial effects of the present invention are as follows：
The present invention is by using the mixed solution comprising water, Water-soluble Ru salt, hydrochloric acid, boric acid and sodium metaphosphate as activation
Agent activates the vinyon of calendering formation, using including water, soluble nickel salt, boric acid, hypophosphorous acid, soluble rare earth
The mixed solution of metal salt and rare earth metal complexing agent is electrolysed as electrolyte, can be improved subsequently in plastic surface galvanizing
The binding force of obtained coating has broad application prospects moreover, the solderability of the product after obtained plating is fine.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Embodiment 1
A kind of vinyon electroplating technology, includes the following steps：
1) vinyon powder, adhesive, accelerating agent and plasticizer are stirred according to the ratio, then by above-mentioned mixing
Object is put into calendering formation in calender；
2) immersion 30min is carried out at 45 DEG C using activator, is cleaned using the mixed solution of water and ethyl alcohol after taking-up,
Then plastics after cleaning are punched into the finished product of required specification, the activator includes 100 parts of water, 0.05 part of ruthenium salt, 0.5
Part hydrochloric acid, 25 parts of boric acid, 3 parts of sodium metaphosphates；
3) supercritical fluid, and the injection by orderly quantitatively controlling supercritical fluid, system are passed through on plastic injection equipment
The plastic products of standby surface layer microporous foam solid core；
Plastic products are electroplated by electroplating technology, the coat of metal with back-off structure are formed, to obtain coating
The strong high performance plastics with the coat of metal, microporous foam layer and solid core three-decker, which are electroplated, with plastics binding force makes
Product, wherein the temperature of plating is 55 DEG C, and the cathode-current density of plating is 5A/dm2, the electrolyte used in the process contains 100
Part water, 30 parts of soluble nickel salts, 4 parts of boric acid and 6 parts of hypophosphorous acid.
After testing, foaming phenomena is not present in the coating for the coated product of band that the present embodiment obtains, and is obtained after being electroplated
Product solderability it is fine.
Embodiment 2
A kind of vinyon electroplating technology, includes the following steps：
1) vinyon powder, adhesive, accelerating agent and plasticizer are stirred according to the ratio, then by above-mentioned mixing
Object is put into calendering formation in calender；
2) immersion 100min is carried out at 65 DEG C using activator, is carried out clearly using the mixed solution of water and ethyl alcohol after taking-up
It washes, then the plastics after cleaning is punched into the finished product of required specification, the activator includes 100 parts of water, 0.2 part of ruthenium salt, 1
Part hydrochloric acid, 20 parts of boric acid, 1 part of sodium metaphosphate；
3) supercritical fluid, and the injection by orderly quantitatively controlling supercritical fluid, system are passed through on plastic injection equipment
The plastic products of standby surface layer microporous foam solid core；
Plastic products are electroplated by electroplating technology, the coat of metal with back-off structure are formed, to obtain coating
The strong high performance plastics with the coat of metal, microporous foam layer and solid core three-decker, which are electroplated, with plastics binding force makes
Product, wherein the temperature of plating is 60 DEG C, and the cathode-current density of plating is 3A/dm2, the electrolyte used in the process contains 100
Part water, 40 parts of soluble nickel salts, 3 parts of boric acid and 3 parts of hypophosphorous acid.
After testing, foaming phenomena is not present in the coating for the coated product of band that the present embodiment obtains, and is obtained after being electroplated
Product solderability it is fine.
Embodiment 3
A kind of vinyon electroplating technology, includes the following steps：
1) vinyon powder, adhesive, accelerating agent and plasticizer are stirred according to the ratio, then by above-mentioned mixing
Object is put into calendering formation in calender；
2) immersion 60min is carried out at 45 DEG C using activator, is cleaned using the mixed solution of water and ethyl alcohol after taking-up,
Then plastics after cleaning are punched into the finished product of required specification, the activator include 100 parts water, 0.1 portion of ruthenium salt, 1 part
Hydrochloric acid, 22 parts of boric acid, 2 parts of sodium metaphosphates；
3) supercritical fluid, and the injection by orderly quantitatively controlling supercritical fluid, system are passed through on plastic injection equipment
The plastic products of standby surface layer microporous foam solid core；
Plastic products are electroplated by electroplating technology, the coat of metal with back-off structure are formed, to obtain coating
The strong high performance plastics with the coat of metal, microporous foam layer and solid core three-decker, which are electroplated, with plastics binding force makes
Product, wherein the temperature of plating is 58 DEG C, and the cathode-current density of plating is 4A/dm2, the electrolyte used in the process contains 100
Part water, 35 parts of soluble nickel salts, 4 parts of boric acid and 5 parts of hypophosphorous acid.
After testing, foaming phenomena is not present in the coating for the coated product of band that the present embodiment obtains, and is obtained after being electroplated
Product solderability it is fine.
Comparative example 1
Comparative example 1 is the embodiment 1 of 104451803 A of CN, and there are foaming phenomenas for obtained coating, and are obtained after being electroplated
Product solderability it is poor.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (20)
1. a kind of plastic electroplating technique, which is characterized in that include the following steps：
1) vinyon powder, adhesive, accelerating agent and plasticizer are stirred, said mixture is then put into calendering
Calendering formation in machine；
2) it is impregnated using activator, is cleaned using the mixed solution of water and ethyl alcohol after taking-up, it then will be after cleaning
Plastics are punched into the blank of required specification, and the activator includes water, Water-soluble Ru salt, hydrochloric acid, boric acid and sodium metaphosphate；
3) it is passed through supercritical fluid on plastic injection equipment, and by the injection of the quantitative control supercritical fluid, prepares table
The plastic products of layer microporous foam solid core；The plastic products are electroplated by electroplating technology, form the coat of metal.
2. electroplating technology according to claim 1, which is characterized in that in the activator, by the amount of water be 100 parts in terms of,
The dosage of the Water-soluble Ru salt is 0.05-0.2 parts, and the dosage of the hydrochloric acid is 0.5-1 parts, and the dosage of the boric acid is 20-
25 parts, the dosage of the sodium metaphosphate is 1-3 parts.
3. electroplating technology according to claim 1 or 2, which is characterized in that in the activator, with the amount of water for 100 parts
The dosage of meter, the Water-soluble Ru salt is 0.1 part, and the dosage of the hydrochloric acid is 1 part, and the dosage of the boric acid is 22 parts, described
The dosage of sodium metaphosphate is 2 parts.
4. electroplating technology according to claim 1 or 2, which is characterized in that the Water-soluble Ru salt is ruthenium trichloride.
5. electroplating technology according to claim 1, which is characterized in that the temperature of the step 2) immersion is 40-65 DEG C.
6. electroplating technology according to claim 5, which is characterized in that the temperature of the step 2) immersion is 45 DEG C.
7. electroplating technology according to claim 1, which is characterized in that the time of the step 2) immersion is 30-100min.
8. electroplating technology according to claim 7, which is characterized in that the time of the step 2) immersion is 60min.
9. electroplating technology according to claim 1, which is characterized in that the electrolyte used in the electroplating technology contains
Water, soluble nickel salt, boric acid, hypophosphorous acid, soluble rare earth metal salt and rare earth metal complexing agent.
10. electroplating technology according to claim 9, which is characterized in that in the electrolyte, by the amount of water be 100 parts in terms of,
The dosage of the soluble nickel salt is 30-40 parts, the dosage of the boric acid is 3-4 parts, the dosage of the hypophosphorous acid is 3-6 parts,
The dosage of the solubility rare earth metal salt is 0.05-0.1 parts, and the dosage of the rare earth metal complexing agent is 0.05-0.5 parts.
11. electroplating technology according to claim 9 or 10, which is characterized in that the soluble nickel salt is selected from nickel chloride, nitre
In sour nickel or nickel sulfate any one or at least two mixture.
12. electroplating technology according to claim 9 or 10, which is characterized in that the solubility rare earth metal salt is selected from chlorine
Change in lanthanum, cerium chloride, gadolinium chloride and ytterbium chloride any one or at least two mixture.
13. electroplating technology according to claim 9 or 10, which is characterized in that the rare earth metal complexing agent is selected from apple
Acid and/or citric acid.
14. electroplating technology according to claim 1, which is characterized in that described adhesive by following parts by weight each component
Composition：20-30 parts of vinyl acetate resin, 5-7 parts of stearic acid, 1-3 parts of chloroform, 0.5-1 parts of carbon tetrachloride, calcium chloride
0.05-0.5 parts, 0.5-1 parts of dimethylbenzene, 1-3 parts of polymethyl acrylate, 8 parts of linear low density polyethylene.
15. the electroplating technology according to claim 1 or 14, which is characterized in that described adhesive is each by following parts by weight
Group is grouped as：30 parts of vinyl acetate resin, 6 parts of stearic acid, 1 part of chloroform, 0.8 part of carbon tetrachloride, 0.5 part of calcium chloride, two
0.5 part of toluene, 1.5 parts of polymethyl acrylate, 8 parts of linear low density polyethylene.
16. electroplating technology according to claim 1, which is characterized in that the accelerating agent is selected from glyoxaline compound.
17. electroplating technology according to claim 16, which is characterized in that the accelerating agent is selected from 2-methylimidazole, 2- second
In base -4-methylimidazole, 2- phenylimidazoles or 2- undecyl imidazoles any one or at least two mixture.
18. electroplating technology according to claim 1, which is characterized in that the plasticizer be selected from trioctyl trimellitate (TOTM) and/
Or trimellitic acid glyceryl ester.
19. electroplating technology according to claim 1, which is characterized in that the electroplating temperature in the step 3) electroplating technology
It is 55-60 DEG C.
20. electroplating technology according to claim 1, which is characterized in that the cathode current in the step 3) electroplating technology
Density is 3-5A/dm2。
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