CN105189815A - Synthetic resin product plating method - Google Patents
Synthetic resin product plating method Download PDFInfo
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- CN105189815A CN105189815A CN201480001183.7A CN201480001183A CN105189815A CN 105189815 A CN105189815 A CN 105189815A CN 201480001183 A CN201480001183 A CN 201480001183A CN 105189815 A CN105189815 A CN 105189815A
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- resin products
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/18—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Toxicology (AREA)
- Chemically Coating (AREA)
Abstract
Disclosed is a synthetic resin product plating method for forming a plating layer, which can be formed in various patterns and has an excellent adhesion force, on a surface of a synthetic resin product in which heavy metal is not contained. The disclosed synthetic resin product plating method comprises: a laser activation step for radiating a laser to a plating region on a surface of a synthetic resin product to form fine pores on the surface; a catalyst adsorption enhancement step for immersing the synthetic resin product in an enhancing solution such that an adsorption enhancing material for enhancing the adsorption of a metal catalyst is attached to the surface of the synthetic resin product; and a metal catalyst adsorption step for immersing the synthetic resin product in a metal catalyst solution such that a metal catalyst is adsorbed onto the surface of the synthetic resin product.
Description
Technical field
The illustrative embodiments of the present invention's design relates to a kind of method for making the coating surface of synthetical resin products (syntheticresinproduct) (plating, plating) have metal level with the pattern of expection.
Background technology
Injection molding synthetical resin products is widely used in manufacturing electronics as smart mobile phone, panel computer etc., its comparatively light and miniaturization, and for reducing production cost.Synthetical resin products is comparatively light, be less limited to and utilize injection molding and formed, and cost is lower.
But synthetical resin products is non-conductor, be therefore applied to needing the parts of electroconductibility to have difficulty.The known certain methods of surface for the formation of conductive metal layer by processing synthetical resin products.Metal level can be applicable to the antenna for radio communication in the housing of mobile electronic device as smart mobile phone and panel computer.
One of Conventional exemplary embodiment that the surface of synthetical resin products is formed metal level comprises: by with an organic solvent etching surface, the adsorptive catalyst metal of synthetical resin products and carrying out electroless-plating (electroless plating, electroless plating, electrolessplating).
Another Conventional exemplary embodiment that the surface of synthetical resin products is formed metal level comprises: the surface laser being comprised the synthetical resin products of heavy metal by etching makes heavy metal expose, and by using crystal seed (seed) to carry out electroless-plating to the heavy metal exposed.
The ordinary method forming metal level on the surface of synthetical resin products is disclosed in Korean patent registration No. 10-0374667, Korean Patent Publication No. 10-2001-0040872 and Korean Patent Publication No. 10-2004-0021614.
But method with an organic solvent has the operating station caused due to lower boiling and to catch fire and owing to being included in the possibility having toxic materials in strong volatile organic solvent and endocrine disrupter and cause the health damaging operator.
In addition, organic solvent rapid solution synthetical resin products, therefore, is difficult to the degree on the surface regulating etching synthetical resin products, thus, be difficult to form smooth coating.Meanwhile, owing to being necessary to use the specific synthetic resins comprising heavy metal, so use the method comprising the synthetical resin products of heavy metal to have the problem of product cost increase.
Summary of the invention
technical purpose of the present invention
According to an exemplary embodiment, inventive concept provides a kind of plating synthetical resin products to form the method for coating, described coating can be formed with different patterns and have strong adhesivity to the surface of synthetical resin products.
The present invention's design additionally provides and does not use volatile organic solvent plating synthetical resin products thus the method reducing environmental pollution and fire hazard.
technical scheme of the present invention
According to an illustrative embodiments of the present invention's design, the method of plating synthetical resin products comprises: carry out laser activation (laservitalization) for the formation of minute groove (Minute pores, minutegroove) by irradiating laser on the plating zones on the surface of synthetical resin products; Catalyst Adsorption promotes, and (Catalyst Adsorption strengthens, catalystadsorbingboost) promote to make to adsorb in solution (strengthening solution, boostsolution) to promote that material can be attached to the surface of synthetical resin products so that synthetical resin products is immersed in; By synthetical resin products being immersed in metal catalyst solution the surface of carrying out metal catalyst absorption and being used for metal catalyst to be adsorbed to synthetical resin products; By synthetical resin products dipping is removed the promotion material of absorption and the surface from metal catalyzer from the synthetical resin products except plating zones in the etch solution and from the surface of synthetical resin products; And make plating zones electroless-plating have metal by making metal catalyst serve as crystal seed.
Electroless-plating to comprise in the copper coating solution that the ethylenediamine tetraacetic acid (EDTA) (EDTA) by being immersed in by synthetical resin products at the temperature of 55 DEG C to 65 DEG C by mixing the copper (Cu) of 2.5g/L to 3g/L, the sodium hydroxide of 8g/L to 9g/L, the formalin of 3g/L to 3.8g/L and 30g/L to 35g/L makes 5 minutes to 10 minutes plating first layers of copper for the formation of the first layers of copper.In addition, the second layers of copper is prepared by being immersed in identical copper solutions by synthetical resin products at the temperature of 40 DEG C to 50 DEG C.
Electroless-plating to be included in the second layers of copper plating protective layer for the formation of the protective layer be made up of nickel (Ni) alloy or tin (Sn) alloy with hardness larger than copper (Cu).
Promote that solution is the tin protochloride (SnCl of 5g to 50g in every 1L water
2) and 10ml to 50ml 36% the mixture of hydrochloric acid (HCl), and Catalyst Adsorption promotes it is be immersed in by synthetical resin products to promote in solution 2 minutes to 8 minutes at 10 DEG C to 30 DEG C.
Metal catalyst solution is the sulfuric acid of every Palladous chloride of 1L water 0.1g to 0.4g and 36% of 10ml to 50ml, or the mixture of the sulfuric acid of every Palladous chloride of 1L water 0.1 to 1g and 98% of 1ml to 100ml.
Etching solution is the mixture of the Neutral ammonium fluoride of every 1L water 50g to 100g, and by synthetical resin products dipping was etched to 3 minutes in the etch solution for 1 minute.
According to an illustrative embodiments of the present invention's design, the method for plating synthetical resin products be included in further laser activation and Catalyst Adsorption promote between by synthetical resin products is immersed in comprise washing composition rinse water (cleansingwater) in and increase ultrasonic vibration and carry out ultrasonic cleaning for cleaning synthetical resin products.
According to an illustrative embodiments of the present invention's design, the method of plating synthetical resin products be included in further laser activation and catalyzer promote between within 5 minutes to 10 minutes, carry out alkaline degreasing (alkali degreasing, alkalidegreasing) for expanding minute groove to the surperficial degreasing of synthetical resin products by being immersed in by synthetical resin products in the skim soln by mixing water and Starso formation.In addition, the method comprises further by synthetical resin products being immersed in the skim soln that in acid solution, neutralization is present on the surface of synthetical resin products.
According to an illustrative embodiments of the present invention's design, the method of plating synthetical resin products comprises further carries out plating pre-treatment (platingpreconditioning) for activating the metal catalyst in plating zones by being immersed in by synthetical resin products in aqueous sulfuric acid (aqueous solution of sulfur-bearing, sulfuricwatersolution).
By synthetical resin products being immersed in the mixed catalytic agent solution (complex catalyst solution promoting solution and metal catalyst solution at 10 DEG C to 30 DEG C, compoundcatalystsolution) within 2 to 8 minutes, carry out Catalyst Adsorption to promote and metal catalyst absorption simultaneously, and by mixing the tin protochloride (SnCl of every 1L water 5g to 50g
2), the hydrochloric acid of the Palladous chloride of 0.1g to 0.4g and 36% of 10ml to 50ml or the tin protochloride (SnCl of every 1L water 5g to 50g
2), the sulfuric acid of the palladous sulfate of 0.1g to 1g and 98% of 1ml to 100ml and prepare mixed catalytic agent solution.
Promote that solution can be comprise cobalt (Co) promotes material solution as absorption.
effect of the present invention
According to design of the present invention, the coating of different pattern can be formed in pure synthetical resin products as on the surface of polycarbonate, it causes increasing fastness to efflorescence (weatherproof) and chemical resistant properties reduce production cost.
In addition, owing to not using volatile organic solvent during operating process, so environmental pollution and fire risk can be reduced, thus convenience and the security of operation is increased.
Accompanying drawing explanation
Fig. 1 shows the schema of the method for the plating synthetical resin products of an illustrative embodiments according to the present invention's design; And
Fig. 2 to Fig. 7 is the decomposition section of the method that the plating synthetical resin products of an illustrative embodiments according to the present invention's design is described with continuous order.
Embodiment
The solution and coating method of the synthetical resin products according to the embodiment of the present invention is more fully described hereinafter with reference to the accompanying drawings.Term as used in this specification is the term used to more suitably describe the preferred embodiments of the present invention, and it changes according to the intention of user or operator or those skilled in the art of the invention.The definition of these terms is based on the overall content of specification sheets.
Fig. 1 shows the schema of the method for plating synthetical resin products, and Fig. 2 to Fig. 7 is the decomposition section of the method that plating synthetical resin products is described with continuous print order.
With reference to figure 1, the method for plating synthetical resin products comprises laser activation (S10), ultrasonic cleaning (S20), alkaline degreasing (S30), neutralization (S40), Catalyst Adsorption promotion (S50), metal catalyst absorption (S60), etching (S70), plating pre-treatment (S80), plating first layers of copper (S90) and plating second layers of copper (S100).Laser manufacture antenna (LMA) is referred to as by the metal antenna (feeler) using the method for plating synthetical resin products to be formed on the surface of synthetical resin products.
Synthetical resin products can be made by not having the pure synthetic resins of heavy metal element.Such as, can by manufacturing synthetical resin products to pure polycarbonate resin injection molding.Synthetical resin products can be mobile equipment as the shell of smart mobile phone and panel computer or housing.
Collective reference Fig. 1 and Fig. 2, laser activation (S10) is by forming a large amount of minute groove (2) by laser radiation to the plating zones (PA) of synthetical resin products (1) with certain density on the surface of synthetical resin products (1), in other words, minute crack.Laser can be diode laser, ultraviolet (UV) laser, excimer laser etc.The diode laser of 800nm to 1100nm wavelength can be ideally used laser.
Ultrasonic cleaning (S20) washs synthetical resin products (1) by be immersed in by synthetical resin products (1) in the rinse water comprising washing composition and to increase ultrasonic vibration.The minute groove (2) formed by laser activation (S10) can have foreign matter as dust, therefore, is difficult to the foreign matter of purging method removing plating zones (PA) by routine.Foreign matter can be removed completely from minute groove (2) by ultrasonic cleaning (S20).
Collective reference Fig. 1 and Fig. 3, alkalescence degreasing (S30) is the surperficial degreasing by being immersed in by the synthetical resin products standing ultrasonic cleaning (S20) to synthetical resin products (1) in the skim soln comprising water and Starso, and expands minute groove (2).
In detail, skim soln is the basic solution made by the metasilicate of every 1L water mixing 40g to 90g, and carries out dipping synthetical resin products wherein at the temperature of 60 DEG C to 70 DEG C.By alkaline degreasing (S30) removing remaining carbon (C) resistates in minute groove (2), and form the groove (2a) expanded.
Neutralization (S40) is by standing synthetical resin products (1) dipping of alkaline degreasing (S30) in an acidic solution for neutralizing the skim soln be retained on the surface of synthetical resin products (1).Acidic solution can be the aqueous hydrochloric acid of 36% hydrochloric acid of 15vol% to 20vol% and the water of 80vol% to 85vol%.Now, can neutralize to 7 minutes by synthetical resin products (1) is immersed in the aqueous hydrochloric acid of 10 DEG C to 30 DEG C 3 minutes.Or, acidic solution can be the aqueous sulfuric acid of the sulfuric acid of 98% of 5vol% to 10vol% and the water of 90vol% to 95vol%, and within (1) 1 minute to 3 minutes, can neutralize by flooding synthetical resin products at the temperature of 40 DEG C to 60 DEG C wherein.
Collective reference Fig. 1 and Fig. 4, Catalyst Adsorption promotes that synthetical resin products (1) is immersed in promote in solution by (S50).By it, will promote that the absorption of metal catalyst absorption promotes that material (5) is adsorbed on the surface of synthetical resin products (1).
According to an embodiment, promote that solution is the mixture of the tin protochloride (SnCl2) of every 1L water 5g to 50g and 36% hydrochloric acid (HCl) of 10ml to 50ml, and absorption promotes that material (5) is tin (Sn).Be immersed in by synthetical resin products (1) at the temperature of 10 DEG C to 30 DEG C and promote in solution 2 minutes to 8 minutes, absorption is promoted, and material (5) can be attached on the whole surface of synthetical resin products (1).In some embodiments, promote that solution can comprise cobalt (Co) and promote material as absorption.
Collective reference Fig. 1 and Fig. 5, metal catalyst absorption (S60) is by promoting that the synthetical resin products (1) of (S50) is immersed in metal catalyst solution by standing Catalyst Adsorption, metal catalyst (6) being adsorbed to the surface of synthetical resin products (1).Metal catalyst solution can be the sulfuric acid of every Palladous chloride of 1L water 0.1g to 0.4g and 36% of 10ml to 50ml, or the mixture of the sulfuric acid of every Palladous chloride of 1L water 0.1g to 1g and 98% of 1ml to 100ml.
Herein, metal catalyst (6) is palladium (Pd).When synthetical resin products (1) is immersed in the metal catalyst solution of 10 DEG C to 30 DEG C 2 minutes to 8 minutes, metal catalyst (6) and absorption promote that material (5) causes formation to be adsorbed to the metallic compound on the whole surface of synthetical resin products (1).
Tin (Sn) has palladium (Pd) avidity (effinity) and attracts palladium (Pd).When tin (Sn) permeates synthetical resin products (1) surperficial, easily permeated the surface of synthetical resin products (1) by the palladium (Pd) that tin (Sn) attracts and deposit.It is darker in safe deposition around than groove (2a) that tin (Sn) and palladium (Pd) permeate groove (2a).
Meanwhile, Catalyst Adsorption promotion (S50) and metal catalyst absorption (S60) can not carried out with continuous print order respectively simultaneously.Illustrating in addition, in the mixed catalytic agent solution of the mixture promoting solution and metal catalyst solution, Catalyst Adsorption promotion (S50) and metal catalyst absorption (S60) within 2 minutes to 8 minutes, can be carried out by being immersed in by synthetical resin products (1) at the temperature of 10 DEG C to 30 DEG C simultaneously.Mixed catalytic agent solution can be the tin protochloride (SnCl of every 1L water 5g to 50g
2), the solution of the hydrochloric acid of the Palladous chloride of 0.1g to 0.4g and 36% of 10ml to 50ml, or the tin protochloride (SnCl of every 1L water 5g to 50g
2), the solution of the sulfuric acid of the palladous sulfate of 0.1g to 1g and 98% of 1ml to 100ml.
With reference to figure 1 and Fig. 6, etching (S70) to stand synthetical resin products (1) dipping of metal catalyst absorption (S60) in the etch solution.
Particularly, prepare etching solution by the Neutral ammonium fluoride of every 1L water mixing 50g to 100g, and by synthetical resin products (1) dipping being carried out etching (S70) in the etch solution for 1 minute to 3 minutes at the temperature of 10 DEG C to 30 DEG C.
By it, promote material (5), that is, tin (Sn) from the surface removing absorption of synthetical resin products (1).In addition, the region of surface except plating zones (PA) of removing synthetical resin products (1), that is, do not have the metal catalyst (6) of (with reference to figure 3) in the region of minute groove (2a), that is, palladium (Pd).Result, by etching (S70), remain the microscopic cavities (airbag, the bubble that are only adsorbed on plating zones (PA), airpocket) metal catalyst (6) in, and eliminate the metallic substance of peripheral region.
Plating pre-treatment (S80) is the metal catalyst (6) by the synthetical resin products (1) standing to etch (S70) being immersed in activation plating zones (PA) in sulphuric acid soln (sulphur-containing solution, sulfuricsolution).Particularly, preparing sulphuric acid soln by the sulfuric acid of 98% and the water of 85vol% to 90vol% that mix 10% to 15%, carrying out plating pre-treatment (S80) by synthetical resin products (1) being immersed in aqueous sulfuric acid 1 minute to 3 minutes at the temperature of 40 DEG C to 60 DEG C.Thus, the metal catalyst (6) in plating zones (PA) activated using in plating process as crystal seed, and to completely removes in the peripheral region of plating zones (PA) metallic substance that part exists.
Tin (Sn) has the character be dissolved in etching solution or aqueous sulfuric acid, and therefore, by etching (S70) and plating pre-treatment (S80), it is removed completely by the surface from synthetical resin products (1).But, the palladium (Pd) be adsorbed in air pocket (2a) deeply can permeate the surface of synthetical resin products (1), although and etching (S70) and plating pre-treatment (S80) also may not be removed.Be adsorbed on groove (2a) palladium (Pd) around and may be adsorbed to the surface of synthetical resin products (1) consumingly, therefore, by etching (S70) and plating pre-treatment (S80) it can be removed by the surface from synthetical resin products (1).
Collective reference Fig. 1 and Fig. 7, plating first layers of copper (S90) and plating second layers of copper (S100) are included in make the metal catalyst of plating zones (PA) (6) serve as specified phase in the metal electroless-plating of crystal seed.
Plating first layers of copper (S90) is immersed in copper coating solution by the synthetical resin products standing plating pre-treatment (S80) (1).Particularly, copper coating solution comprises the ethylenediamine tetraacetic acid (EDTA) (EDTA) of the copper (Cu) of 2.5g/L to 3g/L, the sodium hydroxide of 8g/L to 9g/L, the formalin of 3g/L to 3.8g/L and 30g/L to 35g/L, and carries out plating (S90) by synthetical resin products (1) being immersed in copper coating solution 5 minutes to 10 minutes at the temperature of 55 DEG C to 65 DEG C.In plating first layers of copper (S90) process, the first layers of copper (10) was with the thickness of 2 μm growth in plating zones (PA) in every 5 minutes.
First layers of copper 10 has thickness growth rate faster, but its thickness can not easily be controlled reposefully.Therefore, by plating second layers of copper (S100) but form stable and that smooth grown in thickness is slower the second layers of copper (12).
Particularly, at the temperature lower than the temperature of plating first layers of copper (S90), such as 40 DEG C to 50 DEG C, form plating second layers of copper (S100) by being immersed in the copper coating solution identical with the copper coating solution used in plating first layers of copper by the synthetical resin products (1) standing plating first layers of copper (S90).In plating second layers of copper (S100) process, the second layers of copper 12 with the grown in thickness of 2 μm to 3 μm per hour in the first layers of copper (10).The carrying out time of plating second layers of copper (S100) is according to the variation in thickness of the layers of copper (10,12) of design.
Embodiment may further include plating protective layer (S110).
Plating protective layer (S110) is formed by having than copper (Cu) the more protective layer 14 made of the nickel (Ni) of high rigidity or the alloy of tin (Sn), to protect the layers of copper (10,12) with relatively weak hardness not damaged the second layers of copper (12) is upper.Such as, the single nickel salt of 30g/L can be used to be used for the nickel-boron coating solution of complexing agent for plated nickel-borine Alloy Plating coating for the protection of the dimethyamine borane (DMAB) of layer, 3g/L for the Trisodium Citrate of reductive agent, 25g/L and the sulfuric acid of 25g/L.
1 μm of nickel to 4 μm of thickness-boron alloy protective layer can be formed by being immersed in nickel-boron coating solution by synthetical resin products (1) at 50 DEG C to 65 DEG C.
Although specifically illustrate with reference to its illustrative embodiments and describe the present invention, should be appreciated that when not departing from the spirit and scope of appended claims, various change can be made in form and details wherein.
Industrial usability
The present invention can be applicable to electronics as smart mobile phone and panel computer.
Claims (11)
1. a method for plating synthetical resin products, comprising:
On the surface of described synthetical resin products, laser activation is carried out to form minute groove by irradiating laser on the plating zones of described synthetical resin products;
Described synthetical resin products is immersed in and promotes in solution and carry out Catalyst Adsorption promotion, make to promote that the absorption of metal catalyst absorption promotes that material can be adsorbed to the surface of described synthetical resin products;
By described synthetical resin products being immersed in metal catalyst solution the surface making metal catalyst be adsorbed to described synthetical resin products;
Be used for from the described absorption promotion material of the surface removing of described synthetical resin products with from the surface from metal catalyzer except described plating zones by described synthetical resin products dipping is carried out etching in the etch solution; And
Carry out electroless-plating to described plating zones, described metal catalyst serves as crystal seed.
2. the method for plating synthetical resin products according to claim 1, wherein, described electroless-plating comprises:
By in the copper coating solution that described synthetical resin products is immersed in the ethylenediamine tetraacetic acid (EDTA) (EDTA) of the copper (Cu), the sodium hydroxide of 8g/L to 9g/L, the formalin of 3g/L to 3.8g/L and the 30g/L to 35g/L that comprise 2.5g/L to 3g/L at 55 DEG C to 65 DEG C 5 minutes to 10 minutes plating first layers of copper to form the first layers of copper; And
By described synthetical resin products being immersed in the described copper coating solution identical with the copper coating solution being used for plating first layers of copper plating second layers of copper at 40 DEG C to 50 DEG C to form the second layers of copper.
3. the method for plating synthetical resin products according to claim 2; wherein, described electroless-plating is included in plating protective layer in described second layers of copper further to be formed by having than copper (Cu) the more protective layer made of nickel (Ni) alloy of high rigidity or tin (Sn) alloy.
4. the method for plating synthetical resin products according to claim 1, wherein, by the tin protochloride (SnCl of every 1L water mixing 5g to 50g
2) and 10ml to 50ml 36% hydrochloric acid (HCl) prepare described promotion solution, and,
Wherein, described Catalyst Adsorption promotes to be included in and described synthetical resin products to be immersed at the temperature of 10 DEG C to 30 DEG C in described promotion solution 2 to 8 minutes.
5. the method for plating synthetical resin products according to claim 1, wherein, described metal catalyst solution comprises the sulfuric acid of every Palladous chloride of 1L water 0.1g to 0.4g and 36% of 10ml to 50ml, or the sulfuric acid of every Palladous chloride of 1L water 0.1g to 1g and 98% of 1ml to 100ml.
6. the method for plating synthetical resin products according to claim 1, wherein, described metal catalyst solution comprises the sulfuric acid of every Palladous chloride of 1L water 0.1g to 0.4g and 36% of 10ml to 50ml, or the sulfuric acid of every Palladous chloride of 1L water 0.1g to 1g and 98% of 1ml to 100ml.
7. the method for plating synthetical resin products according to claim 1, wherein, comprise further between described laser activation and described Catalyst Adsorption promote by described synthetical resin products is immersed in comprise washing composition rinse water in and increase ultrasonic vibration and carry out synthetical resin products described in ultrasonic cleaning.
8. the method for plating synthetical resin products according to claim 1, wherein, described method comprises further:
By described synthetical resin products being immersed in the surface alkalinty degreasing to described synthetical resin products in 5 minutes to 10 minutes in the skim soln prepared by mixing water and Starso and expanding described minute groove between described laser activation and described Catalyst Adsorption promote; And
By described synthetical resin products being immersed in the described skim soln that in acidic liquid, neutralization is present on the surface of described synthetical resin products.
9. the method for plating synthetical resin products according to claim 1, wherein, described method is included between described etching and described electroless-plating further by described synthetical resin products being immersed in aqueous sulfuric acid the plating pre-treatment being used for the described metal catalyst activated in described plating zones.
10. the method for plating synthetical resin products according to claim 1, wherein, by at 10 DEG C to 30 DEG C, described synthetical resin products is immersed in comprise described promotion solution and described metal catalyst solution mixed catalytic agent solution in carry out simultaneously described Catalyst Adsorption promote and described metal catalyst adsorb, and
Wherein, described mixed catalytic agent solution comprises the tin protochloride (SnCl of every 1L water 5g to 50g
2), the hydrochloric acid of the Palladous chloride of 0.1g to 0.4g and 36% of 10ml to 50ml, or the tin protochloride (SnCl of every 1L water 5g to 50g
2), the sulfuric acid of the palladous sulfate of 0.1g to 1g and 98% of 1ml to 100ml.
The method of 11. plating synthetical resin products according to claim 1, wherein, described promotion solution comprises cobalt (Co) and promotes material as absorption.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2014-0006890 | 2014-01-20 | ||
| KR1020140006890A KR101608220B1 (en) | 2014-01-20 | 2014-01-20 | Method for metal plating on synthetic resin product |
| PCT/KR2014/004400 WO2015108247A1 (en) | 2014-01-20 | 2014-05-16 | Synthetic resin product plating method |
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| CN105189815A true CN105189815A (en) | 2015-12-23 |
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| CN201480001183.7A Pending CN105189815A (en) | 2014-01-20 | 2014-05-16 | Synthetic resin product plating method |
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| KR (1) | KR101608220B1 (en) |
| CN (1) | CN105189815A (en) |
| WO (1) | WO2015108247A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532240A (en) * | 2016-12-26 | 2017-03-22 | 青岛伟林电子有限公司 | Mobile phone antenna and electroless plating technology thereof |
| WO2022220168A1 (en) * | 2021-04-15 | 2022-10-20 | 東京エレクトロン株式会社 | Substrate processing method, substrate processing device, and storage medium |
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| KR101713205B1 (en) * | 2015-08-18 | 2017-03-09 | 한국생산기술연구원 | Method for manufacturing ground gasket |
| KR101639219B1 (en) * | 2015-12-10 | 2016-07-13 | 인탑스 주식회사 | Resin member is formed in metal surface synthetic part production method |
| US11324123B2 (en) | 2017-04-21 | 2022-05-03 | Amogreentech Co., Ltd | Printed circuit nanofiber web manufacturing method |
| WO2018226076A2 (en) | 2017-06-09 | 2018-12-13 | 주식회사 아모그린텍 | Filter medium, manufacturing method therefor, and filter unit including same |
| KR102673198B1 (en) | 2017-11-15 | 2024-06-07 | 주식회사 아모그린텍 | Composition for manufacturing graphite-polymer composite and Graphite-polymer composites comprising the same |
| KR102393575B1 (en) * | 2020-04-17 | 2022-05-04 | 주식회사 씨엠케미칼 | An one-component type water-based pretreating composition for metal plating a resin article and a method for metal plating a resin article using the same |
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| WO2022220168A1 (en) * | 2021-04-15 | 2022-10-20 | 東京エレクトロン株式会社 | Substrate processing method, substrate processing device, and storage medium |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101608220B1 (en) | 2016-04-01 |
| WO2015108247A1 (en) | 2015-07-23 |
| KR20150086811A (en) | 2015-07-29 |
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