JPH02205686A - Formation of pattern of metallic material - Google Patents

Abstract

PURPOSE:To accurately form a high density pattern of a metallic material with high productivity by patternwise polymerizing a polyacetylene compd. contg. a group VIII or IB element with radiation ray and carrying out electroless plating. CONSTITUTION:A substrate is coated with a compd. having C-C triple bonds and contg. a group VIII element of the periodic table such as Pd or a group IB element such as Ag or Cu and the compd. is polymerized by irradiation. At this time, the compd. is patternwise polymerized by controlled scanning of radiation ray or with a patterned mask. The unreacted compd. is then removed by dissolution in a solvent such as water and a patterned layer of a catalytic material for electroless plating is formed. This catalytic material is subjected to electroless plating with an electroless plating bath contg. an Ni salt, etc. A high quality precise pattern of a metallic material is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to a method of forming a pattern of metal material using electroless plating.

Prior art and its problems Electroless plating is a plating method that utilizes reduction due to contact action on the surface of the material, and is also called chemical plating. Unlike electroplating, it is possible to plate to a uniform thickness even in recessed areas. It has the advantage of being possible. 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 1B of the periodic table is used as an activation catalyst (Japanese Patent Application Laid-Open No. 1986-1999).
No. 43977, DE 2,934,580).

Generally, a conventional method for producing a metal film on a non-conductive or semi-conductive substrate in a currentless manner includes the following steps 1) 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 (such as silver nitrate, gold chloride, etc.) that promotes the precipitation of the desired metal; 1ii) immersion in a bath of tin (palladium chloride or platinum chloride); 1ii) reduction of the metals in the bath by the stannous ions adsorbed on the substrate and/or the reducing agent contained in the electroless metal salt bath applied in the next step; reducing the ions to obtain a catalytically activated surface; iv) treating this catalytically activated surface with a solution of the desired metal in the presence of a reducing agent (i.e. an 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 prepared by introducing tin(n) chloride into a hydrochloric acid/palladium chloride solution, which is considered to be stabilized by stannic acid and tin(IV) oxychloride. For this reason, this method is commonly referred to as ``colloidal activation.'' The colloidal particles are deposited on the substrate surface and in the next step are activated with an appropriate concentration of acid, alkali, or salt to release the protective colloid. The palladium particles are removed to provide the substrate with a catalytically activated surface that acts as catalytic nuclei for subsequent electroless copper or nickel plating.

A water washing step is required between each of the above steps.

However, these activation methods, ie, common 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., L.
ewze Verlag), published by R.

“Plastic Plating” by R. Weiner (Kunststoff Galvanisieru)
(1973).

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 dilute 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 grafts 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 accompanied by 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-58-10417Q,
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. but,
In this case, improvement in adhesion basically depends on the 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. .

In order to deal with this problem, it is conceivable to adopt a full additive method, which has long been attracting attention as a simple method for manufacturing printed wiring boards. However, at present,
This fully additive method has not been actively applied, and manufacturing methods that require complicated processes such as subtractive and semi-additive methods are still the mainstream.

By the way, when forming patterns for printed wiring boards, etc., screen printing is used if the pattern density is small (or not), but photo-etching using a resist is used if the pattern density is high and requires high-precision microfabrication. is applied.

When performing wet etching or dry etching using such a resist, there are many steps and the etching quality is poor. Furthermore, if etching is insufficient, problems such as insufficient plating progress may occur.

(1) Purpose of the Invention An object of the present invention is to provide a method for forming a metal material pattern that can form a metal material pattern with high density and precision and has high productivity.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, in the present invention, 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 formed into a pattern by radiation, and then This method of forming a metal material pattern is characterized in that the patterned catalyst material for electroless plating is subjected to electroless plating to be metallized to form a metal material pattern.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The method for forming a metal material pattern of the present invention uses a polymer derived from a compound having a carbon-carbon triple bond and
A catalyst material for electroless plating containing a group element or a group 1B element is formed into a pattern using radiation, and then electroless plating is applied to the patterned catalyst material for electroless plating to metallize it to form a metal material pattern. It is something to do.

The polymer derived from a compound having a carbon-carbon triple bond in the present invention has 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 thermoplastics such as polyphenol resin, epoxy resin, gelatin, polyvinyl alcohol, polysulfone, diacetyl cellulose, polyvinyl acetate, polystyrene, polyurethane, silicone polymer, polyether polyol, polyimide, and polyvinyl butyral; Examples include various synthetic or natural resins such as thermosetting and reactive resins.

The content 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.

Further, the above polyacetylene polymer may further have other functional groups. Such functional groups may be of any type, but they may be electroless by a general water-based wet method. In order to show higher catalytic ability in the 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 ( Examples include those represented by I).

General formula (1) % formula % () In the above general formula (I), A is a hydrogen atom or a group arbitrarily selected from one or more of the following functional group groups, such as a hydroxyl group, an amino group, an ether group, and a mercapto group. 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 (e.g. 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 1B element (copper, silver, gold, preferably silver, copper), a hydrogen atom, a carboxyl group, or represents a salt, 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 chemical bond connecting the carbon-carbon triple bond and 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, thio group, carbonyl group, oxy group, imino group, sulfinyl group, sulfonyl group, thiocarbonyl group, oxalyl group, azo group, etc., even if it is a combination of two or more of these groups. good.
However, k and β are integers of 1 or more. Further, 5m is an integer greater than or equal to 0.

Preferred specific monomers are listed below, but are not limited to these.

Engineering = Q 0 HC-ICCH, OCH.

CHs CHI C■CCH, CH, OCH, CHi
OCH.

HC”CCHi 0CHa CHt 0CHs (CHs
)s 5iC-C-CHx 0CHx CHz 0CH
z CHx 0CHsHC=CCH* CCHi CH
I CCHi CHx 0CHz CH2NHCHs Monomers of these acetylene compounds can generally be synthesized as follows.

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, propansal. ton, epichlorohydrin,
What is necessary is to condense acrylic acid chloride or the like.

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.

As described in detail later, these compounds are polymerized in a pattern to form a polyacetylene polymer, and in this case, dimers, trimers, oligomers, etc. of these compounds may be used.

Furthermore, when forming a polyacetylene-based copolymer, two or more of these compounds may be used as monomers.

Furthermore, as the above monomer, R is from Group 8 to Group 1.
Although monomers having group B elements are not exemplified, monomers having these metal elements as R among the above-mentioned exemplified monomers may be used.

Those having these metal elements as R are (CH-(C
■C) j) k An acetylene compound represented by (L)-(A) m is reacted with a metal salt such as silver nitrate, palladium chloride, cuprous chloride, chlorauric acid, or chloroauric acid by a known method. can be easily obtained by

For such a reaction, the above acetylene compound may be suspended in an aqueous solution, and the above metal salt may be added to the aqueous solution to carry out the reaction. At this time, if ammonia or organic amines are present, the reaction will be facilitated. -The reaction product can generally be isolated by extraction methods.

The acetylene compound having a Group 8 to Group 1B element thus obtained is determined to be a σ complex or a π complex of acetylide according to the NMR spectrum and IR spectrum.

One or more of such acetylene compounds or their dimers, oligomers, etc. are polymerized to form a polyacetylene polymer.

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. 1
Group B elements include copper, silver, and gold, and among these, silver and copper are most preferred.

One or more of these elements from Group 8 to Group 1B of the periodic table is contained in the catalyst material for electroless plating in the form of an elemental metal, a metal salt, or a metal complex, and in a form bonded or coordinated to the polyacetylene polymer. Furthermore, depending on the case, they may be contained in the form of alloys or various compounds of these.

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) sibaradium (n) complex, tetrakis (triphenylphosphine) palladium complex, di μm chlorotetracarbonyl dirhodium (I) complex,
Examples include dicyclopentadiene-gold(I) chloride.

These are introduced into the catalyst material for electroless plating in the form of molecules as described below, but in some cases, the above-mentioned metals or alloys may be mixed into particles with an average particle size of about 10" to 10". Also, when using an acetylene compound monomer in which a metal is introduced as described above, the metal may be introduced in the form of a bond 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 metals by the reducing agent in the electroless plating bath, and serve as catalyst nuclei during electroless plating.

As the catalyst nucleus, palladium, silver, and copper are preferable among the elements of group 8 or group 1B of the periodic table, as described above.

As the polymer in the present invention, a monomer containing an element of group 8 or group 1B of the periodic table among those represented by the general formula (I) can also be used.

Furthermore, when using a monomer that does not contain the above-mentioned metal elements, the monomer and a metal salt of the above-mentioned element may coexist and be polymerized.

Alternatively, a metal salt or the like may be introduced after forming the polyacetylene polymer.

The metal salt or the like may be introduced by immersing the polyacetylene polymer in a bath (usually an aqueous solution) of the metal salt or the like, or by applying a solution of the metal salt or the like.

The amount of elemental metals, metal complexes, metal salts, etc. of Group 8 or Group 1B of the periodic table present in such polyacetylene polymers is 5 to 5,000, particularly 1, per 100 parts by weight of the polymer.
0-500 is preferred.

Palladium is preferably used as the catalyst core of the catalyst material for electroless plating from the viewpoint of catalytic activity, but the following method may be used to incorporate such palladium into the catalyst material for electroless plating. .

That is, a compound having a carbon-carbon triple bond is polymerized in the presence of a metal element that has a greater ionization tendency than palladium, and the metal element that has a greater ionization tendency than palladium is replaced with palladium.

Examples of metal elements having a greater ionization tendency than palladium include Zn%AI2, FesN1, Co, and C.
Examples include r%Mg%Cd, Sn, and Pb.

As a method for polymerizing in the presence of a metal element as described above, there is a method in which first, the acetylene compound containing such a metal element is used for polymerization.

Acetylene compounds containing such metal elements include:
Specifically, examples include those in which R in the general formula (I) is a metal having a greater ionization tendency than palladium.

There is also a method in which monomers of acetylene compounds that do not have metal elements are polymerized in the presence of a polymerization catalyst that has a metal that has a higher ionization tendency than palladium.

Such polymerization catalysts include salts or complexes of Ag, Mo, W, etc. (for example, Mo C12°, WCfie
, MoCI2 s (Cs Hll)4
Sn, WCAa (CaH8)4Sn, etc.), and various known ones.

In this case, the metal elements constituting the polymerization catalyst will be contained in the polymer, but a metal element with a greater ionization tendency than palladium may also be contained. They may be allowed to coexist during the process, or they may be dispersed after polymerization using the method described below.

Alternatively, a monomer containing such a metal element may be prepared in advance and polymerized at the same time.

The metal element that is present in the polyacetylene polymer and has a greater ionization tendency than palladium is then replaced with palladium.

Specifically, PdCA2, Nag PdCl;! , 4
It may be immersed in a bath of an aqueous solution such as

Another method is to apply a solution.

By adopting such a method, the amount of palladium can be reduced to a small amount, which is advantageous in terms of cost.

In the present invention, monomers, dimers, oligomers, etc. of acetylene compounds are polymerized in a pattern.

Polymerization is performed by radiation, and in order to form a pattern, polymerization may be performed in a pattern by controlling the scanning of radiation, or by using a pattern mask material or the like.

As the pattern mask material, a polyester-based lithium film, a glass dry plate, a chrome mask, etc. can be used, and it may be carried out according to a known method.

Further, CAD may be used to design a complicated pattern.

As described above, the acetylene compound in the present invention has a so-called resist function, and it becomes possible to form a pattern without using a separate resist.

In this sense, the acetylene compound in the present invention can be said to be a type of resist.

The radiation may be appropriately selected from visible ultraviolet (UV), electron beam, Xa, etc. depending on the acetylene compound used.

When using UV, the wavelength is usually 250 to 350 nm, and a high-pressure mercury lamp, Xe lamp, etc. is used, and the wavelength is 10" to 10".
The irradiation amount is approximately 'mJ/cm'.

In addition, in order to increase the resolution of exposure, it is recommended to use ultraviolet light of 200 to 300 nm when performing microfabrication.
For microfabrication using such short wavelength ultraviolet rays, a method using an excimer laser (wavelength: 249 nm) is effective.

Furthermore, in order to cause the reaction to occur with light of a long wavelength, a light absorber that absorbs the light can be added as necessary.

In the present invention, a pattern may be formed in a heat mode using a laser such as a YAG laser.

In this case, dyes, pigments, etc. may be added as light absorbers in order to improve the efficiency of heat shrinkage.

The acetylene compound in the present invention can be called a resist in the above-mentioned sense, and is a negative type compound in which the portion irradiated with radiation becomes difficult to dissolve in a solvent.

For this reason, after forming a polymer in a pattern as described above, the portions that are not irradiated with radiation and do not form a polymer are removed using an appropriate solvent.

As such a solvent, water, alcohol, acetone, etc. are used, and water is particularly preferred.

The line width of the patterned catalyst material for electroless plating thus formed is about 1 to 100-.

The reason why the above-mentioned thin line can be obtained is that when the acetylene compound of the present invention is used as a resist in the above-mentioned sense, it can be said that the resolution is excellent. In addition, the sensitivity is high, and the solubility in a certain solvent (for example, water) between the polymer-formed part and the non-polymer-formed part differs greatly, and a clear pattern image can be formed. Therefore, there is no need to use a separate resist.

In the present invention, the electroless plating catalyst material formed into a pattern 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 substrate.

As for the method of forming the film on the substrate, the simplest method is to apply the above-mentioned seven-layer film onto the substrate using a coating method.

In the case of coating methods, there are methods of curtain coating, dip coating, spray coating, spinner coating, roll coating, etc. from a solution or suspension of chlorine. 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, chloroform, halogen compounds such as methylene chloride, and ethyl acetate. esters such as dimethylacetamide, dimethylformamide 1, amides such as N-methyl-2-pyrrolidone, and nitriles such as acetonitrile.

As a specific example of applying the coating method, azobisisobutyronitrile and exemplified compound (20) are used as thermal polymerization initiators.
A chloroform solution of is applied onto a polymethyl methacrylate substrate using a spin cord or the like, polymerized in a pattern using radiation as described above, and the portions that do not polymerize are removed with water. This is a method such as immersion in a bath of metal salts of group metals.

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, a compound that forms a complex with a metal of group 8 or group 1B of the periodic table, such as silver acetylide of exemplified compounds (1), (6), and (27), is used as a polymer-forming monomer, and this is applied to the substrate. It is applied onto the surface using a spin cord or the like, and then polymerized in a pattern by irradiation with radiation such as ultraviolet light as described above, and the portions that do not polymerize are removed as described above.

In this method, a sufficient amount of metal to serve as a catalyst for electroless plating can be obtained by irradiation with ultraviolet light or the like. 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 create a submicron-thick thin film that has the catalytic function of electroless plating, in which fine metal particles serving as catalyst nuclei are homogeneously dispersed in a polymer with conjugated unsaturated bonds, without using any organic solvent. Can be formed on a non-conductive substrate.

In addition, for example, metal salts, simple metals, alloys, or metal compounds are dissolved or dispersed in a solution or suspension of monomers, and after being applied, they are polymerized in a pattern by radiation as described above, but do not polymerize. You may remove parts.

In the present invention, the amount of the polymer having carbon-carbon unsaturated bonds used is preferably 111 g to 10 g, particularly 20 mg to Ig, per substrate IM. The thickness of the film formed by this polymer or this polymer and other binders is 0.0
01- to 5-1, particularly 0.005- to 0.5- are suitable.

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.

Further, as for the method of forming the film, the Langmuir-Prodgett method may be applied.

The method for producing a monomolecular film by the Langmuir-Prodgett method and for accumulating it is based on the general method described in "New Experimental Chemistry Course Volume 18 Interfaces and Colloids Chapter 6; Nippon Kagaku Extra Line Maruzen".

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)
A horizontal adhesion method may be used, in which the monomolecular film is supported horizontally and the film is attached by touching the monomolecular film 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. If necessary, add ions such as Cd" to 10-" to 10
-'mol/I2 is added.

For example, in the vertical immersion method, it is desirable to use a float type microbalun as the device.

The purified monomer is dissolved in chloroform or the like for spectroscopic analysis to a concentration of 0, 5 to 1, Oa+g/ml. After preparing the monomolecular film, apply a surface pressure of 20 to 25% to the substrate.
Accumulate while maintaining dyn/cm.

As a specific example of applying the Langmuir-Prodgett method, amphiphilic monomers,
For example, exemplified compounds (10), (12), (14), (I
6) was made into a monomolecular cumulative film on a glass substrate, and after polymerization by irradiating it with radiation such as ultraviolet light from a high-pressure mercury lamp in a pattern as described above, the portions that did not polymerize were removed, and the periodic rule was There is a method of immersion in a bath of metal salts of Group 8 or Group 1B.

In addition, in the present invention, when forming a film, depending on the monomer used, vapor phase growth methods, which are broadly classified into PVD and CVD, can also be applied.

Further, in this case, if PVD%CVD is performed using a pattern mask material, direct patterning can be achieved. In the case of CVD, a polymer film is formed in a pattern.

Note that patterning is also possible without using a pattern mask material by, for example, performing light irradiation in a pattern using CVD or the like.

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 woven sheets of polyamides, polyolefins, polyacrylonitrile, polyvinyl halides, cotton or wool or mixtures thereof, or copolymers of the monomers mentioned above ( (including cloth),
These patterned catalyst materials for electroless plating include threads and fibers, aggregates of fibers such as paper, and particulate matter such as silica. Ru. In this way, a metal material pattern is formed.

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 include, but are not limited to, those known for use in electroless plating (e.g., containing an inert substrate and eutectoiding the material into the plating layer). A plating bath can also be used.

For example, any of the plating baths and plating conditions described in books such as "Latest Electroless Plating Technology" by Tokuzo Kobe, General Technology Center (1986) can be used in the present invention.

The metal material pattern obtained in the present invention has a width of about 1 to 100, and can be a thin line of about 1-1, like the pattern of the catalyst material for electroless plating described above.

The method for forming a metal material pattern of the present invention is effective when applied to obtain a high-density and high-precision printed wiring board.

(2) Specific Effects of the Invention According to the present invention, a metal material pattern can be formed with high density and accuracy. It also has excellent properties such as adhesion and excellent conductivity. In this case, since the acetylene compound itself that forms the catalyst material for electroless plating also functions as a so-called resist, there is no need to use a resist again (fine processing becomes possible. Therefore, productivity is increased.

V1 Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained 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 mj 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 with a decant, and add 200 mA of distilled water and 400 mA of chloroform.
m1 was added and extracted. After drying the chloroform layer over anhydrous sodium sulfate, 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, 1 4
H) 3, 4 (broad singlet,
2 H) I R2860cm-' (C-H expansion and contraction) 19
80 cm-' (C=C stretching) 1100 cm-' (C-0 stretching) 0.24 g of silver salt of exemplary compound (1) and 0.36 g of distilled water
and 1.80 g of methanol were mixed and dissolved to obtain a solution with a concentration of 10% by weight.

The above solution IIi was dropped onto a 4.5 cm x 7 cm PET substrate and applied in the form of a thin film using a spin code method.

After that, ultraviolet light from a Xe lamp was applied at approximately 104 mJ/cm.
``The polymer was formed in a pattern by irradiation with a certain amount of radiation.

Next, using water as a solvent, the portions that did not form a polymer were removed.

In this way, a water-insoluble light brown transparent thin film was created in a pattern. The thickness of this thin film was 0.1 -, and 50 to 100 uniform silver particles were dispersed therein.

Moreover, the pattern line width of the formed thin line was 60-.

Next, it was immersed in an alkaline electroless plating copper bath containing 10 g/l of copper sulfate, 15 g/I2 of Rochelle's salt, and 20 ml/I2 of 37% formaldehyde solution and adjusted to pH 12-13 with sodium hydroxide.

After 20 minutes, a tightly adherent layer of copper with a metallic luster had been deposited in a pattern. The surface resistance of the metal surface was 1 mΩ/cm''.

The cross-sectional structure of the metallized film formed in the pattern obtained by the above method was observed using a scanning electron microscope, and the film thickness excluding PET was 0.3 -, and the metal parts were almost uniform and had the same thickness. had.

Furthermore, the copper metallized pattern was good with no defects or the like at the above pattern size.

Example 2 Exemplified compound (12) was added to benzene in an amount of 3×10-”mol/
After dissolving at a concentration of I2, it was developed on an aqueous phase of cadmium chloride (concentration 1 x 10 mol/I2) aqueous solution at pH 5.8. After removing the solvent benzene by evaporation, the surface pressure was reduced to 20
dyne/cm.

While keeping the surface pressure constant, a glass substrate with a sufficiently clean and hydrophilic surface was used as a carrier, and was gently moved up and down in the direction across the water surface at a vertical speed of 1.0 am/+nin to form a diacetylene monomolecular film. was transferred to a glass substrate, and a cumulative film was formed on the 31 layers.

To this, apply ultraviolet light from a high-pressure mercury lamp at approximately 10'mJ/cm.
A polymer was formed in a pattern by irradiation with a dose of 1.

Next, the portion that did not form a polymer was removed using chloroform as a solvent.

In this way, a patterned blue film was formed.

This is determined by the palladium chloride concentration I x 10-”, a+ol
/I2 for 10 minutes and then thoroughly washed with water to obtain a patterned catalyst material for electroless plating.

Next, it was immersed in an alkaline nickel plating bath containing 3 g/β of borane and 10 g/Q of citric acid and adjusted to pH 8.1 with ammonia. After 10 minutes, an effectively adhered shiny patterned nickel layer was deposited.

The surface resistance was 0.1 Ω/cm'', and it was a good nickel metallized pattern with no defects at the above pattern size.

Example 3 10 mg of azobisisobutyronitrile, exemplified compound (2
0) Ig was dissolved in 10 mj of chloroform and applied onto a glass substrate by a spin code method to form a thin film.

After that, ultraviolet light from a high-pressure mercury lamp was applied at approximately 104 mJ/cm.
``A polymer was formed in a pattern by irradiation.

Next, the unformed portion of the polymer was removed using chloroform as a solvent.

Thereafter, it was immersed in an aqueous solution with a silver nitrate concentration of I x 10-' mol/β for 10 minutes, and then washed with water to obtain a patterned catalyst material for electroless plating.

When the glass plate was then immersed in the alkaline electroless copper bath of Example 1 for 20 minutes, a patterned metal layer with copper luster was formed on the glass plate. Its surface resistance is 1mΩ/cm2
It was a good copper metallized pattern with no defects or the like at the above pattern size.

Example 4 The thin film of Example 1 was formed on a glass substrate by a spin code method, and was scanned in a pattern with 249 no+ ultraviolet light using a YAG laser via potassium dihydroxyphosphate (KDP).

It was washed with water and immersed in a dilute hydrochloric acid solution of 500 ppm PdCρ2. Thereafter, when it was treated with the same electroless plating bath as in Example 2, nickel in the form of a fine line pattern was obtained.

Claims (1)

[Claims] (1) 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 formed into a pattern by radiation, and then the pattern is A method for forming a metal material pattern, comprising applying electroless plating to a catalyst material for electroless plating to metallize it to form a metal material pattern.