CN101195911A - Preprocessing solution and method for forming coating metal layer on substrate with plastic surface - Google Patents
Preprocessing solution and method for forming coating metal layer on substrate with plastic surface Download PDFInfo
- Publication number
- CN101195911A CN101195911A CNA2006101659030A CN200610165903A CN101195911A CN 101195911 A CN101195911 A CN 101195911A CN A2006101659030 A CNA2006101659030 A CN A2006101659030A CN 200610165903 A CN200610165903 A CN 200610165903A CN 101195911 A CN101195911 A CN 101195911A
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- acid
- solution
- preprocessing solution
- metal
- aforementioned
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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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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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
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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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
- C23C18/208—Multistep pretreatment with use of metal 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
- C23C18/26—Roughening, e.g. by etching using organic liquids
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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
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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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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Abstract
The invention relates to a pretreatment solution for forming a coating metal layer on a foundation base and the method, the foundation base is equipped with a plastic surface, and the invention in particular relates to the method for forming the coating metal layer on at least one component of the polyamide and the polyoxymethylene plastic.
Description
Technical field
The present invention relates in substrate to form the preprocessing solution and the method for coating metal layer, described substrate has frosting, more specifically to the method that forms coating metal layer at polymeric amide and acetal plastic parts on one of at least.Especially in ornamental plating industry, use this solution and method and come plating polymeric amide or acetal plastic substrate.
Background technology
The polyamide plastics parts have just been begun to electroplate as far back as many years ago.But range of application is narrow always because plating polyamide parts market is limited, so the research work of carrying out in this field seldom.Described first method in the publication of association (AES) the 65th session is electroplated by the U.S. that Washington in 1978 holds, it has brought up to about 1 N/mm with the stripping strength between metal level and plastic components.But,, do not point out the detail of this method except not using the chromic acid.The influence to adhesion strength of the surface tissue that obtains behind first method steps has been described, similar to the situation of acrylonitrile-butadiene-styrene copolymer (ABS) plastic components.In the ABS plastic parts, there is significantly relation between microscopic surface texture and the adhesion strength.
Now, for the pre-treatment of polyamide plastics parts, except described first method, also have two kinds of main optional methods, these optional methods comprise on the one hand with the solution pretreatment component that contains chromium (VI), use solution and sour pretreatment component on the other hand.The pretreated main drawback that uses chromium (VI) is that healthy and environment are harmful to, so its use is limited.In addition, opposite with ABS plastic, polymeric amide shows open relatively polymer architecture, thereby has the sizable water-absorbent up to 6%.This character also will make an appointment with quite a large amount of chromium (VI) to suck in the polymkeric substance, can not easily remove these chromium by cleaning with other chemical treatment.
Therefore, comprise with the above-mentioned another kind of optional method that contains the aqueous solution pre-treatment polyamide plastics parts that mineral acid and solvent (normally glycol ether) make up seemingly favourable.In the method, after implementing pre-treatment, the catalysis plastic components, this step comprises two or three steps: first optional step comprises plastic components is immersed in the polar polymer solution, thereby provides this extremely thin polymer layer to parts surface.This polymkeric substance is used for higher concentration and bigger intensity catalyzer being bonded on the surface of polyamide plastics parts.It will be more reliable will reducing the consumption of expensive catalysts and the further catalysis of parts thus.After from plastic components, washing adhesion solution, by parts are contacted with the solution that contains colloidal palladium it is carried out catalysis usually.Described solution is tart and comprises tin chloride and ideally be very suitable for the nonpolar olefin polymer of catalysis for example ABS or polycarbonate.The catalysis (EP 0 406 859 B1) that this solution is used for the polyamide plastics parts has also been described.
But, verifiedly not necessarily need to use these complexity and expensive catalysts to handle the microcellular polyamide plastic components.The solution that comprises ionic palladium also proves suitable, and this solution is easier preparation and not too expensive.According to the type of catalysis process, after with catalyst treatment, in specific solution, further handle plastic components.For example, if used the colloidal palladium catalyzer, plastic components contacts with so-called promotor, and it will remove the tin sheath (tin sheath) around the colloidal solid.All solution that can dissolve tin (II) may be used to this purpose, for example dilute hydrochloric acid, sulfuric acid, sodium hydroxide and organic acid.By reductive agent, for example borine hydrochlorate (boranates) (dimethylamino borine and alkali metal borohydride) and hypophosphite, the ionic palladium that is adsorbed onto on the used plastic components will be reduced into simple substance (elemental) metallic palladium.
Now, the most normal method of using comprises uses swelling and cleaning solution to handle the polyamide plastics parts, and described solution comprises glycol ether, mineral acid and tensio-active agent.Processing element is after required treatment time in this solution, thoroughly washes this solution and adheres to remnants on the plastic components.Then, in suitable conditioning agent, handle and catalytic member in acid palladium salts solution at last.After being exposed in the reducing solution, to parts nickel plating, electro-coppering and last plating are as the metal of facing, normally nickel or chromium then in electroless nickel plating solutions.
In addition, DE 31 37 587 C2 disclose the polyamide plastics parts that are used for decorative applications with the solution pre-treatment that comprises organic solvent (for example glycol ether) and acid (for example hydrochloric acid).Subsequently, by electroless plated metal coating coated parts, metal adheres well on the parts.
In addition, EP 0 406 859 B1 and EP 0 604 13 1 B1 disclose and have used oxidizing acid, for example chromic acid/sulfuric acid pre-treatment polyamide plastics parts.In addition, EP 0 604 131 B1 also disclose and have used mineral acid, comprise hydrochloric acid, sulfuric acid, phosphoric acid, chromic acid, formic acid and acetate etching polyamide plastics parts.The method of two pieces of documents all also comprises makes the polyamide plastics parts contact with comprising the solution of colloidal palladium with tin (II), removes detin (II) after passing through accelerate process.In addition, EP 0 604131 B1 also disclose use sensitizing agent-activator method or parts have been immersed in the palladium solution reduction solution and handled the polyamide plastics parts.
Considering between each step of aforesaid method needs three cleaning steps usually, relates to 16 steps until whole operations of electroless nickel plating step.
" Kunststoffmetallisierung-Handbuch f ü r Theorie und Praxis " (" Plastics Metallization-Handbook for the Theory and Practice "), EugenG.Leuze Verlag, Saulgau, Germany, 1991, the 47th and the 141-156 page or leaf mentioned the treatment process of another kind of polyamide plastics parts, it relates to the palladium catalyst catalysis plastic components that comprises the palladium coordination compound that contains organic ligand.This organic ligand provides the avidity specific with polyamide surface to coordination compound, it is said that this can influence the adhesivity of the metal level that formed afterwards on plastic components.Slight swelling or " roughening " that the document is also mentioned the polyamide plastics surface will be favourable.With chromic acid and with the acid and the processing of etching reagent will be inapplicable, because these reagent will irreversibly damage plastic components.More particularly, described method comprises at first contacts the polyamide plastics parts with the organic palladium title complex, then parts are carried out intermediate treatment, comprises the amorphous surfaces of swelling parts, uses the etching agent that comprises calcium and aluminium salt, and gives the parts electroless nickel plating at last.
Aforesaid method proves tediously long and is complicated.Need less step to realize in the polyamide plastics substrate that simultaneously itself and surface have the method for the metallic coating of strongly adherent in order under the least possible work, to give polyamide plastics parts metal lining reliably, must to provide.
United States Patent (USP) the 5th, 296, described the method that forms metal level on the polyamide plastics parts surface in No. 020, this method comprises uses the activator prescription of being made up of the aqueous dispersions of organic precious metal, filler, organic solvent and polyether polyols with reduced unsaturation to handle the polyamide plastics parts.More particularly, described organic precious metal is by palladium and alkene, α, and the organometallic compound of beta-unsaturated carbonyl compound, crown ether and nitrile provides.Then, activator compound is reduced to metallic state, perhaps passes through the aqueous dispersions of coordination agent coordination and introducing polyether polyols with reduced unsaturation.Solvent can be a glycol ether, for example ethylene glycol monomethyl ether, diglyme or propylene glycol monomethyl ether acetate, and be used for dissolving organic Pd compound simply.Therefore, use a spot of these solvents.In case in this prescription,, will implement the metallization of plastic components, for example pass through electroless nickel plating by no electric metal plating for example by after the dipping pre-treatment.Can in no electric metal plating bath, directly reduce ionic palladium and not need other step.
In addition, United States Patent (USP) the 5th, 300 discloses for No. 140 and to be used for the base metallization surface, for example the aqueous priming paint of polyamide surface (hydroprimer).By using its thin layer on the basad surface this aqueous priming paint is administered to the no electric metal that is used on the substrate surface subsequently and plates for example nickel plating.Aqueous priming paint also comprises the water dispersible polymers except water, it is selected from the dispersible polyacrylic ester of water, polyhutadiene, polyester, melamine resin, urethane and the polyurethane-urea, and the covalency of ion precious metal, colloid precious metal or precious metal or coordination compound are as metallization catalyzer and filler.Possible activator is palladium and alkene, α, the Organometallic complexes of beta-unsaturated carbonyl compound, crown ether, nitrile and diketone.Can use the ionic metal of salt form equally, for example halogenide.Can be in no electric metal plating bath direct reduction precious metal.
Allegedly aforesaid method has been realized the metal level on coat substrates surface, high-adhesiveness ground.But, shown that catalyst formulation be not very reliable aspect the adhesivity of metal-plated ability (homogeneity of metal-plated) and sedimentary metal level.
United States Patent (USP) the 4th, 554 discloses the another kind of method of electroless plating polyamide plastics parts in No. 183.This method comprises mixture with the halogenide of simple substance periodictable the 1st and the 2nd main group simple substance and the salt of weak mineral alkali and strong inorganic acid at the organic swelling agent of non-etching of polymeric amide or the solution pre-treatment polyamide plastics parts in the solvent, and with the metal organic coordination compounds processing plastic components of for example palladium.Described in document, the coordination compound that uses the alkene comprise functional group and palladium is as metal-organic coordination compounds.Advantageously with its dispersion liquid, and particularly the form of its solution in suitable organic solvent is used metal-organic coordination compounds, and these solvents are that water is immiscible.Provided and only described the example that comprises alkene and the coordination compound solution of palladium in organic solvent.Can in electroless nickel plating baths, directly carry out the reduction of coordination compound.
It is moisture and comprise the shortcoming of pure organic solvent on the contrary that United States Patent (USP) the 4th, 554, the method for describing in No. 183 have wherein contained solution.In the practice, do not use these solution owing to need to reduce total oxygen concn (TOC).In addition, this solution must satisfy following requirement: it should not have the influence of any hostile environment, do not contain solvent with any and carbon bonded halogen, be water base, if and with an organic solvent, these solvents are to be not easy evaporable, to have high burning-point and be not deleterious, for example mutagenesis or produce deformity.Therefore, disclosed solution can not be used for industrial practice in the document.
Therefore, the purpose of this invention is to provide the method that in substrate, forms coating metal layer.
More particularly, the purpose of this invention is to provide, more particularly form the method for coating metal layer above one of at least on polymeric amide and acetal plastic surface at frosting.
Another purpose more of the present invention provides the method that forms coating metal layer on polymeric amide or acetal plastic surface, and described metal level adheres on the described frosting securely.
Another purpose more of the present invention provides on polymeric amide or acetal plastic surface the method that forms coating metal layer, and described method is to be easy to and to require great effort few and therefore implement under low cost.
Another purpose more of the present invention provides on polymeric amide or acetal plastic surface the method that forms coating metal layer, and described method is acceptable on the environment, and aspect healthy, is being acceptable aspect the toxicity of used chemical substance promptly.
Another purpose more of the present invention provides at substrate surface, more particularly forms the preprocessing solution that uses in the method for coating metal layer on polymeric amide or acetal plastic surface.
Another purpose more of the present invention provides and form the preprocessing solution that uses in the method for coating metal layer on polymeric amide or acetal plastic surface, and described solution is effective on the cost.
Summary of the invention
Realized above-mentioned purpose by the preprocessing solution of claim 1 and the method for claim 17.Quoted the preferred embodiment of the invention in the dependent claims.
In the following description, for complete understanding of the present invention is provided, a large amount of concrete details have been provided.But being to be understood that, those skilled in the art can not have to put into practice the present invention under some or all these concrete details.In other situation,, do not describe the known method operation in detail in order to make indigestion of the present invention necessarily.
The term of being mentioned " inorganic part " means at central atom or any neutrality of ion place arrangement or ionic inorganic chemistry material herein, and its quantity depends on central atom or ionic ligancy.Opposite with organic ligand, inorganic part comprises that those do not contain the material of c h bond.
The term of being mentioned " haloid acid " means hydrofluoric acid, hydrochloric acid, Hydrogen bromide and hydroiodic acid HI herein.
The term of being mentioned " pKs " means the negative denary logarithm of Ks herein, and Ks is the dissociation constant of acid in the aqueous solution, produces oxonium ion (H
3O
+).
The term of being mentioned " no electric metal plating bath " means and comprises the metal plating liquid that the coating metal ion can be reduced into the chemical substance of simple substance coating metal herein.For example electroless nickel plating solutions can comprise hypophosphite, diphosphanetetroic acid or dimethylamine borane as reductive agent.
Mean can be with any workpiece of metal level coating, for example plate, other device for molding or powder for the term of being mentioned " substrate " herein.
The term of being mentioned " weight % " means the component mark that comprises in the mixture herein, and this term is represented this mark with the parts by weight of component in per 100 weight part mixtures.
To mean chemical general formula be C to the term of being mentioned " alkyl " herein
nH
2n+1Chemical substance, wherein n is＞0 integer and 1-8 more particularly, more particularly 1-6 and the integer of 1-4 the most in particular.Alkyl can be side chain or non-side chain and preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-and the tertiary butyl.
The term of being mentioned " etching of frosting " means the use chemical substance herein, more specifically says so and frosting immersion solution wherein can be come roughening and modifies frosting.Because this processing, the key of the polymkeric substance of handling or fracture and/or oxidized and/or specific chemical functional group are modified.In the chemical modification frosting, also make this surface hydrophilic.Not only in polymeric amide and polyoxymethylene substrate, and in the ABS substrate, had been found that this effect.If use chromic acid etching processing ABS substrate, partly form carboxylic acid, ketone and aldehyde radical from the polyhutadiene of polymkeric substance, and in the situation of polymeric amide and polyoxymethylene substrate, by strong acid, for example the effect of sulfuric acid, hydrochloric acid, phosphoric acid, acetate or formic acid has reversed the condensation reaction that is used for forming polymeric amide or polymethanal polymer.It is believed that in polyamide plastics because the amino that this reaction forms is given the polyamide surface wetting ability.It is believed that in polyoxymethylene because the hydroxyl that this reaction forms is given this plastic material wetting ability.
The term of being mentioned " swelling of frosting " means with these surfaces of polar organic matter matter swelling herein, it is believed that they can be incorporated in the polymeric matrix, thereby makes its swelling and make its surface softening slightly.Very strong polar solvent is dissolve polymer fully.This dissolving can greatly damage frosting.Therefore, when handling polymeric amide and polyoxymethylene substrate, can only use to cause its slight swollen organic solvent (for example glycol ether),, they be mixed its influence of reduction with water perhaps for strong solvent (for example propyl carbonate, gamma-butyrolactone).
The term of being mentioned " conditioning agent " (promoting noble metal catalyst nuclear to be adsorbed onto polymeric amide and the lip-deep reagent of polyoxymethylene) means the metal deposition for these substrates herein, can influence the chemical substance of plastic-substrates surface properties.Conditioning agent mainly be adsorbed on the frosting and owing to many identical functional groups (for example-the OH base or-the NH yl) increase the hydrophilic organic molecule of substrate.Conditioning agent can comprise the group of lotus positive electricity or negative electricity.
The term of being mentioned " activation " means the frosting that preparation is used for no electric metal plating step subsequently herein, comprises the precious metal that deposits ionic species or colloidal form on frosting.If precious metal is an ionic species, use reducing solution that these precious metal ions are reduced into the simple substance precious metal subsequently, described simple substance precious metal forms noble metal catalyst nuclear.If precious metal is a colloidal form, these colloidal metals are as initial catalyst core.Usually, behind particle deposition, must remove the colloid (booster action) of colloidal solid any protection on every side.In any situation, begin not have the electric metal plating from the solution that comprises coating metal salt and reductive agent then.Usually, can use gold, palladium and platinum and iridium and rhodium, be used for the oxidation (for example being used for depositing silver) of phosphite or formaldehyde reducer as noble metal catalyst.This can cause the self catalyzed reduction as the metal of nickel, copper, iron and cobalt simultaneously.
Preprocessing solution of the present invention and method are used for forming coating metal layer in substrate, described substrate preferably has polymeric amide and polyoxymethylene surface one of at least, described substrate more specifically say so polymeric amide or acetal plastic substrate.Therefore, can use this solution and method to come ornamental polymeric amide of plating or acetal plastic substrate, for example be used for sanitary ware, automotive industry, assemble, be used for jewelry and other application, wherein give the polymeric amide or the acetal plastic substrate metal lining of main use because of its mechanics, chemistry, processing or thermal properties as furniture.
The polyamide plastics substrate can be polyamide 6, polyamide 6 .6, polymeric amide 11 and polymeric amide 12 plastic-substrates, but can be any other polyamide plastics substrate equally.In addition, the polymeric amide or the acetal plastic material of (for example mineral dust, as kaolin or glass fibre) can be handled and possessed filler material to the method according to this invention, and the polymeric amide or the acetal plastic material that do not possess filler material.Have been found that the use art methods can not metal-plated polymeric amide 11 and polymeric amide 12 plastic-substrates.According to their purpose purposes, injection molding polymeric amide and acetal plastic substrate make it have specific shape.
Preprocessing solution of the present invention comprises at least a organic solvent, at least a precious metal and at least a acid that the coating metal ion can be reduced into the ionic species of simple substance coating metal.Method of the present invention comprises: substrate a) is provided; B) substrate is contacted with preprocessing solution; And c), substrate in substrate, forms coating metal layer by being contacted with no electric metal plating bath.
Preprocessing solution of the application of the invention and method of the present invention will overcome the problem of using prior art solution and method to run into:
Owing to comprise acid in the solution, can optimize the adhesivity of the coating metal of using to polymeric amide or acetal plastic substrate, and need not in preprocessing solution to use those solvents that throw into question, described solvent is in toxicity, environmental influence, water miscibility, volatility, burning-point, attack stability, the cost that decomposes and need be problematic aspect carbon bonded halogen for acid.
In addition, in the adherent while of realizing coating metal and polymeric amide or acetal plastic substrate smoothly, solution of the present invention still is aqueous, thereby can make the content minimum of any organic solvent that wherein comprises.Therefore, also will make the TOC minimum.
In addition,, comprise the fact of three cleaning steps, can under low workload, easily implement method of the present invention because pre-treatment only needs four steps before the metal-plated plastic-substrates.This application that also will guarantee this method once more is cheaply.
In addition, owing on plastic-substrates, do not form polymeric film, if use the preprocessing solution that comprises tackiness agent, in the method will be in this film the combined catalyst metal, even use the catalyst metal of lower concentration, also can on all surface position of plastic-substrates, implement metal-plated in no problem ground.Therefore, the concentration of noble metal catalyst can be low, and same preprocessing solution also will be that cost is effective.
Described at least a acid preferably has and is equal to or less than 5, more preferably is equal to or less than 3 and most preferably be equal to or less than 2 pKs.Because acid can be dissolved polymeric amide and polyformaldehyde material usually,, thereby make it can be by other treatment agent moistening and produce certain roughness in its surface so described at least a acid can be attacked the surface of polymeric amide or acetal plastic material.But, different with the pre-treatment of ABS substrate, do not need the roughening frosting with the abundant adhesion that is implemented in the metal level that forms on this frosting and make this roughening minimum to avoid too many surface damage.As if the adhesion that surface tissue can the formed metal level of remarkably influenced.But it is believed that the acid that comprises in the preprocessing solution can dissolve the surface film of polymeric amide or acetal plastic material, thereby the cleaning of generation and polar surface.But, do not observe acid and attack polymeric amide or the acetal plastic material that has dissolved significant quantity.Therefore, Suan influence may be based on another mechanism.Although be not bound by any theory, the inventor thinks that acid makes the hydrogen bond rupture of frosting existence.As if destruction (etching) mechanism of this and chromic acid differs widely, and the latter relates to the fracture C-C, thus the chemical modification frosting.
The origin that has shown substrate to be processed has very big influence to the finished product of wanting metallizing.Especially, for polymeric amide and acetal plastic substrate really like this.Temperature that use during molding process thus, and that be used for forming the mould of plastic components is an important parameters.Usually, do not control molding temperature.But if handle polymeric amide or acetal plastic material, low tool temperature causes forming slight corrugated surface.But the adhesivity that is deposited on the metal level on the frosting will be very high.For this reason, tool temperature is low as far as possible, and for example 25-35 ℃ will be favourable.If use for example upper tool temperature more than 60 ℃, surface quality will be better.But adhesivity will reduce.By in preprocessing solution, using the suitable acid of proper concn can remedy this lower adhesive power numerical value to a certain extent.For example, prove that hydrochloric acid is being favourable under the concentration of about 200 ml/l (37 weight % hydrochloric acid soln), and sulfuric acid, phosphoric acid (no hydrochloric acid) or methylsulfonic acid are inappropriate.C
1-to C
4-carboxylic acid, for example formic acid and acetate, preferable formic acid produces very big adhesive power equally between metal level and frosting.These other sour optimum concn is 200-500 g/l.But must consider that formic acid may be with precious metal, Pd more specifically says so
2+Be reduced into the simple substance precious metal, the palladium of more specifically saying so.
But it is believed that by making it to contact with at least a acid to make that the surface is wettable to be because the chemical functionalization on surface: polyamide plastics comprises amide functional group, thereby it is in the auxiliary formation hydroxy-acid group and the amine groups of can rupturing down of acid.It is hydrophilic that these functional groups become plastic-substrates, therefore can be moistening by the aqueous solution.Similar mechanism provides wetting properties for the acetal plastic surface.
As previously mentioned, described at least a acid even more preferably be selected from haloid acid, formic acid, acetate and lactic acid.Most preferably, haloid acid is a hydrochloric acid.Use these acid, can realize metal level very good adhesivity on polymeric amide or acetal plastic substrate surface.
If preprocessing solution also comprises phosphoric acid except the strong acid of for example hydrochloric acid, found to realize metal level good especially adhesivity on polymeric amide or acetal plastic substrate surface.Most preferably, comprise the phosphoric acid of the aqueous hydrochloric acid of the 37 weight % of about 150ml, about 100ml and the organic solvent of about 50ml in 1 liter of preprocessing solution.If the concentration of hydrochloric acid is 150ml/l in the preprocessing solution, obtain best adhesive power numerical value.
The described at least a organic solvent that comprises in the preprocessing solution can be selected from glycol ether, more particularly has chemical formula R
1-O-gly
x-R
2Glycol ether, R wherein
1Be C
1-to C
6-alkyl, gly are-CH
2-CH
2-O-or-CH
2-CH (CH
3)-O-, wherein x is 1,2,3 or 4, and R wherein
2Be H, C
1-to C
6-alkyl or R
3-CO-, R
3Be C
1-to C
6-alkyl.More preferably described organic solvent is selected from diethylene glycol monoethyl ether and the diethylene glycol ether acetate alone.Their concentration in preprocessing solution can be at 1-990ml/l, in the scope of preferred 15-150ml/l.If the concentration of organic solvent in the concentration range of 50-200ml/l, is the mixture of hydrochloric acid and phosphoric acid as tartaric acid, metal level descends at polymeric amide or the lip-deep adhesivity of acetal plastic.
The adhesivity of the metal level that the remarkably influenced of proof organic solvent forms on polymeric amide or acetal plastic surface.Have been found that glycol ether is specially suitable.The compound of being mentioned proves clearly and satisfies following demand: do not have any deleterious environmental influence, do not contain any and carbon bonded halogen, be water mixable, be not easy evaporable, do not have low ignition point, to acid attack decompose be stable, have low cost and be not deleterious, for example mutagenesis or produce deformity.
Described at least a acid and described at least a organic solvent both also are used for moistening frosting, thereby guarantee that frosting is with the complete of treatment liq and contact reliably.In addition, necessary pre-treatment frosting before metal-plated, thus their pollutent can not disturb no electric metal electroplating method.Because pre-treatment according to the present invention includes only a step and three cleaning steps, so this pre-treatment step can also be removed all contaminants certainly and catalyzer is adsorbed onto on the frosting fully except moistening (hydrophilization) surface.Experiment has shown if use preprocessing solution of the present invention, and some cleaning effects can take place.But, must avoid being adsorbed on serious impurity and fingerprint on the frosting comprehensively.
In preferred embodiments, precious metal is a palladium.In a single day proof becomes metal core with this metallic reducing, it has superior catalyst property.The concentration of palladium in preprocessing solution can be at 10mg/l-2000mg/l, in the scope of preferred 20mg/l-100mg/l.
Can form in preferred embodiments and do not contain any part or only contain inorganic part, halogen ligands for example, therefore chlorine part does not more particularly contain the precious metal of the ionic species of any organic ligand.Most preferably, the precious metal of ionic species is Pd
2+If electroless nickel plating subsequently can use the electrochemistry normal potential than any other metal of the negative hundreds of mV of nickel and therefore can cause nickel deposition, for example iron or nickel.In the aqueous solution, palladium ion will have and coordination center ionic water molecules.Can use Pd with the form of Palladous chloride, Palladous nitrate or palladous sulfate
2+Its concentration is not crucial for the ability of the activation plastic-substrates of wanting metallizing usually.Its too high concentration with and too low concentration can not manifest any negative effect.The concentration that can select precious metal is for being equal to or less than 100mg/l, more particularly be equal to or less than 80mg/l, even more particularly be equal to or less than 60mg/l, even more preferably be equal to or less than 40mg/l and be most preferably 20-40mg/l (perhaps about 30mg/l).Certainly, if reduce precious metal concentration more and more, will postpone electroless metal deposition more and more.But this delay can not bring any injurious effects, does not have electric metal at the most and is plated in for the first time during the plating than slower during subsequently.
Most preferably, preprocessing solution is the aqueous solution.In addition, this embodiment satisfies the demand that pre-treatment should have the TOC of reduction and not have the hostile environment influence.
In addition, preprocessing solution can advantageously not contain any tackiness agent.With United States Patent (USP) the 5th, 296,020 and 5, disclosed embodiment differs widely in 300, No. 140, and the present invention preferably carries out under this tackiness agent not having, thereby do not form film on polymeric amide or acetal plastic substrate surface, this film combines and causes the required catalyst core of no electric metal plating.Thereby, because the many catalyst core in the film are capped and can't contact no electric metal plating bath, so this film will need more catalyst metal to cause no electric metal plating than the inventive method.
The very favorable embodiment of the present invention comprises uses promotion noble metal catalyst nuclear to be adsorbed onto polymeric amide or the lip-deep reagent of polyoxymethylene (conditioning agent).This conditioning agent will preferably be contained in the preprocessing solution.More particularly, promote that noble metal catalyst nuclear is adsorbed onto polymeric amide or the lip-deep reagent of polyoxymethylene can be the water-soluble polymers with polar group, the group of positively charged or negative electricity for example, thus they can mediate the adsorptivity between the contained chemical substance in frosting and the solution.For instance, it can be the polyelectrolyte compound.In a most preferred embodiment, this polyelectrolyte compound can be polyimidazole (polyimidazolium) compound, for example polyimidazole metilsulfate (polyimidazolium methosulfate).Use adsorption enhancer, will obviously strengthen the absorption of the metal level that on polymeric amide or acetal plastic surface, forms.The concentration of this reagent in preprocessing solution can be at 1mg/l-5000mg/l, in the scope of preferred 10mg/l-100mg/l.
Promote the reagent of absorption not only to promote noble metal catalyst to check the absorption of plastic-substrates, and promoted the absorption of catalyzer the supporting element (for example shelf) of any plastic components.This absorption will increase the consumption of precious metal on the one hand, and also cause coating metal on the other hand and deposit on the holding element.Therefore, must the frequent stripping coating metal.But, because promote the reagent of noble metal catalyst nuclear absorption will strengthen the absorption of precious metal, thus its concentration is minimized, every liter of preprocessing solution 20mg Pd for example
2+In addition, if use the reagent that promotes the absorption of noble metal catalyst nuclear, can carry out metal deposition to several polymeric amide or acetal plastic substrate, otherwise substrate can not plating.
In addition, only use hydrochloric acid if in preprocessing solution, do not use phosphoric acid, promote the reagent of noble metal catalyst absorption as if to strengthen the adhesivity that is deposited on the metal level on the plastic-substrates to a certain extent.
In addition, preprocessing solution of the present invention can comprise tensio-active agent.This reagent will reduce the surface tension of solution, thereby can more easily moistening plastic-substrates.Its chemical structure and characteristic are not claimed.Except will realizing the alap surface tension of preprocessing solution, this reagent is also incited somebody to action preferred easy flush away simply and is harmless, especially to animal.For this reason, the nonyl phenol derivative is not preferred.
In order in polymeric amide or acetal plastic substrate, to form conductive layer, can use any no electric metal plating bath.In a preferred embodiment of the invention, coating metal is a nickel.Therefore, because electroless nickel plating is that cost is effectively and because nickel plating solution is stable and the advantage of easy enforcement is provided to decomposing basically, so can use electroless nickel plating solutions deposition the first metal layer.In addition, can need not to use any deleterious compound, for example formaldehyde.
Generally, no electric metal plating bath, more particularly electroless nickel plating solutions comprises at least a metal ion source, more particularly at least a nickel ion source, for example single nickel salt or nickelous chloride; Also have reductive agent, for example at least a hypophosphite, diphosphanetetroic acid, borane compound, for example dimethylamine borane or sodium borohydride, perhaps formaldehyde is if deposited copper; And at least a coordination agent, carboxylic acid for example is as succsinic acid, citric acid, lactic acid, oxysuccinic acid, ethylidene tetraacethyl and their salt; At least a buffer reagent or other pH regulator agent are as acetate/acetate or sodium hydroxide.Hypophosphite and diphosphanetetroic acid are owing to its cost is better than other reductive agent.In addition, coating solution can comprise the additive that prevents the spontaneous decomposition of solution with used as stabilizers.
Method of the present invention has utilized the reductive agent that uses metal deposition solution palladium or other precious metal ion can also be reduced into the fact of simple substance palladium or another kind of simple substance precious metal.Because can use identical reductive agent, so use the reductive agent that comprises in the no electric metal plating bath can reduce precious metal ion for the reduction of precious metal ion and the deposition of coating metal.Therefore, in one embodiment, described method can only comprise four steps (pre-treatment step and three cleaning steps) before no electric metal plating substrate.Hypophosphite and diphosphanetetroic acid proof can be adsorbed onto the lip-deep Pd of polymeric amide or acetal plastic
2+The ion spontaneous reaction forms palladium catalyst nuclear, and it may cause nickel plating to being enough to store hydrogen atom greatly.If the temperature of electroless nickel plating solutions is about 50 ℃, after less than 30 seconds, finish Pd
2+Reduction.Astoundingly, with in independent step, reduce Pd
2+Other method compare Pd
2+Reduction in fact do not postpone.Usually, the electroless nickel plating cost is about 6-12 minute; Therefore can not detect any small delay in the nickel plating solution.Proof has nothing to do with using which kind of electroless nickel plating solutions, and electroless nickel plating is reliable.
Have been found that the method for the present invention that is included in the no electric metal plating bath reduction precious metal ion is reliable for the ability (even metal plating) of metal-plated, although it is believed that with no electric metal plating bath and handle plastic-substrates by cleaning, before taking place to reduce, peel off (strippedoff) and be adsorbed onto precious metal ion on the plastic-substrates to small part.In the case, because can deposit coating metal having peeled off the precious metal place,, but will make the no electropaining cloth metal plating liquid instability that becomes so the precious metal of absorption part is not used in the initiation of no electric metal plating.But this hypothesis does not take place in proof.Otherwise the precious metal that peels off from frosting will trend towards making the metal plating liquid instability.But, do not confirm this phenomenon, and do not observe the increase that contained reductive agent consumes in the metal plating liquid equally.
Preliminary experiment has shown that etching, adjusting and the activation step before used separately can be merged into a step (comprising organic solvent, acid, conditioning agent and catalyzer in preprocessing solution), and the previous steps of reduction activator material and the plating of no electric metal can be merged into another step, carry out cleaning step betwixt three times.Precipitation or negative interference do not take place when preparation preprocessing solution of the present invention.In addition, because the effect of pre-treatment chemical reagent, the conditioning agent material does not peel off from frosting.In addition, etching and activation do not cause the inhomogeneous covering from the teeth outwards of precious metal nuclear frosting the time.
In another embodiment of the invention, after step b) and before step c), substrate is contacted with reducing solution.Described reducing solution preferably comprises at least a reductive agent that the precious metal of described at least a ionic species can be reduced into the simple substance precious metal.Reductive agent can be preferably selected from hypophosphite and diphosphanetetroic acid.By polymeric amide or acetal plastic substrate are contacted with reducing solution, metal-plated possibility or even more reliable, because carry out metal-plated under can be in the preprocessing solution given precious metal concentration, realize the metal covering faster of plastic-substrates surface, perhaps even with precious metal concentration be reduced to low-down value, for example every liter of preprocessing solution 20 mg palladiums.Therefore, as the result of sucking-off from pretreatment baths (drag-out) preprocessing solution, precious metal losses still less makes the consumption of precious metal minimize, so can implement described method very economically.In addition, by the no electric metal plating bath of having removed any substance protection from preprocessing solution, it adheres on the frosting rather than enters in the no electric metal plating bath the most at last.
If use this independent reducing solution to come from Pd
2+Activation causes electroless nickel plating, preferably operates reducing solution being not less than under 3 the pH.In addition, the temperature of this solution preferably is not less than 35 ℃.The concentration of hypophosphite is recommended as below 30g/l in this solution, and about 20g/l is enough (sodium hypophosphites; For other salt or diphosphanetetroic acid is identical volumetric molar concentration).
In pre-treatment step with do not have that to clean proof between the electric metal plating step be not crucial for metal-plastic adhesivity, even metal plating and other requirement.But, must lack as far as possible to prevent formation percolation structure (draining structure) on frosting in pre-treatment and time of using between the cleaning step for the first time.Clean under the situation that spend 1 minute and should in cleaning, efficiently stir plastic-substrates at least for the first time and carry out, thereby from base substrate, remove any organic solvent.
Experiment shown adhesivity as if significantly depend in the polyamide plastics parts suction with and the last degree of planar water in surface.For example, this understanding comes from etching reagent can not pre-treatment polymeric amide or acetal plastic surface, thereby keeps the abundant adhesivity of metal level above it.It is believed that the etching reagent fracture amido linkage or the polyamide plastics material that also ruptures, but it also will introduce the abundant adhesion that therefore more water have also hindered metal level in polymeric matrix owing to its strong hydrophilic nmature.In polyoxymethylene, cause similar effect.For this reason, use aqueous solution processing polymeric amide or acetal plastic substrate seemingly very disadvantageous.But because described method only was made up of four steps before the metal-plated plastic-substrates, and the first metal layer has sealed frosting then, thereby stops any further contact of surperficial and water, has avoided sucking excessive water.In addition, prove that the plastic components that stores metal deposition is favourable in order to strengthen the adhesivity of metal level.Usually, this adhering increase will be finished after at room temperature about 3 days, if but storing temp is increased to for example 60 ℃, can only after several hours, just finish.
Although the roughness on polymeric amide and acetal plastic surface is far below common ABS plastic surface, metal level may be higher than the adhesivity of metal level to the ABS substrate to the adhesivity of polymeric amide or acetal plastic substrate.This observations may more have electrostatic interaction between polar polymeric amide or the acetal plastic surface owing to metal level with than ABS plastic surface.Be adsorbed onto between metal level and the frosting on the interface and be absorbed into any water in the plastic material and spread all over whole plastic material after, obtain this and the higher adhesivity of polymeric amide or acetal plastic surface.Porosity by polymeric amide or acetal plastic material can bring this distribution.
In order to handle plastic-substrates according to the present invention, by their being immersed in solution or, make they and preprocessing solution by spraying or splash solution on the plastic-substrates surface, randomly reducing solution, no electric metal plating bath contact with cleaning liquid., plastic components can be fixed on the shelf for this reason, perhaps be contained in the drum, perhaps transmit, parts are placed on top hanging basket for the described treatment facility of holding member has been equipped with by treatment facility.
With reference to following drawings and Examples the present invention is described more clearly.Embodiment shown in the drawings and Examples does not plan to limit the scope of the invention.
Fig. 1 has shown that the different acid of use is combined in nickel under the different organic solvent concentration/copper layer adhesive power on the polyamide plastics band with acid in preprocessing solution.
Embodiment 1:
In order to prepare preprocessing solution, in the aqueous hydrochloric acid of 1 liter of 37 weight % that comprise 200ml/l diethylene glycol monomethyl ether and 40ml/l, add the conditioning agent of 250 μ l palladium chloride solution (it comprises the palladium salt of 10 weight % concentration (referring to palladium content)), 0.5ml 30 weight %
(trade mark of German BASF) PVI solution and 0.1g sodium lauryl sulphate.Therefore, Pd in the preprocessing solution
2+Concentration be 25mg/l.Formed preprocessing solution is limpid and slightly flaxen.Heat this solution and remain under 40 ℃ the temperature.
3 mm are thick, 5cm is wide and 7cm is long by
(Lanxess, the trade mark of Germany) BM240 (polyamide 6, filler: handled in preprocessing solution 10 minutes, simultaneously gentle agitation plate in solution by the plate of kaolin) making.Then, with cold tap water clean plate, under gentle agitation, in water, kept 2 minutes more then.Then, in the commercially available electroless nickel plating baths that comprises 3g/l nickel and 20g/l sodium hypophosphite, under 45 ℃ temperature with described plate nickel plating 10 minutes.Subsequently at 2.5A/dm
2Cathode current density under to sedimentary nickel dam electro-coppering (
(Atotech, Germany trade mark) Ultra), until the metal bed thickness that obtains about 30 μ m.After cleaning, plate is stored 1 hour down at 70 ℃.Then, from each plate, cut out the wide band of 1cm and use tensile testing machine (
(Instron Corp., the trade mark of USA)) peel off copper from band.The adhesive power that records metal and polyamide plastics parts is 1.10N/mm.
Embodiment 1.1
Table 1: the amount of the Pd on the polyamide plastics plate
| Palladium concentration [mg/l] | Palladium amount [the mg/m of absorption 2] |
| 40 | 12.7 |
| 60 | 18.0 |
| 80 | 23.2 |
| 100 | 25.2 |
| 120 | 30.7 |
Embodiment 1.2:
Carry out the top temperature of other test evaluation preprocessing solution.For this reason, repeat embodiment 1.It is believed that if the polyamide plastics plate that will handle is transferred in the purge tank first time, 40 ℃ ceiling temperature is for guaranteeing that it is suitable not forming striped from the container that comprises preprocessing solution.If select to be higher than 40 ℃ temperature, proof is during transfer evaporated too many solvent, concentrate thereby adhere to preprocessing solution component contained in the liquid film on the frosting,, therefore uneven condition (forming embossment shape structure) takes place at the frosting place further with the frosting reaction.
Embodiment 2:
Repeat the step of embodiment 1.Use the formic acid (about 98 weight %) of 40ml/l to replace hydrochloric acid.After electro-coppering, find that the adhesive power of metal level on plastic tape reaches 1.85N/mm.
Embodiment 3:
Repeat the step of embodiment 1.Use
(E.I.Du Pont de Nemours, the trade mark of USA) 73M40 (polyamide 6 .6) replaces
BM240.The size of plastic components is identical with the front.Measuring metal level is 0.97N/mm at the adhesive power of frosting.
Embodiment 4:
According to the method described in the embodiment 2 handle typically be used for automotive industry and by
BM240 makes and molded indoor handle in the mould with 40 ℃ of tool temperature.After date when 3 days storage is because to such an extent as to very good metal strip fracture of adhesivity or plastic material fracture can't record concrete adhesive power result; Can't on the interface between metal level and frosting, separate during the stripping test.
Embodiment 5:
In order to prepare preprocessing solution, in the aqueous solution of 1 liter of 98 weight % formic acid that comprise 150ml/l diethylene glycol ether acetate alone and 100ml/l, add 0.50ml palladous sulfate solution, it comprises the palladium salt and the 0.1g sodium lauryl sulphate of 4 weight % concentration (referring to palladium content).Therefore, Pd in the preprocessing solution
2+Concentration be 20mg/l.Heat formed preprocessing solution and hold it under 40 ℃ the temperature.
3mm is thick, 5cm is wide and 7cm is long by
The plate that BM240 makes was handled in preprocessing solution 10 minutes, simultaneously gentle agitation plate in solution.Then, with cold tap water clean plate, under gentle agitation, in water, kept 2 minutes more then.Then, in the commercial electroless nickel plating baths that comprises 3g/l nickel and 20g/l sodium hypophosphite, under 45 ℃ temperature, made plate nickel plating 10 minutes.Subsequently to sedimentary nickel dam electro-coppering.After cleaning, plate is stored 1 hour down at 70 ℃.As previously described, the adhesive power of testing and recording between frosting and the metal level is 1.64N/mm.
Embodiment 6:
Palladium ion concentration is under the 50mg/ml in preprocessing solution, uses under different acid and acid combination and the organic solvent (diethylene glycol monoethyl ether) with different concentration, repeats embodiment 1.The temperature of preprocessing solution is 30 ℃.Shown the adhesive power numerical value that records among the figure of Fig. 1.
Fig. 1 has shown that use 150ml/l hydrochloric acid (37 weight %) and 100ml/l phosphoric acid obtain the adhering best result of nickel/copper layer on the polymeric amide band.(for example 50ml/l) realized best adhesivity if organic solvent concentration is set to lower value.In addition, if the concentration of used acid is quite low, preferably the concentration of solvent must be increased to the concentration that is higher than 50ml/l.In fact on the both sides of plate, observe some differences of adhesive power numerical value.Molded condition difference on these both sides owing to plate.
Claims (22)
1. preprocessing solution, it comprises the precious metal and at least a acid of at least a organic solvent, at least a ionic species, and the precious metal of described ionic species can be reduced into the coating metal ion simple substance coating metal.
2. according to the preprocessing solution of claim 1, wherein said at least a acid has and is equal to or less than 5 pKs.
3. according to any one preprocessing solution of aforementioned claim, wherein said at least a acid is selected from haloid acid, formic acid, acetate and lactic acid.
4. according to the preprocessing solution of claim 3, wherein said haloid acid is a hydrochloric acid.
5. according to any one preprocessing solution of aforementioned claim, one of wherein said at least a acid is phosphoric acid.
6. according to any one preprocessing solution of aforementioned claim, wherein said preprocessing solution comprises the phosphoric acid of the aqueous hydrochloric acid of the 37 weight % of about 150ml, about 100ml and the organic solvent of about 50ml in 1 liter.
7. according to any one preprocessing solution of aforementioned claim, wherein said precious metal is a palladium.
8. according to any one preprocessing solution of aforementioned claim, the precious metal of wherein said ionic species does not contain any part or only contains inorganic part.
9. according to any one preprocessing solution of aforementioned claim, the precious metal of wherein said ionic species is Pd
2+
10. according to any one preprocessing solution of aforementioned claim, wherein said at least a organic solvent is selected from has chemical formula R
1-O-gly
x-R
2Glycol ether, R wherein
1Be C
1-to C
6-alkyl, gly are-CH
2-CH
2-O-or-CH
2-CH (CH
3)-O-, wherein x is 1,2,3 or 4, and R wherein
2Be H, C
1-to C
6-alkyl or R
3-CO-, R
3Be C
1-to C
6-alkyl.
11. according to any one preprocessing solution of aforementioned claim, wherein said organic solvent is selected from diethylene glycol monoethyl ether and the diethylene glycol ether acetate alone.
12. according to any one preprocessing solution of aforementioned claim, wherein said preprocessing solution is the aqueous solution.
13. according to any one preprocessing solution of aforementioned claim, wherein said preprocessing solution does not contain any tackiness agent.
14. according to any one preprocessing solution of aforementioned claim, wherein said preprocessing solution also comprises and promotes noble metal catalyst nuclear to be adsorbed onto the reagent on the frosting.
15. according to the preprocessing solution of claim 14, the reagent that wherein said promotion noble metal catalyst nuclear is adsorbed onto on the frosting is the polyelectrolyte compound.
16. according to the preprocessing solution of claim 15, wherein said polyelectrolyte compound is the polyimidazole compound.
17. form the method for coating metal layer in substrate, described substrate has frosting, described method comprises:
A) provide substrate;
B) make described substrate and contact according to any one preprocessing solution of claim 1-16;
C), described substrate in substrate, forms coating metal layer by being contacted with no electric metal plating bath.
18. according to any one method of aforementioned claim, wherein at method steps b) afterwards and at method steps c) before, described substrate is contacted with reducing solution, and described reducing solution comprises at least a reductive agent that the precious metal of described at least a ionic species can be reduced into the simple substance coating metal.
19. according to the method for claim 18, wherein said at least a precious metal is that palladium and described at least a reductive agent are selected from hypophosphite and diphosphanetetroic acid.
20. according to any one method of claim 17-19, wherein said coating metal is a nickel.
21. according to any one method of claim 17-20, wherein said no electric metal plating bath is an electroless nickel plating solutions.
22. according to any one method of claim 17-21, wherein said frosting be in polyamide surface or the polyoxymethylene surface one of at least.
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| TW95147751A TW200827482A (en) | 2006-12-08 | 2006-12-18 | Pre-treatment solution and method of forming a layer of a coating metal on a plastics surface containing substrate |
| EP06077232A EP1942207A1 (en) | 2006-12-08 | 2006-12-18 | Pre-treatment solution and method of forming a layer of a coating metal on a plastics surface containing substrate |
| PCT/EP2007/011201 WO2008068049A1 (en) | 2006-12-08 | 2007-12-10 | Pre-treatment solution and method of forming a layer of a coating metal on a plastics surface containing substrate |
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| CN109778152A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of improvement chemical plating method of high-specific surface area palladium/composite membrane of polymer |
| CN113293362A (en) * | 2021-05-25 | 2021-08-24 | 吉安宏达秋科技有限公司 | Chemical copper plating bulking solution and preparation method and application thereof |
| CN113853452A (en) * | 2019-05-17 | 2021-12-28 | 希德泰克基金会 | Light-permeable metal coating and method for producing same |
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| US9364822B2 (en) | 2013-06-28 | 2016-06-14 | Rohm And Haas Electronic Materials Llc | Catalysts for electroless metallization containing five-membered heterocyclic nitrogen compounds |
| EP3144414B1 (en) * | 2015-09-21 | 2022-11-23 | Airbus Defence and Space GmbH | Enzyme treatment of polyamide objects for metallization purposes |
| CN117178076A (en) * | 2021-03-29 | 2023-12-05 | 哈索赫伯特施密特有限两合公司 | Acid washing of polyamides |
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| US4004051A (en) * | 1974-02-15 | 1977-01-18 | Crown City Plating Company | Aqueous noble metal suspensions for one stage activation of nonconductors for electroless plating |
| DE3339857A1 (en) * | 1983-11-04 | 1985-05-15 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRE-TREATING POLYAMIDE SUBSTRATES FOR CURRENT METALLIZATION |
| DE4111817A1 (en) * | 1991-04-11 | 1992-10-15 | Bayer Ag | FORMULATION FOR ACTIVATING SUBSTRATE SURFACES FOR THEIR CURRENT METALIZATION |
| DE4412463C3 (en) * | 1994-04-08 | 2000-02-10 | Atotech Deutschland Gmbh | Process for the preparation of a palladium colloid solution and its use |
| DE19740431C1 (en) * | 1997-09-11 | 1998-11-12 | Atotech Deutschland Gmbh | Metallising non-conductive substrate regions especially circuit board hole walls |
| DE10259187B4 (en) * | 2002-12-18 | 2008-06-19 | Enthone Inc., West Haven | Metallization of plastic substrates and solution for pickling and activation |
-
2006
- 2006-12-08 CN CN2006101659030A patent/CN101195911B/en not_active Expired - Fee Related
- 2006-12-18 EP EP06077232A patent/EP1942207A1/en not_active Withdrawn
- 2006-12-18 TW TW95147751A patent/TW200827482A/en unknown
-
2007
- 2007-12-10 WO PCT/EP2007/011201 patent/WO2008068049A1/en active Application Filing
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| CN109898116A (en) * | 2012-03-15 | 2019-06-18 | 安美特德国有限公司 | By the method for non-conductance metallization of plastic surface |
| CN104254641A (en) * | 2012-03-15 | 2014-12-31 | 安美特德国有限公司 | Process for metallizing nonconductive plastic surfaces |
| CN104254641B (en) * | 2012-03-15 | 2016-05-18 | 安美特德国有限公司 | Non-electricity is led to the method for metallization of plastic surface |
| CN104169465A (en) * | 2012-03-15 | 2014-11-26 | 安美特德国有限公司 | Process for metallizing nonconductive plastic surfaces |
| CN108890940A (en) * | 2012-05-14 | 2018-11-27 | 汽车专利管理和利用有限公司 | Plastics composite material assembly |
| CN104854216A (en) * | 2012-12-07 | 2015-08-19 | 埃托特克德国有限公司 | Process for metallizing nonconductive plastic surfaces |
| CN107923043A (en) * | 2015-07-30 | 2018-04-17 | 巴斯夫欧洲公司 | By the method for metallization of plastic surface |
| JP2018527460A (en) * | 2015-07-30 | 2018-09-20 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Pretreatment method of plastic surface for plating |
| CN109778152A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of improvement chemical plating method of high-specific surface area palladium/composite membrane of polymer |
| CN108251874A (en) * | 2018-01-24 | 2018-07-06 | 永星化工(上海)有限公司 | Suitable for the preprocessing solution of coating metal layer on the functional resin composition of plating |
| CN113853452A (en) * | 2019-05-17 | 2021-12-28 | 希德泰克基金会 | Light-permeable metal coating and method for producing same |
| CN113293362A (en) * | 2021-05-25 | 2021-08-24 | 吉安宏达秋科技有限公司 | Chemical copper plating bulking solution and preparation method and application thereof |
| CN113293362B (en) * | 2021-05-25 | 2022-02-11 | 吉安宏达秋科技有限公司 | Chemical copper plating bulking solution and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1942207A1 (en) | 2008-07-09 |
| TW200827482A (en) | 2008-07-01 |
| CN101195911B (en) | 2011-06-22 |
| WO2008068049A1 (en) | 2008-06-12 |
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