JPH1180991A - Preparation of metalized material and metalized material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make a non-electroconductive or a semiconductive material such as synthetic resin electroconductive with simple process and to make it possible to plate these materials by electrolytic and direct plating method by bringing the ground layer, formed with the material which has been obtained by the polymerization of a compound having C-C triple bonds in the same molecule, into contact with a solution containing Pd in order to make it electroconductive, and then forming a metal layer on the resulting ground layer by electrolytic plating. SOLUTION: The objective metalized material is prepared by first forming a ground layer by using the material obtained by the polymerization of a compound of the formula on the surface of the substrate, then bringing the resulting ground layer into contact with the solution containing Pd in order to make it electroconductive, and forming a metal layer on the electroconductive ground layer thus obtained by electrolytic plating. The symbols used in the formula; (R-(C≡C)l )k -L-Am are as follows; A is a functional group selected from hydroxy, amino, ether, mercapto, polyoxy ether group, etc.; R is an element from group 8 or 1B of Periodic Table; L is a chemical bond or a binding group having ((k)+(m))-valencies; (k) and (l) are integers each >=1; (m) is 0 or >=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a novel metallized material and a metallized material. The metallized material refers to a material formed by forming a metal film on a base made of a non-conductive material or a semi-conductive material to form a conductive material. Such metallized materials are used, for example, as decorative articles, plastics having metallic luster and weather resistance, conductive members for electronic materials, and the like.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 2-205686 discloses that a compound having a carbon-carbon triple bond in the same molecule is polymerized and electroless plating is performed. Electroless plating is a plating method utilizing reduction by a contact action on a material surface, and is also called chemical plating. This has an advantage that, unlike electrolytic plating, plating can be performed to a uniform thickness even in a concave portion. For this reason, electroless plating is used for a conductive treatment for electroplating a synthetic resin and for manufacturing a thin film of a printed circuit.

[0003] Electroless plating uses formalin as a reducing agent, which has a strong odor, is partially pointed out as carcinogenic, and has a problem with the environment and the human body, such as skin inflammation. Use is being regulated. EDTA is widely used as a chelating agent to keep copper ions alkaline and stable. However, EDTA is difficult to treat by wastewater treatment, and there is a problem that it is combined with heavy metals and redissolved. Due to these environmental problems, electroless copper plating solutions that do not use formalin have also been developed. Incidentally, the formation rate of the metal film obtained by the electroless plating is low.
Even a copper thin film of a relatively thin flexible printed circuit board of about 20 nm is not formed only by electroless plating. Usually, electroless plating is used to form a conductive substrate for electroplating the surface of a synthetic resin as described above, and the process control is quite complicated, and environmentally friendly improvement is desired. Was rare.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a metallized material capable of making a nonconductive or semiconducting substrate such as a synthetic resin conductive by a simple method and enabling direct electrolytic plating. It is to provide a metallized material produced by the method.

[0005]

This and other objects are achieved by the present invention described below. (1) An underlayer formed of a material obtained by polymerizing a compound having a carbon-carbon triple bond in the same molecule represented by the following general formula is formed on the surface of a substrate, and the underlayer contains a palladium element. A method for producing a metallized material, wherein a metallized material is produced by contacting a solution to impart conductivity, and forming a metal layer by an electrolytic plating layer on an underlayer to which the conductivity has been imparted. Formula (R- (C≡C) _l ) _k -L-A _m (wherein A is a hydrogen atom or a hydroxyl group, an amino group, an ether group, a mercapto group, a polyoxyether group, a polyaminoether group, or a polyaminoether group. A thioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof,
It represents a functional group selected from a carboxyl group or a salt thereof, a phosphate group or a salt thereof, and a polymerizable group. R represents an element of Group 8 or Group 1B of the periodic table. L represents a chemical bond or a (k + m) -valent linking group. k and l are integers of 1 or more, and m is 0 or an integer of 1 or more. (2) A compound having a carbon-carbon triple bond in the same molecule represented by the following general formula on the surface of a substrate is treated with a periodic table 8
An underlayer formed of a material polymerized in the coexistence with a Group 1B or Group 1B element is formed, and a solution containing a palladium element is brought into contact with the underlayer to impart conductivity, and the conductivity is imparted. A method for producing a metallized material, comprising: forming a metal layer on a base layer by an electrolytic plating layer to produce a metallized material. Formula (R- (C≡C) _l ) _k -L-A _m (wherein A is a hydrogen atom or a hydroxyl group, an amino group, an ether group, a mercapto group, a polyoxyether group, a polyaminoether group, or a polyaminoether group. A thioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof,
It represents a functional group selected from a carboxyl group or a salt thereof, a phosphate group or a salt thereof, and a polymerizable group. R represents a carboxyl group or a salt thereof, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a silyl group, an aryl group, an aralkyl group, an ester group, a heterocyclic group, an element of Group 8 or Group 1B of the periodic table. L represents a chemical bond or a (k + m) -valent linking group. k and l are integers of 1 or more, and m is 0 or an integer of 1 or more. (3) The method for producing a metallized material according to (1) or (2), wherein the conductivity of the underlayer is imparted to 200 Ω / □ or less by imparting conductivity. (4) A compound represented by the above general formula is used in an amount of 100 to 20.
The method for producing a metallized material according to any one of the above (1) to (3), wherein the metallized material is polymerized by heat treatment in a temperature range of 0 ° C for 0.5 to 90 minutes. (5) The method for producing a metallized material according to (4), wherein the compound represented by the general formula is polymerized by heat treatment in the presence of a nitrate. (6) The method for producing a metallized material according to any one of (1) to (5), wherein the substituent R of the compound represented by the general formula is a Group 1B element of the periodic table. (7) The method for producing a metallized material according to (6), wherein the Group 1B element is silver. (8) The method for producing a metallized material according to any one of the above (1) to (7), wherein A of the compound represented by the general formula is a polyethoxyether group. (9) A solution prepared by adding a surfactant to a solution of the compound represented by the above general formula is prepared, applied to a substrate in the form of a film, and then polymerized. Manufacturing method of such metallized material. (10) a substrate made of a non-conductive material or a semiconductor material, an intermediate layer formed on the surface of the substrate, and an electrolytic plating layer formed on the intermediate layer, wherein the intermediate layer is represented by the following general formula: Composed of a compound derived from a compound having a carbon-carbon triple bond in the same molecule, an alloy of palladium with a Group 8 or 1B element in the periodic table or a palladium element, and a mixture of metal materials forming an electrolytic plating layer A metallized material characterized by being made. Formula (R- (C≡C) _l ) _k -L-A _m (wherein A is a hydrogen atom or a hydroxyl group, an amino group, an ether group, a mercapto group, a polyoxyether group, a polyaminoether group, or a polyaminoether group. A thioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof,
It represents a functional group selected from a carboxyl group or a salt thereof, a phosphate group or a salt thereof, and a polymerizable group. R represents a carboxyl group or a salt thereof, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a silyl group, an aryl group, an aralkyl group, an ester group, a heterocyclic group, an element of Group 8 or Group 1B of the periodic table. L represents a chemical bond or a (k + m) -valent linking group. k and l are integers of 1 or more, and m is 0 or an integer of 1 or more. (11) The flexible printed circuit board according to the above (10), wherein the base is made of a polyimide resin, polyethylene naphthalate or polyethylene terephthalate, and the electrolytic plating layer is formed as a layer formed in a pattern with copper. Metallized material. (12) The metallized material according to the above (10) or (11), wherein the thickness of the electrolytic plating layer is 5 to 20 μm.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. In the present invention, a polymer layer (film) derived from a compound having a carbon-carbon triple bond is formed on a nonconductive material or a semiconductor material substrate, and a solution containing a palladium element in the polymer layer is formed. To form a conductive layer that can be electroplated, and a metal layer (film) is formed on the conductive layer by electrolytic plating to obtain a metallized material. The polymer derived from the compound having a carbon-carbon triple bond in the present invention has carbon-
It has a carbon triple bond or a double bond. As a structural unit constituting the above-mentioned polyacetylene-based polymer, if the basic structural element of the polymer has a carbon-carbon triple bond or a double bond, it is not dispersed in another polymer. It may be blended. Examples of such other polymers include thermoplastic resins such as polyphenol resin, epoxy resin, gelatin, polyvinyl alcohol, polysulfone, diacetylcellulose, polyvinyl acetate, polystyrene, polyurethane, silicone polymer, polyether polyol, polyimide, and polyvinyl butyral. And various kinds of synthetic or natural resins such as thermosetting, thermosetting and reactive. The content of these various synthetic or natural resins is usually about 10 ³ wt% or less of the polyacetylene polymer used as a plating medium material.

The above-mentioned polyacetylene-based polymer is
Further, it may have another functional group. Such a functional group may be of any kind, but in order to exhibit a higher medium function in a general aqueous wet electroplating process, a hydroxyl group, an amino group, an ether group, a polyoxyether It is preferably a group, a polyaminoether group, a polythioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, and more preferably a polyoxyether group. In the present invention, such a compound having a functional group may be separately contained together with the polyacetylene-based polymer and the plating medium material.
As the preferred polyacetylene-based polymer in the present invention, only a homopolymer or a copolymer having a carbon-carbon conjugated unsaturated bond in the main chain or a side chain and the above-mentioned other functional group which may further have It is composed of

A compound (monomer) having a carbon-carbon triple bond from which such a polymer is derived, that is, a compound which provides a basic structure among the constituent elements of such a polymer is represented by the following general formula: It is represented. Group in the general formula _{(R- (C≡C) l) k} -L-A m the formula (I), A is selected arbitrarily to one or more of the hydrogen atoms or functional groups of the following, for example, a hydroxyl group An amino group, an ether group, a mercapto group, a polyoxyether group, a polyaminoether group, a polythioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, or a polymerizable group (for example, a glycidyl group , A vinyl group, an isocyanate group, etc.). A is preferably a polyoxyether group, more preferably an oligoethyleneoxy group.

R is preferably an element of group 8 of the periodic table (eg, nickel, ruthenium, rhodium, palladium, platinum, etc.) or an element of group 1B (copper, silver, gold, preferably silver,
Copper), a hydrogen atom, a carboxyl group or a salt thereof, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, silyl group, aryl group, aralkyl group, ester group or heterocyclic group . In the case where the above hydrogen atom or less is used as R, the polymerization is carried out by a method described later, which is a group 8 element (for example, nickel, ruthenium, rhodium, palladium, platinum, etc.) or a group 1B element (copper). , Silver and gold, preferably silver and copper).

L is a chemical bond or a (k + m) -valent group connecting a carbon-carbon triple bond to A, for example, an optionally substituted alkylene group, an arylene group, an aralkylene group, a vinylene group, a cycloalkylene group, a glutaroyl group. Represents a phthaloyl group, a hydrazo group, a ureylene group, or a thio group, a carbonyl group, an oxy group, an imino group, a sulfinyl group, a sulfonyl group, a thiocarbonyl group, an oxalyl group, an azo group, and the like. There may be. Here, k and l are integers of 1 or more. M is an integer of 0 or more. Preferred specific monomers are listed below, but are not limited thereto.

[0011]

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[0012]

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[0013]

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[0014]

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[0015] These acetylene compound monomers can be generally synthesized as follows. That is,
Compounds having a carbon-carbon triple bond, for example, propiolic acid, propargyl bromide, compounds having other necessary functional groups such as propargyl alcohol and the like, for example, tetraethylene glycol monoethyl ether, maleic anhydride, propane sultone, Epichlorohydrin, acrylic acid chloride and the like may be condensed. The following is an example of a synthesis method.

Synthesis of Exemplified Compound (1) 107 g of triethylene glycol monoethyl ether,
A mixture of 107 g of propargyl bromide and 300 g of anhydrous potassium carbonate is heated and stirred on a water bath for 20 hours. After cooling, insolubles are filtered through celite, and the filtrate is distilled under reduced pressure. Yield 1
20 g colorless and transparent liquid. Boiling point 115 ° C./0.6 mmHg Other compounds can be easily synthesized in the same manner.
As described later, these compounds can be polymerized in a pattern to form a polyacetylene-based polymer. In this case, dimers, trimers, oligomers, and the like of these compounds may be used. When forming a polyacetylene-based copolymer, two or more of these compounds may be used as a monomer. Further, as the above-mentioned monomer, those having a Group 8 to Group 1B element as R are not illustrated, but the above-mentioned exemplified monomers having one or more of these metal elements as R may be used. Is also good.

Those having these metal elements as R are:
_{(H- (C≡C) l) k} -L-A acetylene compound represented by _m and silver nitrate, cuprous chloride, chloroplatinic acid, palladium chloride, metal salts such as chloroauric acid or a mixture with a known method And can be easily obtained by reacting In such a reaction, the above-mentioned acetylene compound may be suspended in an aqueous solution, and the above-mentioned metal salt may be added thereto to carry out the reaction. At this time, when ammonia or organic amines coexist, they often react easily. In general, the reaction product may be isolated by an extraction method. The acetylene compound having a Group 8 to 1B element thus obtained has an NMR spectrum and 1R
According to the spectrum, it is a σ complex or π complex of acetylide. One or more of such acetylene compounds or dimers and oligomers thereof are polymerized to form a polyacetylene polymer.

Examples of Group 8 elements of the periodic table in the present invention include nickel, ruthenium, rhodium and palladium. Group 1B elements include copper, silver and gold, of which silver and copper are most preferred. One or more of the elements of Groups 8 to 1B of the Periodic Table may be contained in a plating medium material in the form of a simple metal, a metal salt or a metal complex, and bound or coordinated to a polyacetylene-based polymer. In some cases, it is contained in the form of these alloys and various compounds. Among these, as metal salts,
Silver nitrate, palladium chloride, cuprous chloride, platinum chloride and the like are preferred. These metal complexes include di-μ-chlorobis (η-2-methylallyl) dipalladium (II)
Complexes, tetrakis (triphenylphosphine) palladium complex, di-μ-chlorotetracarbonyldirhodium (I) complex, dicyclopentadiene-gold (I) chloride and the like. A simple metal such as Group 8 or 1B of the periodic table existing in such a polyacetylene-based polymer;
The amount of the metal complex, metal salt and the like is preferably 5 to 5000, particularly preferably 10 to 500 per 100 parts by weight of the polymer.

As a method of polymerizing in the presence of a metal element as described above, there is a method of first performing polymerization using a compound containing such a metal element as the acetylene compound.
The acetylene compound containing such a metal element is 100
° C. or higher, preferably in a temperature range of 140 to 200 ° C.,
When heated for 0.5 to 90 minutes, it thermally polymerizes and the metal element is reduced at the same time to form a metal colloid. This polymerization is preferably performed in the presence of a nitrate. As the nitrate, sodium nitrate, ammonium nitrate and the like can be preferably used. In the present invention, monomers, dimers, oligomers and the like of the acetylene compound are
It can be polymerized in a pattern. The polymerization can be carried out by radiation. To form a pattern, the polymerization may be carried out in a pattern by controlling the scanning of radiation, or may be carried out in a pattern by using a pattern mask material or the like.

The electroplating medium material preferably applied in the present invention is generally in the form of a film. In the case of forming a film, specifically, a film may be formed on the surface of the base. As a method of forming a film on a substrate, a method of supporting the above-mentioned monomer on a substrate by using a coating method is the simplest method. In the case of a coating method, there is a method of curtain coating, dip coating, spray coating, spinner coating, roll coating or the like from a monomer solution or suspension. The solvent and the concentration used at this time are not particularly limited. Considering the uniformity of the thin film, it is preferable to use a solvent having high solubility, and typical examples include water, ketones such as methanol, acetone and methyl ethyl ketone, chloroform, halogen compounds such as methylene chloride, and ethyl acetate. Esters, dimethylacetamide, dimethylformamide, N-methyl-
Amides such as 2-pyrrolidone and nitriles such as acetonitrile.

When coating with a solution, it is desirable to add a surfactant to the solution. In this case, the addition amount is 0.1 parts by weight per 1000 parts by weight of the polymer-forming monomer.
The amount is preferably from 200 to 200 parts by weight, particularly preferably from 0.3 to 100 parts by weight. The addition of the surfactant makes the coating uniform, and prevents the occurrence of pinholes. Although various surfactants can be used as the surfactant, anionic or nonionic surfactants are preferable. Representative surfactants include sodium dodecylbenzenesulfonate and the like in the anionic system, and N-hexadeca (ethyleneoxy) -N-propylperfluorooctylsulfonamide in the nonionic system. As an example of specifically applying the coating method, a chloroform solution of silver acetylide of azobisisobutyronitrile and the exemplary compound (20) as a thermal polymerization initiator is applied on a polymethyl methacrylate substrate by spin coating or the like, As described above, there is a method in which after polymerizing in a pattern using radiation, portions not polymerized are removed with water.

Further, a compound which forms a complex with a metal of Group 8 or 1B of the periodic table as a monomer for forming a polymer, for example, silver acetylide of exemplified compounds (1), (6) and (27) is used. This is applied on a substrate by spin coating or the like,
Next, as described above, polymerization may be performed in a pattern by irradiation with radiation such as ultraviolet light, and the non-polymerized portion may be removed as described above. In addition, for example, after dissolving or dispersing a metal salt or simple metal, or an alloy or a metal compound in a monomer solution or suspension, and applying this,
As described above, a portion polymerized in a pattern by radiation may be removed. In the present invention, the amount of the polymer having a carbon-carbon unsaturated bond to be used is preferably from 1 mg to 10 g, particularly preferably from 20 mg to 1 g, per m ^{2 of the} substrate (substrate). The thickness of this polymer or a film made of this polymer and another binder is suitably from 0.001 μm to 5 μm, particularly from 0.05 μm to 0.5 μm.

It is to be noted that a known technique of providing a protective layer or an underlayer on the film thus formed or laminating a plurality of layers can be applied. As a method for forming a film, a Langmuir-Blodgett method may be applied. The method of producing a monomolecular film by the Langmuir-Blodgett method and accumulating the same are based on a general method such as "New Experimental Chemistry Course, Volume 18, Interfaces and Colloids, Chapter 6; In this case, even if a vertical dipping method in which the base (substrate) is moved up and down in a direction crossing the liquid surface and the monomolecular film is transferred is used, the base (substrate) is supported horizontally and the film is attached by touching the monomolecular film surface. The horizontal attachment method may be used or any of them may be used. The water used is subjected to ion exchange, removal of organic substances with potassium permanganate, and distillation. The water temperature is set at 15-20 ° C. If necessary, add ^ions such as Cd ²⁺ to 10 ^-3 to 10 ^-4 mol / l
Add.

For example, in the vertical immersion method, it is desirable to use a float type microparan as an apparatus. The purified monomer was dissolved in chloroform or the like for spectral analysis at a concentration of 0.
Dissolve to a concentration of 5 to 1.0 mg / ml. After preparing the monomolecular film, the monomolecular film is accumulated on the substrate while keeping the surface pressure at 20 to 25 dyn / cm. Specific examples of the application of the Langmuir-Blodgett method include the use of the Langmuir-Blodgett method described in JP-A-61-137781, and amphiphilic monomers such as exemplified compounds (10) and (12). , (14), (16) as a monomolecular cumulative film on a glass substrate, and irradiated with radiation such as ultraviolet light from a high-pressure mercury lamp or the like in a pattern as described above and polymerized, There is a method of removing it and immersing it in a bath of a metal salt of Group 8 or 1B of the periodic table.

In the present invention, when a film is formed, a vapor phase growth method roughly classified into PVD and CVD may be applied depending on the monomer used. In this case, if PVD and CVD are performed using a pattern mask material, direct patterning can be performed. And in the case of CVD,
A polymer film is formed in a pattern. Note that patterning can be performed without using a pattern mask material, for example, by performing light irradiation or the like in a pattern by CVD or the like. In the above description, the case where the polymer film is formed in a pattern has been described. However, it goes without saying that the entire surface of the base may be covered with the polymer film.

In the present invention, a non-conductive material or a semiconductor material is used as a substrate for forming a film, and examples thereof include glass, quartz, ceramics, carbon, polyethylene, polyphenol, polypropylene, ABS polymer,
Includes epoxy resin, glass fiber reinforced epoxy resin, polyester, and woven sheet (including cloth) of polyamide, polyolefin, polyacrylonitrile, polyvinyl halide, cotton or wool or a mixture thereof, or a copolymer of the above monomers. , Yarns and fibers, aggregates of fibers such as paper, and particulates such as silica. Examples of the base include those having a layer or film of a nonconductive material or a semiconductor material as described above formed on a metal surface.

The intermediate layer (underlayer) formed as described above
Is contacted with a solution containing palladium. As the solution containing palladium, a dilute aqueous solution of palladium chloride or the like is preferably used.
ppm or more is preferable, and 200 to 1000 ppm is particularly preferable. The contact is performed by immersing the substrate on which the intermediate layer is formed in a bath composed of a solution containing palladium. This immersion is preferably performed for about 10 seconds to 2 minutes. By immersion in the above bath, an alloy of palladium with a Group 8 or 1B element of the periodic table is preferably formed, and the intermediate layer is given conductivity. At this time,
The conductivity of the intermediate layer is 10 to 1000 Ω / □, especially 200
It is preferably Ω / □ or less. The shape of the alloy thus formed is irregular. By the above method, without using any organic solvent, a submicron-thick thin film having a plating medium function, in which fine metal (alloy) particles serving as a conductive medium are homogeneously dispersed in a polymer having conjugated unsaturated bonds, is used. It can be easily formed on a substrate made of a non-conductive material or a semiconductor material.

The substrate on which the layer (film) of the plating medium material has been applied in this way is preferably subjected to electroplating and metallization, preferably a metal material pattern is formed to be a metallized material. The plating bath used in the present invention is preferably a bath containing a nickel salt, a cobalt salt, a copper salt, a gold and a silver salt, or a mixture containing these salts and their mutual or iron salts. This type of plating bath can also use a plating bath containing an inert substrate in the bath and eutecting the substance into the plating film. The electroplating used in the present invention is a method of electrochemically reducing and depositing a metal from an aqueous solution of a metal salt on the surface of a workpiece (cathode) by an external current, and includes zinc, cadmium, tin, nickel, cobalt, iron, A wide range of metal plating is possible, ranging from heavy metals such as copper and chromium, to noble metals such as silver, gold and rhodium. Depending on the intended use, they can be used in a single layer or multiple layers, taking advantage of the characteristics of each metal.

Practical use conditions are described in "Plating Technology Guidebook" (ed. 1985), edited by Tokyo Plating Materials Cooperative Technical Committee.
Years) can be used.
The metallized material produced by the method for producing a metallized material according to the present invention includes a base made of a non-conductive material or a semiconductor material,
An intermediate layer (underlayer) formed on the surface of the substrate and an electrolytic plating layer formed on the intermediate layer, wherein the intermediate layer is formed of carbon-carbon triple in the same molecule represented by the general formula. A mixture of a compound derived from a compound having a bond, an alloy of palladium with a group 8 element or group 1B element or a metal element lower than palladium or a palladium element, and a metal material constituting an electrolytic plating layer I have. In the metallized material of the present invention, the intermediate layer and the electrolytic plating layer cannot be completely separated from each other, and in the intermediate layer, a portion in contact with the substrate has the same intramolecular structure represented by the general formula. , A compound derived from a compound having a carbon-carbon triple bond, an alloy of palladium with a metal element lower than Group 8 or 1B element or palladium of the periodic table, or a high content of the palladium element, and the content of the palladium element is large, and goes to the electrolytic plating layer side. Accordingly, the content of these elements becomes smaller, and finally becomes 0, and the composition shifts to the electrolytic plating layer. Such a configuration can be understood by peeling the intermediate layer and the electrolytic plating layer from the substrate, and measuring this by ESCA.

The thickness of the electrolytic plating layer is 5 to 20 μm.
It is preferred that This thickness is extremely difficult depending on the electroless plating. The width of the thin line of the metal material pattern obtained in the present invention is about 1 to 100 μm, and can be a thin line having a width of about 1 μm. Therefore, the metallized material of the present invention is effective when used for a high-density and high-precision printed wiring board. In this case, the substrate is preferably made of a polyimide resin, polyethylene naphthalate or polyethylene terephthalate, and is preferably a flexible printed board. In particular, in the case of such a wiring board, it is preferable to use copper as the metal material pattern.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. Example 1 A silver salt of the exemplified compound (1) was prepared by the following method. In the light-shielded state, sodium acetate 16.4 g, silver acetate 1
6.7 g were suspended in 200 ml of distilled water at 40 ° C. 20.1 g of Exemplified Compound (1) was added dropwise thereto, and the mixture was stirred for 20 minutes, and then cooled to room temperature. This was neutralized with 7.8 g of sodium hydrogen carbonate, the supernatant was removed by decantation, and 200 ml of distilled water and 400 ml of chloroform were further added for extraction. After the chloroform layer was dried over anhydrous sodium sulfate, chloroform was distilled off under reduced pressure to obtain 29 g (almost quantitative) of a white waxy solid. This material is the silver σ
It was confirmed from the NMR spectrum and the IR spectrum that this was a complex.

NMR δ 1.15 (triplet, 3H) 3.0-40 (multiplet, 14H) 3.4 (broad singlet, 2H) IR 2860 cm ^-1 (CH stretch) 1980 cm ^-1 (C = C stretch) 1100 cm ^-1 (CO stretching) 0.24 g of silver salt of Exemplified Compound (1) and 0.36 g of distilled water,
1.80 g of methanol was mixed and dissolved to obtain a 10% by weight solution.

This was applied on a polyethylene naphthalate substrate by a spin coating method and heated in an oven at 200 ° C. for 3 minutes. Thus, a light brown transparent thin film insoluble in water was produced. The thickness of this thin film is 0.1
At μm, 50-100 A of uniform silver particles were dispersed therein. This was immersed in 500 ppm of a dilute hydrochloric acid solution of PdCl ₂ for 30 seconds. The surface resistance of the thin film is 200Ω /
□, the results of XRD (X-ray diffraction) show that Ag and P
The d peak was shifted, indicating that an AgPd alloy was formed. Ag amount is 60 mg / m ² , Pd amount is 24
mg / m ² estimated. Next, the above-mentioned polyethylene naphthalate substrate was fixed on a glass plate, this was used as a cathode, and a copper-containing plate was used as an anode, and electrolytic copper plating was performed at an interval of 8 cm. The copper plating bath was 200 g / l of copper sulfate, 70 g / l of sulfuric acid, and 50 mg / l of chloride ions. A voltage of 8 V was applied at the beginning, but after 5 minutes, a steady state was reached at ² V at a current density of 1.8 A / dm ^2. Was. 1
After 5 minutes, a polyethylene naphthalate substrate having a copper luster was obtained. The thickness of the copper film obtained on the polyethylene naphthalate substrate was 10 μm.

Example 2 The same experiment as in Example 1 was carried out by using Exemplified Compound (24) as a silver complex, and the same effect as in Example 1 was obtained. Further, a Pd complex of the exemplary compound (27) and an exemplary compound (5)
After polymerization, the same results were obtained when PdCl ₂ was added thereto.

Example 3 A silver complex was prepared using Exemplified Compound (1), and two types were prepared in the same manner as in Example 1 except that 50 mol% of ammonium nitrate was added thereto and no addition was made. This is 15
When the same treatment as in Example 1 was performed except that the heat treatment was performed in a 0 ° C. oven, the surface resistance after contact with palladium was 110Ω / □ for the former and 300 to 700 KΩ / □ for the latter. In the electroplating, the former was overwhelmingly highly active under the conditions of Example 1.

[0036]

According to the present invention, no special pretreatment is required, and a film can be formed by a simple operation such as coating and heating, and is high enough to facilitate electroplating by contact with an aqueous solution of palladium. It is possible to obtain a plating medium film containing a metal having electrical conductivity, thereby easily obtaining a metallized material. As a result, the electroless plating method whose use is suppressed from the viewpoint of environmental protection is not required in the future, and harsh electroplating conditions in the conventional conductive treatment method are not required. Therefore, it is expected that the reliability of the metallized material itself is also high.

Claims (12)

[Claims] An underlayer formed of a material obtained by polymerizing a compound having a carbon-carbon triple bond in the same molecule represented by the following general formula is formed on a surface of a substrate, and a palladium element is formed on the underlayer. To give conductivity by contacting a solution containing
A method for manufacturing a metallized material, comprising: forming a metal layer by an electrolytic plating layer on an underlayer to which the conductivity has been provided to manufacture a metallized material. Formula (R- (C≡C) _l ) _k -L-A _m (wherein A is a hydrogen atom or a hydroxyl group, an amino group, an ether group, a mercapto group, a polyoxyether group, a polyaminoether group, or a polyaminoether group. A thioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof,
It represents a functional group selected from a carboxyl group or a salt thereof, a phosphate group or a salt thereof, and a polymerizable group. R represents an element of Group 8 or Group 1B of the periodic table. L represents a chemical bond or a (k + m) -valent linking group. k and l are integers of 1 or more, and m is 0 or an integer of 1 or more. ) 2. A material obtained by polymerizing a compound having a carbon-carbon triple bond in the same molecule represented by the following general formula on the surface of a substrate in the presence of a Group 8 or 1B element of the periodic table. The formed underlayer is formed, a solution containing a palladium element is brought into contact with the underlayer to impart conductivity, and a metal layer is formed on the underlayer provided with the conductivity by an electrolytic plating layer to form a metal layer. A method for producing a metallized material, comprising producing a metallized material. Formula (R- (C≡C) _l ) _k -L-A _m (wherein A is a hydrogen atom or a hydroxyl group, an amino group, an ether group, a mercapto group, a polyoxyether group, a polyaminoether group, or a polyaminoether group. A thioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof,
It represents a functional group selected from a carboxyl group or a salt thereof, a phosphate group or a salt thereof, and a polymerizable group. R represents a carboxyl group or a salt thereof, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a silyl group, an aryl group, an aralkyl group, an ester group, a heterocyclic group, an element of Group 8 or Group 1B of the periodic table. L represents a chemical bond or a (k + m) -valent linking group. k and l are integers of 1 or more, and m is 0 or an integer of 1 or more. ) 3. The method for producing a metallized material according to claim 1, wherein the conductivity of the underlayer is set to 200 Ω / □ or less by imparting conductivity. 4. A compound represented by the above general formula,
The method for producing a metallized material according to any one of claims 1 to 3, wherein the polymerization is performed by performing a heat treatment in a temperature range of -200C for 0.5-90 minutes. 5. The method for producing a metallized material according to claim 4, wherein the compound represented by the general formula is polymerized by heat treatment in the presence of a nitrate. 6. The method for producing a metallized material according to claim 1, wherein the substituent R of the compound represented by the general formula is a Group 1B element of the periodic table. 7. The method according to claim 6, wherein the Group 1B element is silver. 8. The method for producing a metallized material according to claim 1, wherein A of the compound represented by the general formula is a polyethoxyether group. 9. A solution prepared by adding a surfactant to a solution of the compound represented by the general formula, coating the solution on a substrate in the form of a film, and then polymerizing the solution. Production method of metallized material. 10. A substrate made of a non-conductive material or a semiconductor material, an intermediate layer formed on the surface of the substrate, and an electrolytic plating layer formed on the intermediate layer, wherein the intermediate layer comprises:
A compound derived from a compound having a carbon-carbon triple bond in the same molecule represented by the following general formula, an alloy of palladium with a Group 8 or 1B element of the periodic table or a palladium element, and a metal constituting an electrolytic plating layer A metallized material comprising a mixture of materials. Formula (R- (C≡C) _l ) _k -L-A _m (wherein A is a hydrogen atom or a hydroxyl group, an amino group, an ether group, a mercapto group, a polyoxyether group, a polyaminoether group, or a polyaminoether group. A thioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof,
It represents a functional group selected from a carboxyl group or a salt thereof, a phosphate group or a salt thereof, and a polymerizable group. R represents a carboxyl group or a salt thereof, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a silyl group, an aryl group, an aralkyl group, an ester group, a heterocyclic group, an element of Group 8 or Group 1B of the periodic table. L represents a chemical bond or a (k + m) -valent linking group. k and l are integers of 1 or more, and m is 0 or an integer of 1 or more. ) 11. The flexible printed circuit board, wherein the substrate is made of polyimide resin, polyethylene naphthalate or polyethylene terephthalate, and the electrolytic plating layer is made of a copper-patterned layer. Metallized material. 12. The electrolytic plating layer having a thickness of 5 to 20 μm.
12. The metallized material of claim 10 or 11, wherein m is m.