KR20110029602A - Preparation method of polyphenylenesulfide shaped body with plating layer and the shaped body - Google Patents

Preparation method of polyphenylenesulfide shaped body with plating layer and the shaped body Download PDF

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Publication number
KR20110029602A
KR20110029602A KR1020090087350A KR20090087350A KR20110029602A KR 20110029602 A KR20110029602 A KR 20110029602A KR 1020090087350 A KR1020090087350 A KR 1020090087350A KR 20090087350 A KR20090087350 A KR 20090087350A KR 20110029602 A KR20110029602 A KR 20110029602A
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KR
South Korea
Prior art keywords
polyphenylene sulfide
molded body
plating layer
sulfide molded
producing
Prior art date
Application number
KR1020090087350A
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Korean (ko)
Inventor
최병문
Original Assignee
주식회사 신진테크
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Priority to KR1020090087350A priority Critical patent/KR20110029602A/en
Publication of KR20110029602A publication Critical patent/KR20110029602A/en

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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
    • C23C18/1651Two or more layers only obtained by electroless plating
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22Roughening, e.g. by etching
    • C23C18/24Roughening, e.g. by etching using acid aqueous solutions
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating
    • C23C18/30Activating or accelerating or sensitising with palladium or other noble metal
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron

Abstract

The present invention comprises the steps of (a) surface treatment of a polyphenylene sulfide molded body; And (b) forming a plating layer on the surface of the surface-treated polyphenylene sulfide molded body.

Polyphenylene Sulfide, Plating, Nickel

Description

Manufacturing method and molded body of polyphenylene sulfide molded body with a plated layer {PREPARATION METHOD OF POLYPHENYLENESULFIDE SHAPED BODY WITH PLATING LAYER AND THE SHAPED BODY}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyphenylene sulfide molded article, and more particularly, to form a metal plating layer on surfaces of electronic, telecommunication parts, acoustic imaging parts, automobile parts, and mechanical parts made of polyphenylene sulfide. The present invention relates to a method for producing a lensulfide molded article requiring a light weight of a product and a metal plating layer, and a molded article obtainable by the same method.

Polyphenylene sulfide is a resin having high rigidity and excellent chemical resistance, and having a very high heat resistance and having ovarian resistance. Polyphenylene sulfide can be reinforced with inorganic fillers such as glass fibers to impart very high heat resistance, strength, rigidity and excellent dimensional stability, and at the same time, it belongs to a heat resistant engineering plastic having excellent processability as a thermoplastic resin. Polyphenylene sulfides having such characteristics include parts of electric and electronic products such as IC cards, connectors, tape recorder head mounts, parts of home appliances such as dryer parts, hood cutters, pick-up bases, and DAT cylinder bases. It is used for moving parts such as imaging parts, water pump impellers, lamp reflectors, and mechanical parts such as copier gears.

As in the field of communication, there is a need to develop a material that can replace the metal (mainly aluminum), which can reduce the weight and conduct electrical conductivity.However, the etching process is performed due to the physical and chemical properties of polyphenylene sulfide. It is difficult to do the plating itself, or even when plating, there are many problems in terms of stability or practical use due to partial plating or poor adhesion.

The present invention has been proposed to solve the problems of the prior art as described above,

The purpose is to form a metal plating layer on the surface of the electronic, electrical communication parts, acoustic imaging parts, automobile parts, and mechanical parts made of polyphenylene sulfide, and to provide a light-weighted or electrically conductive coating layer. It is to provide a method for producing a phenylene sulfide molded body.

The technical problem of the present invention as described above is achieved by the following means.

(1) (a) surface treating a polyphenylene sulfide molded body; And

(b) A method for producing a polyphenylene sulfide molded body with a plating layer comprising the step of forming a plating layer on the surface of the polyphenylene sulfide molded body surface-treated.

(2) The method of claim 1,

The surface treatment step of the polyphenylene sulfide molded body,

(a1) cleaning the surface of the polyphenylene sulfide molded body;

(a2) removing and etching contaminants on the cleaned polyphenylene sulfide molded body surface; And

(A3) A method for producing a polyphenylene sulfide molded body with a plating layer comprising the step of adjusting the flatness of the surface of the etched polyphenylene sulfide molded body.

(3) The etching step according to claim 2, wherein the etching step of step (a2)

(a2-1) primary etching using a solution consisting of chromic acid and sulfuric acid; And

(a2-2) A method for producing a polyphenylene sulfide molded article having a plating layer including a second etching step using a nitric acid solution.

(4) The method of paragraph 2,

Method of producing a polyphenylene sulfide molded body formed with a plating layer, characterized in that it further comprises the step of neutralizing the surface of the molded body after the etching step of (a2).

(5) The method of paragraph 1,

Method for producing a polyphenylene sulfide molded body with a plating layer further comprising the step of metallizing the surface of the polyphenylene sulfide molded body.

(6) the method of paragraph 1,

Method for producing a polyphenylene sulfide molded body with a plating layer further comprising the step of metallizing the surface of the polyphenylene sulfide molded body.

(7) the method of paragraph 5,

The metallization step is a method for producing a polyphenylene sulfide molded body formed with a plating layer, characterized in that by adsorbing palladium.

(8) the method of paragraph 1,

The plating layer is a method for producing a polyphenylene sulfide molded body formed with a plating layer, characterized in that formed by an electroless plating process.

(9) The method according to 1,

Forming the plating layer is

(b1) forming a plating layer made of a first metal on a surface of the polyphenylene sulfide molded body;

(b2) forming at least one plating layer made of a second metal on the first metal plating layer; And

(b3) A method for producing a polyphenylene sulfide molded article having a plating layer including a step of drying the polyphenylene sulfide having a plating layer formed thereon.

(10) The method according to 9,

The first metal is at least one selected from the group consisting of nickel and copper, the method for producing a polyphenylene sulfide molded article having a plating layer.

(11) The method according to 9,

The second metal is at least one member selected from the group of nickel, copper, zinc, and chromium.

(12) A polyphenylene sulfide molded body having a plating layer obtained in accordance with claim 1 formed therein.

According to the present invention, a metal plating layer can be formed on the surface of electronic, electrical communication parts, acoustic imaging parts, automobile parts, and mechanical parts made of polyphenylene sulfide, and the plating layer having a plating layer capable of lightening the product or providing electrical conductivity can be formed. A phenylene sulfide molded body is provided.

Hereinafter, the content of the present invention will be described in more detail.

The present invention comprises the steps of (a) surface treatment of a polyphenylene sulfide molded body; And

(b) a method of manufacturing a polyphenylene sulfide molded body having a plating layer formed thereon, the method including forming a plating layer on a surface of the polyphenylene sulfide molded body that has been surface-treated.

In the present invention, the polyphenylene sulfide molded body is not only a molded body containing polyphenylene sulfide alone, but also a main material thereof, and a mixture in which predetermined organic compounds (including polymers) and inorganic compounds (including polymers) are added thereto. The molded object which consists of a composition is also included.

Surface treatment step (a) of the polyphenylene sulfide molded body according to the present invention is a pretreatment step for forming a plating layer on the polyphenylene sulfide molded body. Preferably, the surface treatment step includes cleaning the surface of the polyphenylene sulfide molded body (a1); (A2) removing and etching contaminants on the cleaned polyphenylene sulfide molded body surface; And adjusting the flatness of the surface of the etched polyphenylene sulfide molded body (a3).

The step (a1) is a process of chemically washing the surface of the polyphenylene sulfide molded body using a washing liquid, for example, methylene chloride, trichloroethylene (TCE), xylene or the like may be used as the washing liquid. By such a washing process, the surface of the molded body can obtain a surface for maintaining the optimum adsorption force with the metal catalyst.

The step (a2) is a step of removing contaminants on the surface of the polyphenylene sulfide molded body and etching, and the step of removing contaminants on the surface of the molded body is performed by degreasing using a deposition degreasing agent (for example, product name PROCLEAN 151). Can be. At this time, it is preferable that the deposition degreasing agent is a solution of 20 to 40 g / L to a deposition temperature of 40 to 60 ℃, deposition time 2 to 6 minutes. If the above conditions are exceeded, contaminants present on the surface of the molded body may not be sufficiently removed during the deposition process.

The etching process is a process for roughening the surface of the molded body in order to form the plating layer smoothly, and may be performed at least first. For example, an etchant consisting of 200-400 g / L chromic acid and 100-200 ml / L sulfuric acid is treated on the surface of the molded body at a temperature of 60 to 70 ° C. for 3 to 15 minutes to form irregularities on the surface and chemically. Imparts hydrophilicity. A surface irregularity may be secondarily formed by subjecting the molded article subjected to the primary etching process to an etching process at room temperature for 10 minutes using nitric acid.

When chromic acid is included in the composition of the etching solution as described above, it is preferable to perform a neutralization reaction using 50 ml / L hydrochloric acid or the like to remove the chromium component from the surface of the polyphenylene sulfide molded body. This neutralization reaction is preferably treated for 30 seconds to 2 minutes at room temperature.

Finally, the step (a3) is a process of adjusting the flatness by treating the surface of the etched polyphenylene sulfide molded body with a surfactant. Examples of the surfactant that can be used in this process may be used alone or in combination of two or more of the positive or negative ion-based surfactant, it is sufficient to prepare and use at a concentration of 5 to 20%. The treatment temperature of the surfactant is preferably 20 to 60 ° C., and the treatment time is 10 to 20 minutes. If the treatment conditions are not suitable, there is a problem that the surface is not smoothed and the surface is not uniform.

It is preferable to metallize the surface of the polyphenylene sulfide molded body which is a non-metal after the said surface treatment process is completed. The metallization process is to smoothly perform the subsequent process of forming the plating layer, which is performed by adsorbing a metal such as palladium on the surface of the molded body. Adsorption of palladium may be achieved by, for example, adsorbing a composition liquid consisting of 0.2 to 2 g / L palladium and 100 to 200 ml / L hydrochloric acid to the surface of the surface-treated molded body at a temperature of 20 to 30 ° C. for 20 to 30 minutes. have. At this time, impurities (eg, tin) present in the adsorption process of metal components such as palladium may be removed by treating a solution such as 5 to 10% of ACC. At this time, as processing conditions, 20-30 degreeC and 30 second-about 20 minutes are preferable.

After completing the metallization process (or catalyst activation process), a plating layer is formed on the surface of the polyphenylene sulfide molded body. Preferably, the plating layer includes at least one or more plating layers, and an electroless plating process may be used.

The forming of the plating layer may include forming a plating layer of a first metal on a surface of the polyphenylene sulfide molded body (b1); (B2) forming a plating layer of at least one layer of a second metal on the first metal plating layer; And (b3) drying the polyphenylene sulfide on which the plating layer is formed.

Examples of the first metal in the step (b1) is at least one selected from the group of nickel and copper, preferably nickel is used. The first metal plating layer is a plating solution composed of 50ml / L EN800NB-M (Youngjin Plachem, Korea), 50ml / L EN8000NB-N (Youngjin Plachem, Korea) and 50ml / L EN8000NB-B (Youngjin Plachem, Korea). It can be formed by electroless plating for 30 to 60 minutes at 60 to 90 ℃. This first metal plating layer functions as a base metal layer.

The second metal plating layer is formed on the first metal plating layer by the step (b1). Examples of the second metal are at least one selected from the group of nickel, copper, zinc, chromium and tin, and nickel is preferably used. The second metal plating layer is a process for adjusting the surface roughness of the molded product finally obtained. This step is preferably formed at least two or more layers using an electroless gold rate gold process. For example, a plating solution consisting of 60 ml / L ENCHEM M-2001-A (Winstar Korea, Korea) and 150 ml / L ENCHEM M-2001-B (Winstar Korea, Korea) was used for 30 to 60 minutes at 80 to 90 ° C. It can be formed by electroless plating.

The plated molded body is dried by hot air for 30 to 60 minutes at 80 to 90 ° C. by step (b3) to be finalized.

The polyphenylene sulfide molded body in which the plating layer obtained by the above process is formed is excellent in surface roughness characteristics, and it becomes possible to give especially light weight to electrical conductivity of components used for various industrial products.

Therefore, the molded article obtained according to the present invention can be used when a metal surface is required on the surface in electronic, telecommunication parts, acoustic imaging parts, automobile parts and mechanical parts.

Hereinafter, the present invention will be described in detail by the following examples. However, the following examples are only illustrated to aid the understanding of the present invention, and the scope of the present invention is not limited to the following examples.

≪ Example 1 >

The polyphenylene sulfide molded body whose surface was cleaned with trichloroethylene was dipped in 40 g / L of PROCLEAN 151 for 6 minutes at 40 ° C. to remove contaminants on the surface. Thereafter, an etchant composed of 400 g / L chromic acid and 200 ml / L sulfuric acid was used to etch primarily at 60 ° C. for 15 minutes. The secondary etching treatment was performed by treating the surface of the primary-etched molded body at room temperature with a stock solution of nitric acid for 10 minutes. In order to remove the chromium powder present on the surface of the etched molded body, 50 ml / L hydrochloric acid was neutralized by treating at room temperature for 2 minutes. Subsequently, 10% of the surfactant was treated in a subsequent step, followed by a surface adjustment process at 25 ° C. for 15 minutes. Thereafter, palladium was adsorbed on the surface by treatment at 25 ° C. for 30 minutes with a solution composed of 0.2 g / L palladium and 150 ml / L hydrochloric acid for catalysis. 5% ACC was treated at 25 ° C. for 2 minutes to remove impurities such as tin present on the surface of the molded body.

50 ml / L EN800NB-M (Young In Plachem, Korea), 50 ml / L EN8000NB-N (Young In Plachem, Korea), and 50 ml / L EN8000NB-B Youngin Plachem, Korea) was treated with a plating solution for 30 minutes at 60 ℃ to form a nickel base plated layer. Subsequent process consists of 60ml / L ENCHEM M-2001-A (Winstar Korea, Korea), 150ml / L ENCHEM M-2001-B (Winstar Korea, Korea) and 30 wt% PTFE on the nickel base plated layer. The plating solution was treated and subjected to an electroless plating process at 80 ° C. for 30 minutes to form a secondary nickel plated layer.

As described above, it has been described with reference to a preferred embodiment of the present invention, but those skilled in the art various modifications and changes of the present invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

Claims (12)

(a) surface treating the polyphenylene sulfide molded body; And (b) A method for producing a polyphenylene sulfide molded body with a plating layer comprising the step of forming a plating layer on the surface of the polyphenylene sulfide molded body surface-treated. The method of claim 1, The surface treatment step of the polyphenylene sulfide molded body, (a1) cleaning the surface of the polyphenylene sulfide molded body; (a2) removing and etching contaminants on the cleaned polyphenylene sulfide molded body surface; And (A3) A method for producing a polyphenylene sulfide molded body with a plating layer comprising the step of adjusting the flatness of the surface of the etched polyphenylene sulfide molded body. The method of claim 2, The etching step of step (a2) (a2-1) primary etching using a solution consisting of chromic acid and sulfuric acid; And (a2-2) A method for producing a polyphenylene sulfide molded article having a plating layer including a second etching step using a nitric acid solution. The method of claim 2, Method of producing a polyphenylene sulfide molded body formed with a plating layer, characterized in that it further comprises the step of neutralizing the surface of the molded body after the etching step of (a2). The method of claim 1, Method for producing a polyphenylene sulfide molded body with a plating layer further comprising the step of metallizing the surface of the polyphenylene sulfide molded body. The method of claim 1, Method for producing a polyphenylene sulfide molded body with a plating layer further comprising the step of metallizing the surface of the polyphenylene sulfide molded body. The method of claim 5, The metallization step is a method for producing a polyphenylene sulfide molded body formed with a plating layer, characterized in that by adsorbing palladium. The method of claim 1, The plating layer is a method for producing a polyphenylene sulfide molded body formed with a plating layer, characterized in that formed by an electroless plating process. The method of claim 1, Forming the plating layer is (b1) forming a plating layer made of a first metal on a surface of the polyphenylene sulfide molded body; (b2) forming at least one plating layer made of a second metal on the first metal plating layer; And (b3) A method for producing a polyphenylene sulfide molded article having a plating layer including a step of drying the polyphenylene sulfide having a plating layer formed thereon. 10. The method of claim 9, The first metal is at least one selected from the group consisting of nickel and copper, the method for producing a polyphenylene sulfide molded article having a plating layer. 10. The method of claim 9, The second metal is at least one member selected from the group of nickel, copper, zinc, and chromium. The polyphenylene sulfide molded body in which the plating layer obtained by Claim 1 was formed.
KR1020090087350A 2009-09-16 2009-09-16 Preparation method of polyphenylenesulfide shaped body with plating layer and the shaped body KR20110029602A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111748806A (en) * 2020-07-21 2020-10-09 江苏悦锌达新材料有限公司 Roughening liquid for polyphenylene sulfide and composite material thereof, preparation method and use method thereof
KR20200144716A (en) 2019-06-19 2020-12-30 대영엔지니어링 주식회사 Wet surface treatment method of nonconductive plastic
CN112940504A (en) * 2021-02-03 2021-06-11 河源市皓吉达通讯器材有限公司 Method for reducing refractive index of optical channel material of camera

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200144716A (en) 2019-06-19 2020-12-30 대영엔지니어링 주식회사 Wet surface treatment method of nonconductive plastic
CN111748806A (en) * 2020-07-21 2020-10-09 江苏悦锌达新材料有限公司 Roughening liquid for polyphenylene sulfide and composite material thereof, preparation method and use method thereof
CN111748806B (en) * 2020-07-21 2022-08-23 江苏悦锌达新材料有限公司 Roughening liquid for polyphenylene sulfide and composite material thereof, preparation method and use method thereof
CN112940504A (en) * 2021-02-03 2021-06-11 河源市皓吉达通讯器材有限公司 Method for reducing refractive index of optical channel material of camera

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