JPH01104782A - Catalytic material for electroless plating and metallized material using same - Google Patents

Abstract

PURPOSE:To provide proper activity to a catalytic material for electroless plating and to enable the formation of a metallized material having superior characteristics by electrroless plating, by incorporating a polymer of a compd. having a triple bond CidenticalC and a group VIII or IB element into the catalytic material. CONSTITUTION:A polymer of a compd. having a triple bond CidenticalC, e.g., polyacetylene is incorporated into a caralytic material for electroless plating and one or more group VIII or IB elements such as Au, Ag and Pd are further incorporated in the form of simple substances, complexes, salts, etc. The catalytic material is metallized by electroless plating with Cu, etc. The resulting metallized material is applicable to various uses because it has superior adhesion of the plating and electrical conductivity.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to a novel catalyst material for electroless plating and a metallized material using the same. Prior art and its problems Electroless plating is a plating method that utilizes reduction by contact action on the surface of a material, and is also called chemical plating. Unlike electroplating, this has the advantage of being able to plate to a uniform thickness even in recessed areas. For this reason, electroless plating is used for conductive treatment for electroplating synthetic resins and for manufacturing thin films for printed circuits. When applying this electroless wet chemical plating to non-metallic surfaces,
It is known that a compound containing an element of group 8 or group IB of the periodic table is used as an activation catalyst (Japanese Patent Application Laid-Open No.
No. 7-43977, DE 2,934,580). A conventional method for the currentless production of metal coatings on electrically non-conducting or semi-conducting substrates comprises the following steps i) to iv). i) cleaning the substrate surface, immersing it in a bath containing stannous chloride or other stannous salts, and rinsing with water; ii) adding a metal salt (e.g. silver nitrate, gold chloride, etc.) that promotes the precipitation of the desired metal; 1ii) the metal ions of the bath are reduced by the stannous ions adsorbed onto the substrate and/or by the reducing agent contained in the electroless metal salt bath applied in the next step; iv) treating the catalytically activated surface with a solution of the desired metal in the presence of a reducing agent (i.e. electroless metal salt); bath treatment) to deposit the desired metal, such as copper, nickel or cobalt. This method and similar methods are usually called ``ionization activation.''
It is called. For example, German Patent No. 1,197,720 describes a method for activating the surface of a polymeric substrate during plating. In this method, a colloidal solution of metallic palladium is created by introducing tin(II) chloride into a hydrochloric acid/palladium chloride solution, which is thought to be stabilized by stannic acid and tin(IV) oxychloride. It will be done. For this reason, this method is commonly referred to as "colloidal activation." These colloidal particles are deposited on the substrate surface and in the next step are activated with an appropriate concentration of acid, alkali or salt, the protective colloid is removed and the palladium particles form, providing a catalytically activated surface on the substrate. . These palladium particles act as catalyst nuclei for subsequent electroless copper or nickel plating. A water washing step is required between each of the above steps. However, these activation methods, i.e. in-shell prior art techniques, have the following drawbacks. First of all, in order to complete a catalytically activated surface to which electroless plating can be applied, several processing steps (activation, sensitization, water washing, etc.) are required, making the process complicated. However, it is expensive. Secondly, this method is not widely applicable, but rather is generally limited to substrates whose surfaces have been pretreated by chemical or mechanical means. The necessity of pretreating the substrate before chemical plating and subsequent electroplating is explained by Eugen G.
ewze Verlag), published by R. Weiner (R,W
“Plastic Plating” by Einerl (Kunsts)
(197)
3) is also described. This pretreatment generally consists of etching the surface of the substrate (often a polymer) using, for example, chromic sulfuric acid, followed by several water washes followed by detoxification using a sodium bisulfite solution, followed by a water wash. This step is then followed by a suitable activation, such as the ionization activation or colloidal activation described above. Etching changes the polymer surface, resulting in the formation of bits and voids. This is only possible with certain polymers, examples being ABS polymers, biphasic multicomponent krafts or copolymers such as high-impact polystyrene;
Alternatively, there are biphasic homopolymers such as partially crystalline polypropylene. Additionally, the use of chromium sulfate or other oxidizing agents is associated with a deterioration of physical properties such as notch impact strength and electrical surface resistance of the underlying polymeric material. Techniques for improving the adhesion of catalyst nuclei to the substrate include JP-A-57-43977, JP-A-58-104170,
There is a method using a metal complex having in one molecule a group that binds to a metal and a group that shows affinity for a substrate, such as the one disclosed in JP-A-61-15984. However, improvement in adhesion in this case basically depends on adsorption of the metal complex onto the substrate, and a satisfactory degree of adhesion has not been achieved. Thirdly, if metal particles such as metal palladium adsorbed on the surface of the substrate are even partially arranged densely, undesirable conduction may occur when a printed wiring pattern is formed by electroless plating. . The fully additive method has long been attracting attention as a simple method for manufacturing printed wiring boards. However, due to these problems, this fully additive method has not been actively applied at present, and manufacturing methods that require complicated processes such as subtractive and semi-additive methods are still mainstream. . ■ Purpose of the Invention The purpose of the present invention is to provide a catalyst material for electroless plating having an activity suitable for performing electroless plating, and a metallized material with excellent properties by performing electroless plating using the catalyst material and metallizing it. Our goal is to provide the following. III. DISCLOSURE OF THE INVENTION These objects are achieved by the present invention as described below. That is, the catalyst material for electroless plating of the present invention is carbon-
It contains a polymer derived from a compound having a carbon triple bond and an element from group 8 or group IB of the periodic table. Furthermore, the metallized material of the present invention can be applied to a catalyst material for electroless plating containing a polymer derived from a compound having a carbon-carbon triple bond and an element of group 8 or group IB of the periodic table. It has been made into a metal. ■Specific structure of the invention The specific structure of the present invention will be explained in detail below. The catalyst material for electroless plating of the present invention contains: 1. a polymer derived from a compound having a carbon-carbon triple bond; It is contained in the form of complexes containing elements, metal salts, etc. In the present invention, such a catalyst material for electroless plating is subjected to electroless plating to be metallized, and this is used as a metallized material. The compound-derived polymer having a carbon-carbon triple bond in the present invention is a polyacetylene-based polymer having a carbon-carbon triple bond or double bond in the main chain or side chain. As for the organic moiety constituting the above polyacetylene polymer, if the basic constituent elements of the polymer have a carbon-carbon triple bond or double bond, it may be further dispersed or dispersed in other polymers. May be blended. Examples of such other polymers include polyphenol resin, epoxy resin, gelatin, polyvinyl alcohol, polysulfone, diacetyl cellulose, polyvinyl acetate, polystyrene, polyurethane, silicone polymer, polyether polyol, polyimide, polyvinyl butyral, polythioether, Thermoplastics such as polyethylene, polyamide, polyvinyl chloride, fluororesin, polyacrylate, polyester, polybutadiene, melamine resin, maleic resin, alkyd resin, amyldine,
Examples include various synthetic or natural resins such as thermosetting and reactive resins. The amount of these various synthetic or natural resins is usually about 10"wt% or less of the polyacetylene polymer used as the catalyst material for electroless plating. Furthermore, the above polyacetylene polymer may have other functional groups as well. Although such functional groups may be of any type, in order to exhibit higher catalytic ability in the intrashell aqueous wet electroless plating process,
It is preferably a hydroxyl group, an amino group, an ether group, a polyoxyether group, a polyaminoether group, a polythioether group, a sulfino group or a salt thereof, a sulfo group or a salt thereof, or a carboxyl group or a salt thereof. In the present invention, a compound having such a functional group may be separately contained together with a polyacetylene polymer and a catalyst material for electroless plating. Preferred polyacetylene polymers in the present invention include only homopolymers or copolymers having a carbon-carbon conjugated unsaturated bond in the main chain or side chain and the above-mentioned other optional functional groups. It consists of: Preferred compounds (monomers) having a carbon-carbon triple bond from which such polymers are derived, that is, compounds that provide the basic structure among the constituent elements of such polymers, have the following general formula (I ). General formula (I) (R-(CmiC),)k-(L)-(A) 11° In the above general formula (I), A is a hydrogen atom or any one selected from the following functional group group. One or more selected groups, such as hydroxyl group,
Amino group, ether group, mercapto group, polyoxyether group, polyaminoether group, polythioether group,
Sulfino group or its salt, sulfo group or its salt, carboxyl group or its salt, or polymerizable group (
For example, glycidyl group, vinyl group, isocyanate group, etc.)
etc. R is a group 8 element of the periodic table (for example, nickel, ruthenium, rhodium, palladium, platinum, etc., preferably palladium) or a group IB element (copper, silver, gold, preferably silver, gold), a hydrogen atom, a carboxyl group, or a salt thereof, or an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, silyl group, aryl group, aralkyl group, ester group or heterocyclic group, each of which may be substituted; L is a carbon-carbon triple bond; A chemical bond connecting A or a (k+m)-valent group, such as an optionally substituted alkylene group, arylene group, aralkylene group, vinylene group, cycloalkylene group, glutaroyl group, phthaloyl group, hydrazo group, ureylene group, or It represents 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 may be a combination of two or more thereof. However, k and nin are integers equal to or larger than l.
Moreover, m is an integer of 0 or more. Preferred specific monomers are listed below, but the invention is not limited to these. :e, :e
:c :c :c
-N's cry Φ
= = UCJ ^ A A /+ ^
^-N -arm -Φ ~ C%J ('J four
~ Nv ++ +++
++ ++ -engineering
= Q O The monomers of these acetylene compounds can be synthesized in the following manner. That is, compounds having a carbon-carbon triple bond, such as propiolic acid, propargyl bromide, propargyl alcohol, etc., and compounds having other necessary functional groups, such as tetraethylene glycol monoethyl ether, maleic anhydride, propane. What is necessary is to condense sultone, epichlorohydrin, acrylic acid chloride, etc. An example of a synthesis method is given below. Synthesis of Exemplary Compound (1) Tetraethylene glycol monoethyl ether 107g
, propargyl bromide 107g, anhydrous potassium carbonate 300g
The mixture was heated and stirred on a water bath for 20 hours. After cooling,
Insoluble matter is filtered through Celite, and the filtrate is distilled under reduced pressure.
Yield 120g Colorless and transparent liquid, boiling point 115℃10
．． 6mmHg Other compounds can be easily synthesized in the same manner. These compounds are polymerized to form the polyacetylene polymer of the present invention as described in detail later, and in this case, dimers, trimers, oligomers, etc. of these compounds may be used. Furthermore, when forming a polyacetylene copolymer, two or more of these compounds may be used as monomers. Furthermore, as the above monomer, as R, Group 8 to I
Although monomers having group B elements are not exemplified, monomers having the above-mentioned exemplified metal elements as R may also be used. Those having these metal elements as R are (CH-(CI
IC), ), -(L)-(A-) can be easily obtained by reacting an acetylene compound represented by A- with a metal salt such as silver nitrate, palladium chloride, cuprous chloride, or nickel chloride by a known method. In such a reaction, the above acetylene compound may be suspended in an aqueous solution or an appropriate organic solvent, and the above metal salt may be added to the suspension.At this time, a catalytic amount of iodine in the organic base may be added. The reaction is often carried out in the coexistence of cupric chloride or sodium radoxide in methanol.Also, the use of stabilizing ligands such as triphenylphosphine makes it easy to isolate the reaction product. The acetylene compound having a group 8 or group IB element obtained in this way is found to be an acetylide complex or a π complex by NMR spectrum and IR spectrum. As mentioned above, silver, palladium, and copper are preferable as elements, but especially silver,
Palladium and gold are preferred. One or more of such acetylene compounds or their dimers, oligomers, etc. are polymerized to form the polyacetylene polymer of the present invention. As methods for synthesizing the polymer in the present invention, many methods such as radical polymerization using heat, light, gamma rays, etc., ionic polymerization, and other polymerization methods using transition metal complex catalysts have been reported in miscellaneous articles and reviews, and many known methods are used. Both are applicable [Usp, Khim, Vol. 45, No. 4, pp. 695-741 (
(1976)]. Recently, along with the development of conductive polymers and research on optical recording materials,
A new synthesis method for polymers with conjugated unsaturated bonds has been developed.
It has been reported. For example, Macromolecule
s Vol. 14, No. 2, pp. 233-236 (1981),
J, Amer, Chem, Soc, Vol. 102, No. 27, pp. 7940-7944 (1980), JP-A-61-1
No. 37781, etc. can be referred to. The degree of polymerization of these polymers is determined by the synthesis conditions or the structure of the monomers used, and therefore, preferred polymers from oligomers to polymers with a high degree of polymerization are used depending on the conditions of use. However, in the present invention, it is preferable to use a material that has an extremely high degree of polymerization and is insoluble in solvents such as dimethylformamide. The presence of double bonds derived from the acetylene monomer is observed by the FTIR spectrum, and in some cases, the presence of triple bonds is also observed. Note that various gas phase polymerization methods can also be used as the polymerization method. Examples of the gas phase polymerization method include a gas phase polymerization method in which bilibinyl alcohol containing ferric chloride is applied to a substrate, and after drying, polymerization is carried out by contacting with virol vapor, and other various carbon
VD method etc. can be used. In addition to these polymerization methods, electrolytic polymerization, which is an effective method for creating functional polymer thin films, can also be used. Examples of the Group 8 elements of the periodic table in the present invention include nickel, ruthenium, rhodium, and palladium.
Among these, palladium is most preferred. Examples of the IB group elements include copper, silver, and gold, and among these, silver and gold are most preferred. One or more of these Group 8 to IB elements of the periodic table are present in the catalyst material for electroless plating of the present invention in the form of an elemental metal, a metal salt, or a metal complex, and are bonded or coordinated to the acetylene polymer. In some cases, they are contained in the form of their alloys and various compounds. Among these, preferred metal salts include silver nitrate, palladium chloride, cuprous chloride, and platinum chloride. In addition, these metal complexes include di-μm chlorobis(
η-2-methylallyl) cibaradium (II) complex, tetrakis(triphenylphosphine) palladium complex,
Examples include diμm chlorotetratonyl dirhodium (I) complex, 1.4゜7.10.13-penkoxycyclododecane sodium tetrachlorovanadinite, dicyclopentadiene-gold (I) chloride, etc. . These compounds can also be dispersed as particles having an average particle size of about 0.01 to 1 tile, for example. Further, when using an acetylene compound monomer in which a metal is introduced as described above, the metal may be introduced in the form of bonding or coordination to the polyacetylene polymer. However, in this case, as described below, it is generally precipitated in the form of metal during polymerization. These metal salts, metal complexes, etc. are reduced to metal by the reducing agent in the electroless plating, and serve as catalyst nuclei during electroless plating. As the catalyst nucleus, palladium, silver, and gold are preferable among the elements of group 8 or group IB of the periodic table, as described above. As the polymer in the present invention, monomers containing elements of group 8 or group IB of the periodic table among those represented by the general formula (I) can also be used. Further, when using a monomer that does not contain the above-mentioned metal element, a compound (monomer) having a carbon-carbon triple bond may be polymerized in the coexistence of a metal salt or a metal complex of the above-mentioned element. Alternatively, after forming the polyacetylene polymer, a metal salt or the like may be introduced as described in detail later. Among these metal elements, monovalent copper, silver, trivalent gold, divalent palladium, and tetravalent platinum can be used not only as monomer polymerization catalysts, but also as catalyst nuclei for electroless plating in the polymer film. It can be used as Divalent palladium is a particularly useful element in this regard. The amount of elemental metals, metal complexes, metal salts, etc. of group 8 or IB of the periodic table present in such polyacetylene polymers is 5 to 5,000 parts by weight per 100 parts by weight of the polymer of the present invention.
, particularly preferably 10 to 500. The catalyst material for electroless plating of the present invention may be in the form of a film, particles, or fibers. In the case of forming a film, specifically, a thin film may be formed on the surface of the substrate. As for the method of forming a thin film on a substrate, there is a method of supporting the thin film on the substrate using the above-mentioned monomers using a vapor phase growth method, an electrolytic polymerization method, a Langmuir-Prodgett method, a coating method, or the like. As described above, in the present invention, since the thin film is supported on the substrate and then polymerized on the substrate, it has extremely strong adhesion. This leads to a significant improvement in adhesion, which is a drawback of conventional electroless plating. When forming a film, it may be formed by various methods, and the simplest method is a coating method. In the case of coating methods, there are methods such as curtain coating, dip coating, spray coating, spinner coating, and roll coating from a monomer solution or suspension. The solvent and concentration used at this time are not particularly limited. Considering the uniformity of the thin film, it is desirable to use a solvent with high solubility. Typical examples include water, methanol, acetone, ketones such as methyl ethyl ketone, These include halogen compounds such as chloroform and methylene chloride, esters such as ethyl acetate, amides such as dimethylacetamide, dimethylformamide, and N-methyl-2-pyrrolidone, and nitriles such as acetonitrile. In addition, pattern printing typified by screen printing may be applied. Screen printing may be performed using a viscous solution or paste using a screen and a squeegee according to a known method. In this case, in order to make a paste, it is most preferable that the combination of the metal element and the monomer that serves as the catalyst core itself has an appropriate viscosity. It may be mixed with a vehicle together with a metal compound. After forming the film in this manner, it is polymerized using the method described above. Further, a polyacetylene polymer may be applied, but as mentioned above, the polymer used preferably has a high degree of polymerization, so it is preferable to perform polymerization after applying the monomer. Note that it is possible to apply a known technique of providing a protective layer or a base layer on the film thus formed, or of laminating a plurality of layers. Another example of preparing a film of a catalyst material for electroless plating by applying the film formation method and polymerization method described above is to use the Langmuir-Prodgett method described in JP-A-61-137781. A monomolecular cumulative film of amphiphilic monomers, such as exemplified compounds (10), (14), and (16), was formed on a glass substrate, and after polymerization by irradiating the film with ultraviolet light from a high-pressure mercury lamp, There is a method of immersing in a bath of metal salts of Group 8 or Group IB. As a bath for metal salts, etc., an aqueous solution may usually be used. In addition, a solution of a metal salt or the like may be applied or a metal salt monomer may be used. The above example is a topochemical polymerization method that utilizes the orientation of acetylene bonds, but as an example using a more advanced polymerization method, azobisisobutyronitrile and exemplified compound (20) are used as a thermal polymerization initiator. This is a method in which a chloroform solution is applied onto a polymethyl methacrylate substrate using a spin cord or the like, heated (for example, at 80°C for 40 minutes), and then immersed in a bath containing metal salts of Group 8 or Group IB of the periodic table. . The metal salts impregnated into the membrane by these methods are reduced to metal, for example, by a reducing agent in the electroless plating bath or by applying a reducing bath before the electroless plating bath. In addition, as another method, a compound forming a complex with a metal of Group 8 or Group IB of the periodic table is used as a polymer-forming monomer, such as exemplified compounds (1), (6),
The silver acetylides (27) and (40) are applied onto a substrate using a spin cord or the like, and then polymerized by heating or irradiation with ultraviolet light. In this method, sufficient metal is obtained by heating or irradiation with ultraviolet light to serve as a catalyst for electroless plating. In some cases, some metal complexes exist, but due to the action of the reducing agent in the electroless plating bath, these metal complexes also change to function as catalyst nuclei. With this method, it is possible to easily remove submicron-thick thin films that have the catalytic function of electroless plating, in which fine metal particles serving as a catalyst are homogeneously dispersed in a polymer having conjugated unsaturated bonds, without using any organic solvents. It can be formed on a conductive substrate. In the present invention, the amount of the polymer having carbon-carbon unsaturated bonds used is preferably 1 mg to 10 g, particularly 20 mg to 1 g, per rn'' of the substrate. The thickness is 0.001-5, especially 0.005
J1M1 to 0.54 is appropriate. In addition, for example, a metal salt, an elemental metal, an alloy, or a metal compound may be dissolved or dispersed in a monomer solution or suspension, and then applied and then polymerized. The above-mentioned Langmuir-Prodgett method for producing monolayers and accumulating them is the method described in "New Experimental Chemistry Course Volume 18 Interfaces and Colloids Chapter 6; Nippon Kagaku Extra Line Maruzen". Comply with. In this case, even if a vertical dipping method is used in which the monomolecular film is transferred by moving the substrate up and down in a direction across the liquid surface, the substrate (substrate)
You can use either the horizontal adhesion method, in which the membrane is supported horizontally and the membrane is attached by touching the monomolecular membrane surface.The water used is subjected to ion exchange, removal of organic matter with potassium permanganate, and distillation. The water temperature is set at 15-20°C. C as necessary
Add 10-3 to 10-4 mol/4 of ions such as Dissolve to a concentration of 0,5-1,0 mg/msI.After preparing the monomolecular film, apply a surface pressure of 20-25 d to the substrate.
Accumulate while maintaining yn/cm. In the present invention, the substrate for forming a film includes, for example,
copper, iron, titanium, glass, quartz, ceramics, carbon,
Polyethylene, polyphenol, polypropylene, AB
S polymers, epoxy resins, glass fiber reinforced epoxy resins, polyesters, and also polyamides, polyolefins, polyacrylonitrile, polyvinyl halides, cotton or wool or mixtures thereof, or copolymers of the monomers listed above. Textile sheets (including cloth)
Includes fiber aggregates such as yarns and fibers, paper, and particulate materials such as silica. In addition, in the present invention, a film may be formed by depositing a monomer by a vapor phase growth method instead of a coating method. Vapor phase growth methods can be broadly classified into physical vapor deposition methods (PVD) and chemical vapor deposition methods (CVD). Examples of PVD include a vacuum evaporation method, an ion blating method, and a sputtering method. - For CVD, thermal CVD, Blaz VCV
D (PCVD), optical CVD, etc. In the present invention, any method may be applied. Vacuum deposition is carried out according to conventional methods as follows.
Acetylene monomer is evaporated by direct heating in a coil or boat made of W, Mo, Ta, etc., or by indirect heating in a crucible made of quartz, alumina, or beryllia. At this time, resistance heating, high frequency heating, or the like is used as a heating method to heat the monomer to a temperature selected depending on the characteristics of the monomer, usually above its melting point. The pressure is usually 10-”torr.
The following shall apply. There are many sputtering methods, and any of them may be used, and various methods such as 2-pole, 4-pole sputtering, magnetron sputtering, etc. can be applied. Target material is acetylene monomer, voltage is about 1 to 5 kV, power density is about 20 to 200 W/[rr1, pressure is from 10-3 to
The condition may be about 10-'torr. For ion brating, any of the direct current method, high frequency method, cluster ion beam method, and hot cathode method may be applied. In either method, the vapor obtained by evaporating the acetylene monomer to be formed into a thin film is partially ionized and accelerated toward the substrate to form a film. The heating method may be appropriately selected from the above four methods. The pressure is usually about 10-6 to 10-'' torr, and the substrate is preferably subjected to ion bombardment, surface cleaning, and heating and temperature raising treatments.After these PVD processes, the above-mentioned polymerization is usually performed, and then Metal elements may be introduced as necessary, and may be introduced before polymerization. In these PVD methods, polyacetylene polymers are used as evaporation sources and targets, and in some cases, monomers and metal salts are combined. It is also possible to use a mixture of or the catalyst material for electroless plating of the present invention containing a polymer and a metal.Thermal CVD may be carried out using an acetylene monomer as a source according to a known method.As a carrier gas: H2
, Ar, N2, etc., and the reaction for forming the thin film may be performed at normal pressure or low pressure (about 10 to 10 torr), which may be selected as appropriate. At this time, the substrate temperature is 60 to 200
The temperature should be around ℃. PCVD can be performed by applying a known technique by activating acetylene monomer gas with plasma. The substrate temperature is about 20 to 150°C, and the pressure is 0.
Approximately 1 to 10 torr, gas flow rate 20 to 80 c
m"/min, and the input power may be about 50 to 150 W. PhotoCVD uses acetylene monomer gas as a source,
The activation may be carried out according to a known method by appropriately selecting the light used for activation (near ultraviolet to vacuum ultraviolet light, laser light, etc.). The substrate temperature in this case may be about 20 to 80°C. Each of these CVD methods usually deposits a polymer film, so
-RQ does not require polymerization as described above. However, if necessary, the above-mentioned polymerization is performed. In such a case, the metal may be introduced by incorporating it into the monomer, or a metal source may be used together with the monomer, and furthermore, after forming the deposited film, it may be immersed in a bath of metal salt, etc. as described above. You can also do something like this. In addition, a metal element may be introduced after the above-mentioned gas phase polymerization. Electropolymerization, like normal electrochemical measurements, generally involves 3
Electrode type (i.e., working electrode, counter electrode, and reference electrode) is used.The working electrode can be a variety of metal or semiconductor electrodes depending on the purpose, the counter electrode is usually a platinum or carbon electrode, and the reference electrode can be a platinum or carbon electrode. is a saturated calomel electrode (Satura
tedCalomel Electrode; 5CE
) and A g /A g+ electrodes are used. As the electrolytic polymerization cell, a glass container having a structure in which a working electrode chamber and a counter electrode chamber are separated by a sintered glass filter or the like is used. This is to prevent the products produced at the working electrode and counter electrode from mixing. The electrolyte must contain at least the monomer to be polymerized and a supporting electrolyte to provide sufficient conductivity to the solution.
Furthermore, a pH buffer solution or the like is added if necessary. Examples of electrolytic modes for electrolytic polymerization include constant potential electrolysis, potential drag electrolysis, constant current electrolysis, and alternating current electrolysis. The main role of the electrode reaction in the electrolytic polymerization method is to generate polymerizable active species on the electrolytic surface. Therefore, the voltage applied to promote the reaction is sufficient if the voltage necessary for this generation is applied to the electrode. , unless there is a special purpose, applying a voltage higher than this may accelerate the progress of side reactions,
It is desirable to avoid this as it may cause decomposition of the formed polymer film. The thin polymer films produced have a variety of functions, ranging from conductive ones with conductivity close to those of metals to completely insulating ones, and electrodes coated with this electropolymerized film can be used to connect the electrode and the thin film. It can be applied to various fields as a new composite electrode material that integrates the following. Furthermore, this polymerization method has a wide range of applications as a method for producing "chemical modification" of the surfaces of various electrodes (metal, semiconductor, carbon electrodes, etc.). In addition, when it is made into a film form, it may be formed into a film form as it is, or it may be peeled off from the substrate after film formation and used. In order to make the catalyst material for electroless plating of the present invention into granules, it may be granulated by a known method such as suspending it in a dispersion medium such as water and subjecting it to suspension polymerization. If the monomer does not contain a metal element, then a metal is introduced as described above, if necessary. In this case, particles having a particle size of about 0.1 μm to 1 mm can be obtained. In addition, in order to make it into a fibrous material, a known method such as an extrusion method is used after preparing the polymer, as detailed in Fiber Science Yoshin, Fiber Handbook, Raw Materials Edition, Maruzen (1968). Bye. The catalyst material for electroless plating thus obtained is metallized by electroless plating. The electroless plating bath used in the present invention is preferably a bath containing nickel salts, cobalt salts, copper salts, gold and silver salts, or mixtures of these salts with each other or with iron salts. . Plating baths of this type, including but not limited to those known for use in electroless plating, contain an inert substrate and eutectoid the material into the plated film. A plating bath can also be used. For example, ``Latest electroless plating technology'' supervised by Homoto Kobe (published by the General Technology Center) P43 Nickel plating bath, P44
Any of the plating baths and plating conditions described in Cobalt Plating Bath, P100 Copper Plating Bath, P2O4 Cobalt/Nickel Plating Bath, etc. can be used in the present invention. In the thus obtained metallized material of the present invention, the plating component permeates and immobilizes the catalyst material for electroless plating, and the entire material has electrical conductivity. In this case, the surface resistance is 5 to 10-2Ω/in the case of copper plating.
It's about the size of a mouthful. Therefore, for materials with a thin film formed on the base, the base (substrate)
Since the surface in contact with is also conductive, it is possible to easily achieve electrical conduction through the through-holes of the multilayer board. Further, a pattern can be formed by a full additive method and used for a printed wiring board. In addition, we also provide terminal plating, electromagnetic shielding materials, photomasks and hard blanks for IC boards, flexible wiring boards, wear-resistant N
It can be applied to various uses such as i-plating, bright plating films, resistance heating elements, internal electrodes and internal conductors of inductors and capacitors as ceramic elements, magnetic recording media, optical recording media, conductive fibers, and conductive fillers. A feature of the catalyst film in the metallized material of the present invention is that the metal film formed through it has high stability against stress such as heat. It is believed that this is because the metal film formed by electroless plating grows from within the polymerized thin film, and this film can easily absorb the difference in thermal expansion coefficient between the substrate and the metal. In the conventional surface activation method, the catalyst nuclei had to be arranged two-dimensionally on the substrate surface, but in the catalyst membrane of the present invention, they are dispersed three-dimensionally at a low density to achieve the same level of activity. Since this can be obtained, there is no practical concern about undesirable conduction. In the metal material of the present invention, granular materials can be used as conductive fillers and conductive particles. Furthermore, fibrous materials can be used as conductive fibers, decorative fibers, and intermediate fibers. Furthermore, a film-like material can be used as a flexible printed circuit board. According to the present invention, extremely high catalytic activity can be obtained when palladium is used.・It is also possible to obtain high catalytic activity even with silver, which is much cheaper than palladium. Such high catalytic activity is thought to be due to the carbon-carbon unsaturated bond making some contribution to the metal particles that serve as catalytic nuclei. It is also possible to obtain a metal coating that firmly adheres to surfaces that are generally difficult to plate without pre-etching. Thin films containing polymers derived from compounds containing this carbon-carbon triple bond, when formed, provide very tight adhesion to the substrate surface, either due to chemical reaction or adsorption with the substrate surface or due to the monomers being attached to the substrate. This is thought to be based on a physical planar anchor effect because a polymerized film is formed after uniform wetting depending on the unevenness. (2) Specific effects of the invention According to the present invention, a catalyst material for electroless plating that has excellent catalytic activity and is suitable for electroless plating can be obtained. In this case, it can be formed into various forms such as film, granules, and fibers depending on the purpose and use. In addition, since electroless plating is performed using such a catalyst material for electroless plating to produce a metallized material, it has excellent properties such as adhesion. It has electrical conductivity and can be used in various applications. In this case as well, it is possible to take various forms such as film, granule, and fibrous forms, as described above. When forming a film on a substrate, the film can be formed in various patterns. Vl, Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown to explain the present invention in further detail. Example 1 A silver salt of Exemplified Compound (1) was prepared by the following method. 16.4 g of sodium acetate, 1 g of silver acetate in a light-shielded state
6.7 g was suspended in 200 mu of distilled water at 40°C. 20.1 g of Exemplified Compound (1) was added dropwise to this, stirred for 20 minutes, and then cooled to room temperature. Neutralize this with 7.8 g of sodium hydrogen carbonate, remove the supernatant liquid by decantation, and add 200 mR of distilled water and 400 mR of chloroform.
mu was added and extracted. After drying the chloroform layer over anhydrous sodium sulfate, the chloroform was distilled off under reduced pressure to obtain 29 g (quantitatively) of a white waxy solid. 'It was confirmed from the NMR spectrum and IR spectrum that this substance was a silver σ complex. MR δ 1 , 1 5 (triplet, 3 H) 3
, 0~40 (multiplet, 14H
)3, 4 (broad singlet,
2 H) I R2860cm-' (C-H expansion and contraction) 19
80cm"' (CwC expansion and contraction) 1100cm-' (C-0 expansion and contraction) 0.24g of silver salt of exemplary compound (1) and 0.36g of distilled water
and 1.80 g of methanol were mixed and dissolved to obtain a solution with a concentration of 10% by weight. 1 m5 of the above solution 4.5cm x 7cmP ETb
The solution was dropped onto the acetate and coated in a thin film using a spin code method. This was heated on a hot plate at 180° C. for 15 minutes to form a light brown transparent thin film insoluble in water. Then copper sulfate 10g/I2, Rochelle's salt 15g/12 and 37% formaldehyde solution 20m51/12
The sample was immersed in an alkaline electroless plating copper bath containing sodium hydroxide and adjusted to pH 12 to 13. After 20 minutes, a tightly adherent layer of copper with a metallic luster had been deposited. The surface resistance of the metal surface was 4.0Ω/mouth. The cross-sectional structure of the metallized film obtained by the above method was observed using a scanning electron microscope, and the film thickness excluding PET was 0.
．． The metal part was approximately uniform and had the same thickness. In addition, the thickness of the light brown transparent thin film immediately after heat treatment is 0.1 μm.
There were 50 to 100 uniform silver particles dispersed within it. Example 2 0.05 g of silver salt of exemplary compound (1) prepared in Example 1
was dissolved in 2.28 g of distilled water to obtain a solution with a concentration of 2% by weight. Heating and electroless copper plating were performed in the same manner as in Example 1 except that this was applied with a wire bar.
A translucent film with a copper metallic luster was obtained. Its surface resistance is 8.3Ω/mouth. I tried peeling it off with Sellotape, but it didn't come off at all. Example 3 Exemplified compound (6) was replaced with Exemplified compound (1) in Example 1.
In the same way as silver salt, 1 g of O was added to chloroform l m
It was dissolved in u to make a solution with a concentration of 9% by weight. This was coated, heated, and electroless copper plated in the same manner as in Example 1. An opaque film with a copper metallic luster was obtained. The surface resistance of this metal surface was 1.0Ω/hole. Example 4 0.24 g of silver salt of exemplary compound (1) prepared in Example 1
, dissolve 1.0 g of gelatin in 8 m of distilled water, and add the solution 5.
mM was applied onto the PET with a wire rod. After air drying, this was left on a hot plate at 180° C. for 15 minutes, and then immersed in the same electroless copper plating bath as in Example 1 and crushed. 40 minutes later,
The film showed a uniform copper coating with a metallic luster on the surface in contact with the PET, but there was no conductivity on the surface in contact with the liquid. Example 5 Silver salt of exemplary compound (1) prepared in Example 1 0.22
g was dissolved in 1 mR of chloroform, applied in the same manner as in Example 1, irradiated with a high-pressure mercury lamp for 40 minutes, and then immersed in the same electroless steel plating bath as in Example 1. 20
After minutes, a metal film with a copper luster was obtained. The surface resistance was 20 to 38 Ω/mouth. Example 6 Exemplified compound (9) was made into a silver salt in the same manner as in Example 1,
Its silver salt 0.24g, N-hydroxymethylacrylamide 0.24g, distilled water 1m$1, methanol 1m5
A solution obtained by mixing and dissolving 1 was applied in the same manner as in Example 1, irradiated for 10 minutes under a high-pressure mercury lamp, heated at 100°C for 10 minutes, and then added to the same alkaline electroless copper plating bath as in Example 1. immersed in. The surface resistance of the metallized film obtained was 150 to 180 Ω/hole. Example 7 Exemplified compound (12) was added to benzene in an amount of 3×10-” mol.
After dissolving at a concentration of /n, it was developed on an aqueous phase of cadmium chloride (concentration: I x 10-" mol/min) aqueous solution at pH 5.8. After the solvent benzene was removed by evaporation, the surface pressure was set to 20 dyne/n. While keeping the surface pressure constant, the carrier was made of a glass substrate with a sufficiently clean and hydrophilic surface, and the vertical speed was increased to 1 cm in the direction across the water surface.
The diacetylene monomolecular film was transferred to a glass substrate by gently moving it up and down at 0 cm/min, and an accumulated film was formed in 31 layers. This was uniformly and sufficiently exposed to 254 nm ultraviolet light to form a blue film on the whole. This is determined by the palladium chloride concentration I x 10-”mol/4
After 10 minutes of immersion in an aqueous solution of (washed with water), an alkaline nickel plating bath containing 30 g/β nickel chloride, 3 g/12 dimethylaminoporane and 10 g/ρ citric acid and adjusted to pH 8.1 with ammonia was added. After 10 minutes, an effectively adhered and shiny nickel layer was deposited.The surface resistance was 3.8Ω.
/It was a mouth. Example 8 10 mg of azobisisobutyronitrile, exemplified compound (2
0) 1 g was dissolved in 10 all of chloroform, and this was applied onto a glass substrate by a spin code method to form a thin film. After heating this at 100'C for 30 minutes, it was immersed in an aqueous solution with a silver nitrate concentration of I x 10'mol/I2 for 10 minutes, and then thoroughly washed with water. It was then immersed in the alkaline electroless copper bath of Example 1 for 20 minutes. As a result, a metal layer with copper luster was formed on the glass plate. Its surface resistance was 20 Ω/mouth. Example 9 0.22 g of Exemplified Compound (1) and 0.1 g of silver nitrate in a fine powder frame
7 g were mixed and stirred for 20 minutes under ultrasonic dispersion to produce a pale yellow transparent viscous solution. It was confirmed from the NMR spectrum that this substance was a silver π complex. This was dissolved in 8 mu of methanol. The above solution 1 was dropped onto a 4.5 cm x 7 cm PET base and coated into a thin film using a spin code method. This was heated on a hot plate at 180° C. for 15 minutes to form a light brown transparent thin film insoluble in water. Next, it was immersed in the electroless plating copper bath of Example 1. After 20 minutes, a tightly adherent layer of copper with a metallic luster had been deposited. The surface resistance of the metal surface was 0.5Ω/hole. Example 10 Exemplary compound +510.18 and 30 mg of palladium chloride/sodium dichloride were dissolved in 2 g of methanol. When heating and electroless copper plating was performed in the same manner as in Example 1 except that this was applied with a wire bar, a translucent film with copper metallic luster was obtained within 1 minute after dipping.
Its surface resistance is 0.5Ω/mouth. I tried peeling it off with sellotape, but it didn't come off at all. Example 11 Exemplified compound (22) 0,20 g and palladium chloride.
30 mg of sodium dichloride was dissolved in methanol 2-. This was applied as a thin film on a glass substrate undercoated with 2% colloidal silica by a spin code method, and after heating on a 180° C. hot plate for 10 minutes, electroless copper plating was performed. An opaque film with a copper metallic luster was obtained. The surface resistance of this metal surface was 10Ω/mouth. Example 12 0.17 g of Exemplified Compound (6) and 0.99 g of cuprous chloride were dissolved in distilled water, and 5 m51 of the solution was applied onto PH7 using a wire rod. After air drying, this was left on a hot plate at 180° C. for 15 minutes, and then immersed in the same electroless copper plating bath as in Example 1. After 20 minutes, a uniform copper coating with metallic luster appears on the film, and its surface resistance is 1Ω.
/It was a mouth. Example 13 A methanol solution of 1 mQ of the silver salt of Exemplified Compound (1) prepared in Example 9 was applied in the same manner as in Example 1, and after irradiation with a high-pressure mercury lamp for 40 minutes, the same solution as in Example 1 was applied. Immersed in an electroless copper plating bath. After 20 minutes, a metal film with copper luster was obtained. This surface resistance was 0.1Ω/hole. Example 14 Exemplified compound (27) 0,20 g and silver nitrate 0.17 g
was made into a silver salt in the same manner as in Example 9, mixed with 8 ml of methanol, 1 ml of the dissolved solution was applied in the same manner as in Example 1, heated at 150°C for 10 minutes, and this was mixed with 8 ml of methanol. It was immersed in the same alkaline electroless copper plating bath as in 1. The surface resistance of the metallized film obtained was 1Ω/mouth. Example 15 0.22 g of Exemplified Compound (1) and 30 mg of palladium chloride/sodium dichloride were mixed with 2 ml of methanol,
It was coated onto a glass substrate in the same manner as in Example 1 in the form of a single film, and heated on a 180° C. hot plate. Next, cobalt sulfate 0.08 mol/4. Sodium hypophosphite 0,2 mol/g, sodium tartrate 0,
5 mol/1, boric acid 0, 5 mol/I2 with Na
OH was added to prepare an electroless cobalt bath at pH 9.
When immersed in this 90° C. bath for 20 minutes, a metallic layer with silver luster was formed. Its surface resistance was 10Ω/mouth. Example 16 A cotton cloth was immersed for 1 minute in 50 m$1 of the solution of Example 15. This was heated at 100° C. for 30 minutes, and then thoroughly washed with water. Then, in the alkaline electroless copper bath of Example 1,
After soaking for a minute, a cloth was formed that had a copper luster throughout. Its surface resistance was 20Ω/mouth. Example 17 Plasma polymerization was performed using Exemplified Compound (33) using a glass substrate. In this case, the carrier gas is argon, the gas flow rate is 145 [g/min, and the input power is 100
W, and the pressure was 21 orr. The plasma polymerized film thus obtained was immersed for 10 minutes in an aqueous solution with a palladium chloride concentration of I x 10-" mol, 1, and then thoroughly washed with water. Next, in the same manner as in Example 1, an electroless copper plating bath was used. A metal film with copper luster was formed (thickness: 0.3 μm).
The surface resistance was 1Ω/mouth. Example 18 60 g of silica gel was added to 50 m$1 of the solution of Example 15 and mixed well. This was spread on a steel plate and heated in an electric furnace at 150°C for 10 minutes. When this was gradually added to the alkaline electroless steel bath of Example 1 and stirred, fine particles of silica gel surrounded by copper were produced after 20 minutes. Example 19 Using Exemplified Compound (37), a film was formed by vacuum evaporation using a glass substrate. In this case, the pressure is 10-”torr, and the hearth temperature is 300°C.
And so. The palladium chloride concentration I x 10-3 mol/I
After being immersed in the aqueous solution of No. 2 for 10 minutes, it was thoroughly washed with water. Next, in the same manner as in Example 1, a metal film having copper luster was formed using an electroless copper plating bath. The surface resistance was 2Ω/mouth. Example 20 The solution of Example 15 was applied as a thin film onto high-quality paper in the same manner as in Example 2, and heated on a 150° C. hot plate. Then nickel chloride 24 g/fi, sodium hypophosphite 20 g/I2, ammonium citrate 60 g
/12, containing 40 g/β of boric acid, pH 8 with NaOH,
It was immersed in a 90°C nickel plating bath prepared at 5°C. After 5 minutes, a fine paper with a nickel shine was obtained.
The surface resistance was 5Ω/mouth. Example 21 Commercially available silk thread 20 in methanol solution in Example 15
cm was immersed for 10 seconds, and then immersed in the same electroless nickel plating bath as in Example 21. After 1 minute, a metallic system with a nickel luster was obtained.
The surface resistance was 15Ω/mouth. Example 22 The methanol solution of Example 15 was applied onto high-quality paper in the same manner as in Example 2, heated on a 150° C. hot plate for 10 minutes, and then immersed in the same electroless copper plating bath as in Example 1. After 5 minutes, a paper with a copper luster was obtained. Surface resistance is 0
．． It was 5Ω/mouth. I tried peeling it off with sellotape, but it didn't come off at all. Example 23 100 mU of the same aqueous solution as in Example 2 was prepared, and a glass fiber reinforced epoxy resin substrate was immersed in it to form a thin film. After heating this at 150° C. for 10 minutes, it was thoroughly washed with water. Next, it was immersed in the same electroless copper plating bath as in Example 1. After 20 minutes, a metal film (thickness 0.64) with copper luster was obtained. Surface resistance is 0. It was 1Ω/mouth. I tried peeling it off with sellotape, but it didn't come off at all. Example 24 A glass fiber reinforced epoxy resin substrate was immersed in the solution of Example 23 to form a thin film. After heating this at 150° C. for 10 minutes, it was thoroughly washed with water. Next, it was immersed in the same electroless nickel plating bath as in Example 2. After 5 minutes, a substrate with a nickel shine was obtained. The surface resistance was 5Ω/1TII. I tried to peel it off by pasting cellophane tape on it, but it didn't come off completely.Next, after patterning it with photoresist, ED
A nickel wiring pattern was created by eluting unnecessary portions of nickel with a TA and iron aqueous solution, and then eluting the photoresist with a sodium hydroxide aqueous solution. Example 25 Through holes were formed using a high-speed punching machine in a glass fiber-reinforced epoxy resin substrate whose both sides were patterned with negative-type dry photoresist. After immersing 22 g of silver salt of Exemplified Compound (1) in 200 mu of distilled water for 1 minute, the solution was heated at 150° C. for 10 minutes. After thoroughly washing it with water, it was immersed in the same electroless copper plating bath as in Example 1. After 20 minutes, it was taken out. The copper pattern is neatly formed, and the surface resistance is 0.
The resistance was 1Ω/hole, and both sides were electrically connected through through holes, allowing it to be used as a double-sided board. After that, unnecessary portions of the resist were removed using sodium hydroxide. Example 26 Through holes were formed in a glass fiber reinforced epoxy resin substrate using a high speed punching machine. This was immersed in the methanol solution of Example 15 for 20 seconds, and then heated at 150° C. for 10 minutes. This was thoroughly washed with water. Next, it was immersed in the same electroless nickel plating bath as in Example 20. After 5 minutes, it was taken out. The surface resistance was 5Ω/hole, and both sides were electrically connected through through holes, allowing it to be used as a double-sided board.

Claims (2)

[Claims] (1) A catalyst material for electroless plating characterized by containing a polymer derived from a compound having a carbon-carbon triple bond and an element of group 8 or group 1B of the periodic table. (2) A catalyst material for electroless plating containing a polymer derived from a compound having a carbon-carbon triple bond and an element of group 8 or group 1B of the periodic table is metallized by electroless plating. Characteristic metallized materials.