CN100480423C - Electroless plating method and electrically nonconductive plating object with plating film formed thereon - Google Patents
Electroless plating method and electrically nonconductive plating object with plating film formed thereon Download PDFInfo
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- CN100480423C CN100480423C CNB2005800008197A CN200580000819A CN100480423C CN 100480423 C CN100480423 C CN 100480423C CN B2005800008197 A CNB2005800008197 A CN B2005800008197A CN 200580000819 A CN200580000819 A CN 200580000819A CN 100480423 C CN100480423 C CN 100480423C
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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
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
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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
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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
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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
- C23C18/42—Coating with noble metals
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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
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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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
- C23C18/48—Coating with alloys
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Abstract
The invention relates to a plating film without catalyst process to form high adhesive without electric plating on the non-conductive object, wherein it adds the conductive medium (2) with catalytic to the oxidization of reducer (R) into the plating bath (1) of the reducer (R) that outputting metallic ion and the metallic ion (M+) for forming plating film (5); the metallic ion receives the electron generated by the oxidization of reducer to be reduced and output at the surface medium (2); and the output metal is adhered on the surface of medium 92); via impacting object (4) with medium (2), the metal (3) is compressed on the surface of object (4), and using said metal (3) as core, to form plating film (5).
Description
Technical field
The present invention relates to the electroless process of non-conductive plated body and form the non-conductive plated body of plated film based on this electroless process.
Background technology
Decorate in the various fields such as electrode formation of plating, electronic devices and components, all need form metallic membrane.In the formation of metallic membrane, often use plating.Plated body is under the non-conductive situation, in order to form metallic membrane, can not use plating usually, and uses electroless plating.Be typically in the electroless plating and add reductive agent in plating bath, utilization makes metal separate out on the surface of plated body by the electronics of the oxidizing reaction generation of this reductive agent.This method for plating is known as the electroless plating of autocatalysis type.
In the electroless plating of autocatalysis type, the surface that need make plated body has catalytic activity to the oxidizing reaction of reductive agent.Therefore, in the past generally such as for example Japanese Patent spy open 2002-314309 communique (patent documentation 1) record, by plated body is immersed in the catalyst solution that contains Pd (palladium) in advance, thereby make the surface catalysis sensitization of plated body.
Catalyzer katalysis in the electroless plating of autocatalysis type that should be with Pd be main component is the strongest, also has the many advantages of reductive agent kind applicatory, industrial most widely used.
Yet in the time of plated body will being immersed in the catalyst solution that contains Pd, existing as the pre-treatment that is used to give the Pd catalyzer needs degreasing process and etching work procedure etc. to make manufacturing process's complicated problems.In addition, the problem that also has the Pd costliness.In addition, also exist the middle layer that constitutes by Pd between plated body and the plated film to weaken the problem of plated film to the adhesive power of plated body as catalyst residue.
Open in the 2003-183843 communique (patent documentation 2) the Japanese Patent spy, disclosed following method for plating: the conductive electrode that is formed at the plated body surface is partly used the metal ion that adds the formation plated film carry out electroless method for plating with the plating bath of the reductive agent that this metal ion is separated out, it is characterized in that, in plating bath, drop into the conductive medium that shows catalytic activity for the oxidizing reaction of reductive agent with plated body.
In the method for plating that patent documentation 2 is put down in writing,, also can divide to form the electroless plating film in electrode part even partly do not carry out giving of above-mentioned Pd catalyzer at electrode.Yet not the forming of plated film for the plated body that is made of electrical insulator in the patent documentation 2 disclosed.
Patent documentation 1: the Japanese Patent spy opens the 2002-314309 communique
Patent documentation 2: the Japanese Patent spy opens the 2003-183843 communique
The announcement of invention
The problem that invention will solve
The object of the present invention is to provide and to give operation without prior catalyzer for non-conductive plated body and form the electroless process of plated film.
The present invention also aims to provide the non-conductive plated body that has formed the high plated film of adhesive power.
Solve the method for problem
The present invention uses the metal ion that has added the formation plated film to carry out electroless method for plating with the plating bath of the reductive agent that this metal ion is separated out to non-conductive plated body, it is characterized in that the conductive medium that makes oxidizing reaction for reductive agent show catalytic activity contacts with plated body.
In the electroless process of the present invention, for conductive medium is more effectively contacted with plated body, better be to prepare the container that the permission plating bath passes through, in this container, drop into non-conductive plated body and conductive medium, with the container that dropped into non-conductive plated body and conductive medium at the plating bath internal rotation, shake or vibrate.
In the electroless process of the present invention, better be by above-mentioned metal ion is separated out on conductive medium, make the metal of separating out attached on the conductive medium, by conductive medium is contacted with non-conductive plated body, to transfer on the non-conductive plated body attached to the precipitating metal on the conductive medium, on non-conductive plated body, form plated film thus.
In preferred the 1st embodiment of electroless process of the present invention, the main component of plated film is made of Ni, Co, Au or Pt or their alloy, reductive agent contains phosphate compound, surperficial at least at least a kind of containing among Ni, Co, Au and the Pt of conductive medium.
In preferred the 2nd embodiment of electroless process of the present invention, the main component of plated film is made of Ni, Co, Au or Pt or their alloy, reductive agent contains boron compound, surperficial at least at least a kind of containing among Ni, Co, Au and the Pt of conductive medium.
In preferred the 3rd embodiment of electroless process of the present invention, the main component of plated film is made of Ni, Co or Pt or their alloy, and reductive agent contains nitrogen compound, and conductive medium surface at least contains among Ni, Co and the Pt at least a kind.
In preferred the 4th embodiment of electroless process of the present invention, the main component of plated film is made of Cu, Ag or Au or their alloy, and reductive agent contains aldehyde compound, and conductive medium surface at least contains among Cu, Ag and the Au at least a kind.
The present invention has still formed to be selected from the non-conductive plated body of the plated film that a kind of metal among Ni, Co, Cu, Ag, Au and the Pt or their alloy be main component at least.It is characterized in that, plated film forms by above-mentioned electroless process of the present invention, and feature is that also plated film is in following state simultaneously: the layer that constitutes by the material that is shown catalytic activity by the reductive action to described reductive agent and directly bonding with non-conductive plated body not.
The effect of invention
Adopt electroless process of the present invention, owing to do not need in advance non-conductive plated body to be carried out giving of catalyzer such as Pd, thus can not need complicated step, and form plated film at low cost.
In addition, adopt electroless process of the present invention, because plated film directly is not bonded on the non-conductive plated body by the middle layer that is made of Pd catalyzer etc., so can obtain for the high plated film of the adhesive power of plated body.
The simple declaration of accompanying drawing
[Fig. 1] Fig. 1 is the graphic extension figure that adopts the plated film forming process of electroless process of the present invention.
The explanation of symbol
1 electroless plating bath
2 conductive mediums
3 precipitating metals
4 non-conductive plated bodies
5 plated films
The best mode that carries out an invention
At first, electroless process of the present invention is described.
In brief, electroless process of the present invention is to use the metal ion that adds the formation plated film with the plating bath of the reductive agent that this metal ion is separated out non-conductive plated body to be carried out electroless method for plating, it is characterized in that the conductive medium that makes oxidizing reaction for reductive agent show catalytic activity contacts with plated body.
Referring to Fig. 1, describe in more detail.Shown in Fig. 1 (a), contained metal ion (M in electroless plating bath 1
+) katalysis by conductive medium 2 accepts the oxidizing reaction (R → 0+e by reductive agent (R)
-) electronics (e that produces
-) and be reduced, separate out surface easily attached to conductive medium 2.Thus, at first in the surface attachment of conductive medium 2 from metal ion (M
+) precipitating metal 3.
Then, shown in Fig. 1 (b), be attached to precipitating metal 3 on the conductive medium 2, shown in Fig. 1 (c), transfer to the surface of plated body 4 by when conductive medium 2 clashes into non-conductive plated body as shown by arrows, pressing attached or wiping the surface that is attached to plated body 4.Thus, 3 pairs of plated bodies of precipitating metal 4 on surface of transferring to plated body 4 are by anchor effect and bonding.
Then, be nuclear with the precipitating metal 3 that is bonded on the plated body 4, shown in dotted line among Fig. 1 (c), precipitating metal 3 is constantly separated out on plated body 4, forms plated film 5.Particularly precipitating metal 3 has under the situation of catalytic activity for reductive agent, form the nuclear of aforesaid precipitating metal 3 after, along with the expansion of the plated film 5 that forms, plated film 5 quickens to form.
Above-mentioned plated film 5 be in not the layer that constitutes by the material that shows catalytic activity by reductive action to described reductive agent and directly with non-conductive plated body 4 adherent states.
As concrete embodiment, better be to use following method: prepare the container that the permission plating bath passes through, in this container, drop into non-conductive plated body and conductive medium, container by will having dropped into non-conductive plated body and conductive medium at the plating bath internal rotation, shake or vibrate, non-conductive plated body is contacted effectively with conductive medium.At this moment, can preferably use the used such tube (barrel) of common electrochemical plating as said vesse.In addition, also can make its rotation, shake or vibrate with the state that tube tilts.
The method for plating that method for plating more of the present invention and patent documentation 2 are put down in writing, do not need prior catalyzer such as Pd to give with making the conductive medium that reductive agent is shown catalytic activity be common aspect plated body contacts.But, in the method for plating that patent documentation 2 is put down in writing, have at plated body electrical conductor such as electrode part, plated film only electrical conductor partly form have on this point more different.
Promptly, in the method for plating that patent documentation 2 is put down in writing, when the electrical conductor medium with catalytic activity contacts with the surface of the electrical conductor part of plated body, near the oxidizing reaction of generation reductive agent this point of contact, the electronics that is produced by this oxidizing reaction flow on the electrical conductor of plated body.Near the electrical conductor in the plating bath metal ion is accepted the electronics on this electrical conductor, and metal is separated out on electrical conductor.Only on electrical conductor, form plated film by repeating this reaction.
On the other hand, on the electrical insulator part of plated body except that the electrical conductor part, owing to do not have the electronics that oxidizing reaction produced of reductive agent to flow, so the mechanism of being put down in writing according to patent documentation 2 can not form plated film.But,,, infer that also should have plated film forms if according to the mechanism of the invention described above, promptly transfer on the plated body and adherent mechanism separating out the precipitating metal that adheres on the conductive medium when the conductive medium bump plated body in the electrical insulator part.Yet the mechanism that adopts patent documentation 2 to be put down in writing owing to the metal ion in the plating bath preferentially precipitate on the electrical conductor part, thereby does not almost have plated film to form on the electrical insulator part.
In sum, even use identical metal ion and the identical conductive medium that reductive agent is had catalytic activity, whether contain the electrical conductor part according to plated body, the mechanism that plated film forms can be different fully.That is, method for plating of the present invention is owing to being purpose to form plated film on electrical insulator, so in fact do not contain the electrical conductor part as the plated body of object of the present invention.
Because method for plating of the present invention is based on aforesaid mechanism, so the situation of the method for plating of being put down in writing with described patent documentation 1 is compared, perhaps the surface of being put down in writing as patent documentation 2 that will form plated film is that the situation of electrical conductor is compared, and film forming speed is slower.But as mentioned above, if film forming speed becomes faster after considering the nuclear that forms the precipitating metal with autocatalysis, then this point can not become problem in practicality.
As mentioned above, adopt method for plating of the present invention, the metal ion in the plating bath is main at first separates out having on the conductive medium of catalytic activity, contacts with plated body by conductive medium then, and precipitating metal is transferred on the plated body also bonding.With this adherent precipitating metal is nuclear, by the autocatalysis formation plated film of precipitating metal.Thus, even plated body is non-conductive, also can gives operation and form the electroless plating film without prior catalyzer.
Conductive medium surface at least must be that the reductive agent in the plating bath is shown catalytic activity.Below, the metallic element of the kind of operable reductive agent and the formation conductive medium that adapts with it is described.
Reductive agent can exemplify phosphate compound, boron compound, nitrogen compound and the aldehyde compound etc. that generally are widely used.Relevant for the research report that these reductive agents is had the metal of catalytic activity.
For example, reported that Au, Ni, Co and Pt are to the sodium hypophosphite (NaH as phosphoric acid class reductive agent
2PO
2) oxidizing reaction have catalytic activity (big wild Quan, Ruo Linli, Chun-shan Mountain will youth work be " in the electroless plating for catalytic activity (the No Electricity of the anodised metal of sodium hypophosphite
め っ I To お け Ru time Ami リ Application
Na ト リ ウ system ア ノ-De
To is to The Ru metal matchmaker activity) ", the metallic surface technology, the 34th volume, No. 12, nineteen eighty-three, pp.594-599).
Therefore, use under the situation of phosphoric acid class reductive agent, the metal on the surface by constituting conductive medium at least uses at least a kind among Au, Ni, Co and the Pt, can give operation and form the plated film of Ni, Co, Au, Pt etc. on the surface of non-conductive plated body without prior catalyzer.
In addition, reported that reductive agent uses sodium borohydride (NaBH
4) and DMAB ((CH
3)
2NHBH
3) wait under the situation of boron compound, Ni, Co, Pt and Au have catalytic activity to the oxidizing reaction of these boron compounds, and (big wild Quan, Ruo Linli, Chun-shan Mountain will youth work are " in the electroless plating for catalytic activity (the No Electricity of the anodised metal of sodium borohydride and dimethylamine borane
め っ I To お け Ru ホ ウ water
Na ト リ ウ system お I び ジ メ チ Le ア ミ Application ボ ラ Application ア ノ-De
To is to The Ru metal matchmaker activity) ", electrochemistry, the 53rd volume, No. 3,1985, pp.196-201).
Therefore, use under the situation of boron compound as reductive agent, the metal on the surface by constituting conductive medium at least uses at least a kind among Au, Ni, Co and the Pt, can give operation and form the plated film of Ni, Co, Au, Pt etc. on the surface of non-conductive plated body without prior catalyzer.
In addition, reported that reductive agent uses the hydrazine (N as nitrogen compound
2H
4) situation under, Ni, Co and Pt are to N
2H
4Oxidizing reaction have catalytic activity (big wild Quan, Ruo Linli, Chun-shan Mountain will youth work be " in the electroless plating for catalytic activity (the No Electricity of the anodised metal of formaldehyde and hydrazine
め っ I To お け Ru ホ Le system ア Le デ ヒ De お I び ヒ De ラ ジ Application ア ノ-De
To is to The Ru metal matchmaker activity) ", electrochemistry, the 53rd volume, No. 3,1985, pp.190-195).
Therefore, use under the situation of nitrogen compound as reductive agent, the metal on the surface by constituting conductive medium at least uses at least a kind among Ni, Co and the Pt, can give operation and form the plated film of Ni, Co, Pt etc. on the surface of non-conductive plated body without prior catalyzer.
In addition, reported that reductive agent uses under the situation of formaldehyde (HCHO), Cu, Au and Ag have catalytic activity (big wild Quan, Ruo Linli, Chun-shan Mountain will youth work to the oxidizing reaction of HCHO, the catalytic activity of the anodised metal of formaldehyde and hydrazine " in the electroless plating for ", electrochemistry, the 53rd volume, No. 3,1985, pp.190-195).
Therefore, use under the situation of aldehyde compound as reductive agent, the metal on the surface by constituting conductive medium at least uses at least a kind among Cu, Au and the Ag, can give operation and form the plated film of Cu, Au, Ag etc. on the surface of non-conductive plated body without prior catalyzer.
More than, to method for plating of the present invention the relation of preferred plating bath and conductive medium be illustrated.Above-mentioned explanation is divided into phosphate compound, boron compound, nitrogen compound and aldehyde compound 4 classes to reductive agent to be carried out, but method for plating of the present invention is not limited to above-mentioned 4 classes.The metal ingredient on metal ingredient in the plating bath and conductive medium surface can certainly be considered other combination in addition so long as the reductive agent that adopts is shown catalytic activity.
In addition, about conductive medium, so long as its surface has electroconductibility and reductive agent is had catalytic activity and gets final product at least, it doesn't matter for inner electroconductibility and catalytic activity.
About the size of conductive medium, can suitably select according to the size of plated body.If the size of conductive medium and plated body represents with volume that respectively the volume of conductive medium better is about 1/1000～1/1 of a plated body volume.If conductive medium is too small, then owing to when clashing into plated body, press a little less than the power of attached precipitating metal, tunicle forms slowly.On the other hand, if conductive medium is excessive, then because low with the hit probability of plated body, tunicle forms slowly.
The various conditions of plating bath, for example the kind of various additives such as the concentration of concentration of metal ions, reductive agent, pH, temperature and stablizer and tensio-active agent and amount etc. need according to suitably adjusting corresponding to the kind of selected reductive agent of the method for plating that will implement and metal ion.
Then, the non-conductive plated body that uses method for plating of the present invention to form the electroless plating film is described.
As previously mentioned, non-conductive plated body of the present invention is to have formed to be selected from the non-conductive plated body of the plated film that at least a kind of metal among Ni, Co, Cu, Ag, Au and the Pt or their alloy be main component, it is characterized in that above-mentioned plated film is in not by by with for example Pd being the metal of main component or layer that compound constitutes and directly and plated body adherent state.
Thus, adopt the present invention, owing to do not need the operation of giving of prior catalyzer such as Pd, so between plated body and plated film, there is not the middle layer.Therefore, the adhesive power of plated film improves.
The prerequisite of non-conductive plated body is that the surface portion that forms plated film at least is non-conductive.Do not form the non-conductive problem that do not become of the plated body inside of plated film.If the surface exists under the situation of electrical conductor part, because aforesaid reason electrical insulator part can not form plated film, therefore outside scope of the present invention.
In addition because plated body is non-conductive, plated film of the present invention to plated body by anchor effect and directly bonding.Therefore, the surfaceness on the surface of plated body is big more, and the adhesive power of plated film is big more.The surface roughness Ra of plated body better is more than 0.1 μ m, is more preferably more than 1 μ m.
After using method for plating of the present invention for example to form the Ni plated film, can form the displacement Au coating that generally adopts usually on its surface.In addition, formation Sn coating is also no problem.
Below, based on embodiment more specifically, electroless process of the present invention and non-conductive plated body are described.
As non-conductive plated body, prepare the dielectric ceramics unit of the cubic of 100 long 3mm, wide 3mm and high 7mm.
On the other hand, prepare to have the following composition and the plating bath of condition.
Metal-salt: copper sulfate 0.04 mol
Reductive agent: formaldehyde 0.70 mol
Coordination agent: EDTA 0.08 mol
pH：12.0
Bathe temperature: 45 ℃
Then, be 1.90 * 10 at internal volume
4m
3Shake in the tube and to drop into above-mentioned 100 dielectric ceramics unit, drop into the Cu ball of 8.6g (about 1500) the about 0.7mm of diameter simultaneously, this is shaken tube is impregnated in the above-mentioned plating bath, carry out pneumatic blending on one side, on one side with 8～16 back and forth/minute speed make and shake tube and shook 60 minutes, form the Cu plated film on the unitary surface of dielectric ceramics.
By carrying out electroless plating as mentioned above, can be without prior catalyst treatment operation, and form the Cu plated film that does not have bond strength and separate out the about 2.0 μ m of thickness of uneven problem.The thickness of plated film is measured by fluorescent X-ray film thickness gauge (セ イ コ-イ Application ス Star Le メ Application Star corporate system SEA5120).The dielectric ceramics unit of above-mentioned formation plated film is suitable as dielectric resonator.
As non-conductive plated body, prepare the plastics system framework of 100 long 5mm, wide 5mm and high 1.5mm.
On the other hand, the weak former ユ-ジ ラ イ ト system " エ バ シ-Le De TN " as the Ni-P alloy baths of selling on the market prepared is bathed temperature and is set at 63 ℃ as plating bath.
Then, be 1.90 * 10 at internal volume
4m
3Shake in the tube and to drop into above-mentioned 100 plastics system frameworks, drop into the Ni ball of 7.9g (about 1500) the about 0.7mm of diameter simultaneously, this is shaken tube is impregnated in the above-mentioned plating bath, carry out pneumatic blending on one side, on one side with 8～16 back and forth/minute speed make and shake tube and shook 60 minutes, at the surface of plastics system framework formation Ni-P tunicle.
By carrying out electroless plating as mentioned above, can be without prior catalyst treatment operation, and form the Ni-P plated film that does not have bond strength and separate out the about 6.0 μ m of thickness of uneven problem.The plastics system framework of above-mentioned formation plated film is suitable as electromagnetic shielding material.
As non-conductive plated body, prepare the Al of 100 about 3.0mm of diameter
2O
3Spheroid.
On the other hand, as plating bath, pH is set at 6.7 to prepare difficult to understand wild pharmacy system " ト Star プ ケ ミ ア ロ イ B-1 " as the Ni-B alloy baths of selling on the market, bathes temperature and is set at 60 ℃.
Then, be 1.90 * 10 at internal volume
4m
3Rotating cylinder in drop into above-mentioned 100 Al
2O
3Spheroid drops into the Ni ball of 7.9g (about 1500) the about 0.7mm of diameter simultaneously, this rotating cylinder is impregnated in the above-mentioned plating bath, Yi Bian carry out pneumatic blending, Yi Bian with 0.05s
-1The speed of rotation of (=3rpm) makes rotating cylinder rotation 40 minutes, at Al
2O
3The surface of spheroid forms the Ni-B tunicle.
By carrying out electroless plating as mentioned above, can be without prior catalyst treatment operation, and form the Ni-B plated film that does not have bond strength and separate out the about 1.5 μ m of thickness of uneven problem.The Al of above-mentioned formation plated film
2O
3Spheroid is suitable as the low temperature heating element.
Claims (8)
1. electroless process, it is to use has added the plating bath that forms the metal ion of plated film and make the reductive agent that described metal ion separates out, the electroless process that forms plated film on non-conductive plated body by electroless plating, it is characterized in that,
Possesses preparation shows the conductive medium of catalytic activity to the oxidizing reaction of described reductive agent operation;
And, make the operation of described conductive medium and described non-conductive plated body bump in order on described non-conductive plated body, to form described plated film.
2. electroless process as claimed in claim 1, its feature also is, the operation and the operation that in described container, drops into described non-conductive plated body and described conductive medium that also possess the container that the plating bath that prepare to allow constitutes described plating bath passes through, the described operation that makes conductive medium and non-conductive plated body bump possess the described container that will drop into described non-conductive plated body and described conductive medium at described plating bath internal rotation, shake or vibrate in, the step that described non-conductive plated body is contacted with described conductive medium.
3. electroless process as claimed in claim 1, its feature also is, make in the operation of described conductive medium and non-conductive plated body bump, described metal ion is separated out and on described conductive medium, make described conductive medium and described non-conductive plated body bump and will transfer on the described non-conductive plated body attached to the described precipitating metal on the described conductive medium attached to described conductive medium.
4. electroless process as claimed in claim 1, its feature also is, the main component of described plated film is made of Ni, Co, Au or Pt or their alloy, and described reductive agent contains phosphate compound, surperficial at least at least a kind of containing among Ni, Co, Au and the Pt of described conductive medium.
5. electroless process as claimed in claim 1, its feature also is, the main component of described plated film is made of Ni, Co, Au or Pt or their alloy, and described reductive agent contains boron compound, surperficial at least at least a kind of containing among Ni, Co, Au and the Pt of described conductive medium.
6. electroless process as claimed in claim 1, its feature also is, the main component of described plated film is made of Ni, Co or Pt or their alloy, and described reductive agent contains nitrogen compound, and described conductive medium surface at least contains among Ni, Co and the Pt at least a kind.
7. electroless process as claimed in claim 1, its feature also is, the main component of described plated film is made of Cu, Ag or Au or their alloy, and described reductive agent contains aldehyde compound, and described conductive medium surface at least contains among Cu, Ag and the Au at least a kind.
8. non-conductive plated body, it is to have formed to be selected from the non-conductive plated body of the plated film that at least a kind of metal among Ni, Co, Cu, Ag, Au and the Pt or their alloy be main component, it is characterized in that,
Described plated film forms by each the described electroless process in the claim 1～7, and described plated film is in following state: the layer that constitutes by the material that is shown catalytic activity by the reductive action to described reductive agent and directly bonding with described non-conductive plated body not.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP279707/2004 | 2004-09-27 | ||
| JP2004279707 | 2004-09-27 | ||
| PCT/JP2005/015066 WO2006035556A1 (en) | 2004-09-27 | 2005-08-18 | Electroless plating method and electrically nonconductive plating object with plating film formed thereon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1842615A CN1842615A (en) | 2006-10-04 |
| CN100480423C true CN100480423C (en) | 2009-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800008197A Expired - Fee Related CN100480423C (en) | 2004-09-27 | 2005-08-18 | Electroless plating method and electrically nonconductive plating object with plating film formed thereon |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4311449B2 (en) |
| KR (1) | KR100760254B1 (en) |
| CN (1) | CN100480423C (en) |
| TW (1) | TW200619419A (en) |
| WO (1) | WO2006035556A1 (en) |
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|---|---|---|---|---|
| JP5445818B2 (en) * | 2008-04-28 | 2014-03-19 | 日立化成株式会社 | Electroless plating method and activation pretreatment method |
| JP5408462B2 (en) * | 2008-04-28 | 2014-02-05 | 日立化成株式会社 | Electroless plating method and activation pretreatment method |
| KR101612476B1 (en) | 2013-11-22 | 2016-04-14 | 한국생산기술연구원 | Electroless copper plating solution composition and methods of plating copper using the same |
| WO2015076549A1 (en) * | 2013-11-22 | 2015-05-28 | 한국생산기술연구원 | Electroless copper plating solution composition and electroless copper plating method using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50118931A (en) * | 1974-03-04 | 1975-09-18 | ||
| EP0058772B1 (en) * | 1981-02-21 | 1985-02-06 | Karl Enghofer Metallwarenfabrik GmbH | Combination spectacles |
| US5227223A (en) * | 1989-12-21 | 1993-07-13 | Monsanto Company | Fabricating metal articles from printed images |
| JP2000264761A (en) * | 1999-03-16 | 2000-09-26 | Mitsuboshi Belting Ltd | Surface treating agent for plating of ceramic substrate and plating method using same |
-
2005
- 2005-08-18 CN CNB2005800008197A patent/CN100480423C/en not_active Expired - Fee Related
- 2005-08-18 JP JP2006537647A patent/JP4311449B2/en not_active Expired - Fee Related
- 2005-08-18 KR KR1020067004667A patent/KR100760254B1/en active IP Right Grant
- 2005-08-18 WO PCT/JP2005/015066 patent/WO2006035556A1/en active Application Filing
- 2005-08-26 TW TW094129384A patent/TW200619419A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP4311449B2 (en) | 2009-08-12 |
| WO2006035556A1 (en) | 2006-04-06 |
| TW200619419A (en) | 2006-06-16 |
| JPWO2006035556A1 (en) | 2008-05-15 |
| CN1842615A (en) | 2006-10-04 |
| TWI305238B (en) | 2009-01-11 |
| KR20060069488A (en) | 2006-06-21 |
| KR100760254B1 (en) | 2007-09-19 |
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