JP2010239080A - Method for forming conductive film, method for manufacturing printed wiring board, and conductive film material - Google Patents

Abstract

A method for forming a conductive film excellent in flexibility and thermal shock resistance of a resin layer contributing to adhesion between a conductive film and a substrate, a method for manufacturing a printed wiring board including the method for forming the conductive film in the process, and A conductive film material is provided.
(A) a step of forming a resin layer comprising a compound having a radical polymerizable group and a thermoplastic resin on an organic resin substrate; (b) an electroless plating catalyst or a precursor thereof; Forming a resin layer capable of adsorbing an electroless plating catalyst or a precursor thereof containing a resin having a functional group that interacts with the compound and a compound having a radical polymerizable group, (c) an electroless plating catalyst or a precursor thereof A method for forming a conductive film, comprising: a step of applying an electroless plating catalyst or a precursor thereof to a layer capable of adsorbing a body; and (d) a step of performing electroless plating to form an electroless plating film. .
[Selection figure] None

Description

  The present invention relates to a method for forming a conductive film and a conductive film material obtained by the method, and more particularly to a method for forming a conductive film suitable for a method for manufacturing a printed wiring board such as a semiconductor package substrate and a flexible printed wiring board. The present invention relates to a conductive film material useful for manufacturing a printed wiring board obtained by the manufacturing method and the forming method.

2. Description of the Related Art Conventionally, a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
As a method for producing such a metal pattern material, a “subtractive method” is mainly used. In this subtractive method, a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal film formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image. In this method, the metal film is etched to form a metal pattern, and finally the resist is removed.
In the metal pattern obtained by this method, the adhesion between the substrate and the metal film is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, there is a problem that the high frequency characteristics when used as a metal wiring are deteriorated due to the unevenness of the obtained metal pattern at the substrate interface. In addition, in order to obtain a metal pattern with excellent adhesion between the metal film and the substrate, it is necessary to treat the substrate surface with a strong acid such as chromic acid in order to make the substrate surface uneven. There is a problem that a complicated process is necessary.

  In order to solve this problem, plasma treatment is performed on the surface of the substrate, a polymerization initiating group is introduced on the surface of the substrate, a monomer is polymerized from the polymerization initiating group, and a surface graft polymer having a polar group is generated on the substrate surface. By performing this surface treatment, a method for improving the adhesion between the substrate and the metal film without roughening the surface of the substrate has been proposed (see, for example, Non-Patent Document 1). However, this method requires a large-scale apparatus such as a plasma generator in order to form the graft polymer on the substrate surface. In order to solve this problem, a method of providing a polymerization initiation layer on the substrate surface has been proposed. As the technique, there is a method in which a polymerization initiation layer composed of an initiator and a polyfunctional monomer is provided and a graft polymerization reaction is performed (for example, see Patent Document 1). However, in these methods, the polymerization initiation layer to be provided is a thermosetting resin, and it is hard to follow expansion and contraction due to heat, so there is a concern that cracks and the like may occur during a heat cycle in which heating and cooling are repeated. There was room for improvement in flexibility.

JP 2000-80189 A

Advanced Materials 2000 No. 20 1481-1494

An object of the present invention is to solve various problems in the prior art and achieve the following objects.
A first object of the present invention is to provide a method for forming a conductive film excellent in flexibility and thermal shock resistance of a resin layer that contributes to adhesion between the conductive film and the substrate, and a method for manufacturing a printed wiring board using the method. It is to provide.
A second object of the present invention is to provide a conductive film material having high photosensitivity and high productivity, in addition to high adhesion to a substrate, obtained by the conductive film formation method of the present invention. .
A further object of the present invention is to provide a conductive film material useful for the production of a printed wiring board obtained by the conductive film forming method of the present invention.

As a result of intensive studies, the present inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention.
That is, the method for forming a conductive film of the present invention comprises (a) a compound having a radical polymerizable group (hereinafter, appropriately referred to as a radical polymerizable compound) and a thermoplastic resin on an organic resin substrate. A step of forming a resin layer (resin layer A) comprising: (b) a resin having a functional group that interacts with an electroless plating catalyst or a precursor thereof and a radical polymerizable compound; A step of forming a resin layer (resin layer B) capable of adsorbing the precursor; (c) an electroless plating catalyst or precursor thereof on the resin layer (resin layer B) capable of adsorbing the electroless plating catalyst or precursor thereof; And (d) performing electroless plating to form an electroless plating film.

Preferred embodiments of the present invention include those shown in <2> to <7> below.
<2> The method for forming the conductive film, wherein the resin layer B further contains a radical generator.
<3> The method for forming the conductive film, wherein the radical polymerizable compound has a molecular weight of 5,000 or more and 200,000 or less.
<4> Resin having a resin layer (resin layer B) capable of adsorbing the electroless plating catalyst or a precursor thereof having a functional group that interacts with the electroless plating catalyst or the precursor formed on the resin layer A A method for forming the conductive film, which is a resin layer formed by applying energy to a resin composition layer containing bismuth and chemically bonding the resin composition layer with an adjacent resin layer A.

<5> The thermoplastic resin is polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / styrene copolymer, acrylic resin, polyamide, polyacetal, polycarbonate, The method for forming the conductive film, which is at least one selected from the group consisting of polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, and cyclic polyolefin.
<6> The method for forming the conductive film, wherein the functional group that adsorbs the electroless plating catalyst or its precursor is selected from a cyano group, a substituted or unsubstituted amino group, and a nitrogen-containing heterocyclic group.
In addition, the formation method of the electrically conductive film of the said this invention can be used suitably for manufacture of a printed wiring board.

The conductive film material of the present invention comprises, on an organic resin substrate, a thermoplastic resin layer containing a compound having a radical polymerizable group, a resin layer containing an electroless plating catalyst or a precursor thereof, a conductive film,
In this order.

  As described above, the present invention adds a radically polymerizable compound that reacts with radicals to the resin layer immediately above the base material, and the adjacent layer contains a radically polymerizable compound, more preferably an initiator system. Both photosensitivity and high adhesion strength between adjacent resin layers can be achieved.

In the configuration of the present invention, the resin layer (resin layer A) formed in the step (a) contains a radically polymerizable polymer compound and a thermoplastic resin, and thus exhibits high adhesion strength, particularly the resin layer A. It is useful for improving flexibility. The adhesion development mechanism includes a radical polymerizable compound contained in a resin composition that adsorbs an electroless plating catalyst or a precursor thereof contained in the resin layer (resin layer B) formed in step (b) when energy is applied. A radical is generated from a radical generator that reacts or is a preferred component and exists immediately above the substrate, and is contained in the resin layer (resin layer A) adjacent to the resin layer (B). Since a chemical bond is formed by reacting with a polymer compound, high adhesion strength can be expressed. A mechanism for forming a chemical bond by such a reaction is hereinafter referred to as a “graft-to mechanism”. In the case where the resin layer A does not contain a radical polymerizable compound, the graft-to mechanism does not function and thus high adhesion strength is not exhibited.
As energy applied for improving the adhesion between the resin layer A and the resin layer B, heat, light, and a combination of both can be used.
At this time, when light having a short wavelength of less than 300 nm is used for energy application, the resin layer B is cured by the radical polymerizable compound contained in the resin layer B, and the radical polymerizable compound contained in the resin layer A is also used. By reacting, adhesion between the resin layer A and the resin layer B is also ensured. When the exposure wavelength is 300 nm or more, the resin layer B preferably contains a radical generator. In that case, the radical generated from the radical generator causes the curability of the resin layer B, the resin layer A, and the resin layer. Adhesion with B is improved.

In the present invention, a radical generator is preferably contained in the resin composition that adsorbs the electroless plating catalyst or a precursor thereof for the purpose of improving the sensitivity when using light. When the resin layer B does not contain a radical generator, the resin layer A preferably contains a radical generator.
As the radical generator, by adding a thermal radical generator or a photo radical generator, radicals are generated from the radical generator, and the resin composition (resin layer B) that adsorbs the electroless plating catalyst or its precursor. ) Are photocured in a chain and react with the radically polymerizable compound contained in the resin layer A immediately above the substrate (graft-to mechanism) to form a chemical bond. Thereby, surface modification can be performed without requiring a large-scale apparatus such as a plasma generator. Moreover, when using light energy as energy, the photosensitivity at the time of exposure can be improved.

According to the present invention, a conductive film having excellent adhesion to a substrate can be formed, and a conductive film having excellent flexibility and thermal shock resistance of a resin layer contributing to the adhesion between the conductive film and the substrate is formed. An electrically conductive film forming method and a printed wiring board manufacturing method using the method can be provided.
According to the present invention, the conductive film material obtained by the method for forming a conductive film of the present invention has high photosensitivity and high productivity in addition to high adhesion to a substrate, and is useful for the production of a printed wiring board. Can be provided.

Hereafter, each process in the electrically conductive film formation method of this invention is demonstrated sequentially.
<(A) The process of forming the resin layer (resin layer A) containing a radically polymerizable compound and a thermoplastic resin on an organic resin base material>
Hereinafter, this process may be referred to as a resin layer A formation process or (a) process.
(Organic resin base material)
First, the organic resin base material will be described. Although there is no restriction | limiting in particular about the organic resin base material applicable to the electrically conductive film formation method of this invention, It can use for various base materials as listed below.
For example, epoxy resin substrate, polyimide substrate, PET substrate, PEN substrate, or cellulose triacetate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polytetrafluoroethylene, cycloolefin polymer, polyphenylene ether, polyphenylene oxide A substrate formed from a resin such as a liquid crystal polymer, a benzocyclobutene resin, a polyethersulfone, a polyetherimide, a polyarylate, an aramid resin, a phenol resin, a bismaleimide triazine resin, or a cyanate resin can be used.
Moreover, the glass epoxy board | substrate which is an epoxy resin containing glass cloth (glass fiber) is also included by the organic resin board | substrate in this invention.
As the base material, a flat base material (various substrates) is generally used, but the base material is not necessarily limited to a flat base material, and a base material having an arbitrary shape such as a cylindrical shape can also be used. .

In this specification, the thermoplastic resin layer containing the radical polymerizable compound formed in the step (a) is referred to as a resin layer A.
Examples of the thermoplastic resin suitably used for forming the resin layer A in the present invention include polyethylene (high density / medium density / low density), polyolefin resin (polypropylene, cyclic polyolefin, etc.), polyvinyl resin (polyvinyl chloride, Polyvinylidene chloride, polyvinyl acetate, polytetrafluoroethylene, etc.), polystyrene resin (polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / styrene copolymer (AS), etc.), acrylic resin, polyamide -Based resins, polyester-based resins (polycarbonate, polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, etc.), polyacetal resins, and the like are exemplified, but the present invention is not limited thereto.

  Among these, from the viewpoint of adhesion to an organic substrate, polystyrene resins (acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / styrene copolymers, butadiene / styrene copolymers, etc.), acrylic resins Polyester resins (polybutylene terephthalate, polyethylene terephthalate, etc.) are preferable, and polystyrene resins (ABS resin, acrylonitrile / styrene copolymer, butadiene / styrene copolymer, etc.) are more preferable.

  Acrylonitrile / butadiene / styrene resin is a resin generally called ABS. The synthesis method includes a graft method and a polymer blend method. In the graft method, acrylonitrile, latex, and styrene are polymerized. In the polymer blend method, rubber and additives are added to acrylonitrile / styrene copolymer (AS resin) and mixed. Acrylonitrile / styrene copolymer and butadiene / styrene copolymer refer to polymers obtained by copolymerizing respective monomers.

  The content of the binder polymer in the resin composition used for forming the resin layer A is preferably used in the range of 40% by mass to 99.9% by mass, and in the range of 60% by mass to 97% by mass. More preferably it is used.

(Compound having radical polymerizable group: radical polymerizable compound)
The resin layer A in the present invention contains a radical polymerizable compound. The radically polymerizable compound used here is a compound having a photoradical polymerizable double bond, and preferred examples include acrylate compounds, methacrylate compounds, vinylbenzyl compounds, vinylbenzyl ether compounds, bismaleimide compounds, and the like. Can be mentioned.
In the present invention, the radical polymerizable double bond in the polymerizable compound that can be used for the resin layer A may be of any kind as long as it is a functional group such as an allyl group, a (meth) acryloyl group, or a styryl group. In particular, those having a (meth) acryloyl group which is an ethylenically unsaturated group are preferred from the viewpoint of radical polymerizability.
From the viewpoint of curability and strength improvement, it is preferably a polyfunctional compound having a plurality of polymerizable double bonds in one molecule, and from the viewpoint of flexibility of the resin layer A, a plurality of compounds are contained in the molecule. A polymerizable polymer compound having a polymerizable double bond is preferred.

  Examples of the radical polymerizable compound that can be used in the present invention include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Preferably, an ester of an unsaturated carboxylic acid and a polyfunctional aliphatic alcohol compound, or an amide of an unsaturated carboxylic acid and a polyfunctional aliphatic amine compound is used. In addition, monofunctional or polyfunctional isocyanates or addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with monofunctional or polyfunctional isocyanates or amides having nucleophilic substituents such as hydroxyl groups, amino groups, mercapto groups, etc. Alternatively, a dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines and thiols, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.

  Specific examples of the radical polymerizable compound that is an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, propylene glycol diacrylate, Neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, polyester acrylate oligomer Etc.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Examples include hexanediol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, and sorbitol hexamethacrylate.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol tetritaconate And sorbitol hexaitaconate.

  Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol tetracrotonate, and sorbitol hexadicrotonate.

As the polymerizable compound according to the present invention, a polymerizable polymer compound is preferable. The molecular weight of the polymerizable polymer compound is preferably 5000 or more from the viewpoint of the flexibility of the resin layer A and the adhesion to the resin layer B, and more preferably a molecular weight of 10,000 or more. In view of handling properties when forming the resin layer A, the molecular weight is preferably 200000 or less, more preferably 150,000 or less.
As the polymerizable polymer compound, a polymer compound having a structure in which a polymerizable group is pendant on the side chain of the polymer main chain is preferable.

In the present invention, polymers suitable for the polymerizable polymer compound in which a polymer group is pendant on the side chain of the polymer main chain (hereinafter, appropriately referred to as a specific polymerizable polymer) are the following i) to iii). It can be synthesized by the synthesis method shown.
i) a method of polymerizing a monomer having a radical polymerizable group;
ii) a method of polymerizing monomers including a monomer having a double bond precursor, and then introducing a double bond by treatment with a base or the like;
iii) A method in which a monomer having a reactive group is polymerized to form a polymer, a monomer having a radical polymerizable group capable of reacting with the reactive group in the polymer is reacted to introduce a double bond (polymerizable group) Among these, the method ii) and the method iii) are preferable from the viewpoint of synthesis suitability.

  In addition, when synthesizing the specific polymerizable polymer in the synthesis methods i) to iii), another monomer may be used as a copolymerization component from the viewpoint of compatibility with the binder. As the other monomer, a general radical polymerization monomer is used, and examples thereof include a diene monomer and an acrylic monomer. Of these, unsubstituted alkyl acrylic monomers are preferred. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) methacrylate Etc. can be preferably used.

As the monomer having an interactive group used in the synthesis methods i) to iii), any monomer can be used as long as it is a monomer having the above-described polar group or non-dissociable functional group. Specific examples include the following.
These may be used alone or in combination of two or more.
<I) Method of polymerizing a monomer having a radical polymerizable group>
Examples of the monomer having a radical polymerizable group used in the synthesis method i) include allyl (meth) acrylate and compounds shown below.

<Ii) A method of polymerizing monomers including a monomer having a double bond precursor, and then introducing a double bond by treatment with a base or the like>
Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula (a).

In the above formula (a), A is an organic atomic group having a polymerizable group, R ^{1 to} R ³ are each independently a hydrogen atom or a monovalent organic group, and B and C are removed by elimination reaction. It is a leaving group, and the elimination reaction here means that C is extracted by the action of a base and B is eliminated. B is preferably eliminated as an anion and C as a cation.
Specific examples of the compound represented by the formula (a) include the following compounds.

  Preferred examples of the base used in the elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, Examples include potassium hydrogen carbonate and sodium hydrogen carbonate. Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like. Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases may be used alone or in combination of two or more.

  Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

  The amount of the base used may be equal to or less than the equivalent to the amount of the specific functional group (the leaving group represented by B or C) in the compound, or may be equal to or more than the equivalent. Moreover, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

<Iii) Polymerizing a monomer having a reactive group to form a polymer, reacting a monomer having a radical polymerizable group capable of reacting with the reactive group in the polymer, and introducing a double bond (polymerizable group) Method>
The polymer used in the synthesis method of iii) is synthesized by radical polymerization of a monomer having an interactive group, a monomer having a radical generation site, and a monomer having a reactive group for introducing a double bond. The
Examples of the monomer having a reactive group for introducing a double bond include monomers having a carboxyl group, a hydroxy group, an epoxy group, or an isocyanate group as the reactive group.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, vinyl benzoate, Aronics M-5300, M-5400, M-5600 manufactured by Toagosei, acrylic ester PA, HH manufactured by Mitsubishi Corporation, and Kyoeisha Chemical Co., Ltd. Examples thereof include light acrylate HOA-HH manufactured by Nakamura Chemical Co., Ltd., NK ester SA, A-SA, and the like.
As hydroxy group-containing monomers, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (meth) acryloyl -3-hydroxy-adamantane, hydroxymethyl (meth) acrylamide, 2- (hydroxymethyl)-(meth) acrylate, methyl ester of 2- (hydroxymethyl)-(meth) acrylate, 3-chloro-2-hydroxypropyl ( (Meth) acrylate, 3,5-dihydroxypentyl (meth) acrylate, 1-hydroxymethyl-4- (meth) acryloylmethyl-cyclohexane, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1-methyl-2- Acryloyloxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 1-methyl-2-acryloyloxyethyl-2-hydroxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxy- 3-chloropropylphthalic acid, Aronix M-554, M-154, M-555, M-155, M-158 manufactured by Toagosei Co., Ltd., Bremer PE-200, PE-350 manufactured by NOF Corporation PP-500, PP-800, PP-1000, 70PEP-350B, 55PET800, and lactone-modified acrylates having the following structures can be used.
_{CH 2 = CRCOOCH 2 CH 2 [} OC (= O) C 5 H 10] n OH
(Where R is a hydrogen atom or a methyl group, and n = 1 to 5)

Moreover, as a monomer which has an epoxy group, glycidyl (meth) acrylate, Daicel Chemical's cyclomers A and M, etc. can be used.
As the monomer having an isocyanate group, Karenz AOI and MOI manufactured by Showa Denko can be used.
In addition, the polymer used in the synthesis method of iii) may further contain another copolymerization component.
In the synthesis method of iii), as a monomer having a polymerizable group to be reacted with a polymer having a reactive group, a monomer having a functional group of the following combination is used, depending on the type of the reactive group in the polymer. be able to.
That is, (reactive group of polymer, functional group of monomer) is a combination shown below.
For example, (carboxyl group, carboxyl group),
(Carboxyl group, epoxy group),
(Carboxyl group, isocyanate group),
(Carboxyl group, benzyl halide),
(Hydroxyl group, carboxyl group),
(Hydroxyl group, epoxy group),
(Hydroxyl group, isocyanate group),
(Hydroxyl group, benzyl halide),
(Isocyanate group, hydroxyl group),
(Isocyanate group, carboxyl group),
(Epoxy group, carboxyl group) and the like can be listed.
Specifically, the following monomers can be used.

The specific polymerizable polymer in the present invention synthesized as described above has a radical polymerizable unit in an amount of 5 mol% to 100 mol% based on the entire copolymer unit of the polymer compound from the viewpoint of reactivity (curability and polymerizability). It is preferable that it is contained, More preferably, it is 10 mol%-100 mol%.
Specific examples of the specific polymerizable polymer that can be suitably used in the present invention are shown below by units constituting the polymer, but the present invention is not limited thereto. In addition, the number written together with each unit is the polymerization molar ratio of the unit, and the one without the number indicates a homopolymer of the unit. The molecular weight of the following specific polymerizable polymer is in the range of 5,000 to 200,000. The molecular weight was measured by dissolving the polymer in THF and measuring the molecular weight using Tosoh high speed GPC (HLC-8220GPC). The molecular weight was calculated in terms of polystyrene.

  The addition amount of the radical polymerizable compound to the composition for forming the resin layer A is preferably 1% by mass to 40% by mass from the viewpoint of high adhesion strength expression by the graft-to mechanism with the adjacent resin layer. More preferably, it is 5 mass%-20 mass%.

<Other additives>
The resin composition for forming the resin layer A may contain various additives depending on the purpose as long as the effects of the present invention are not impaired in addition to the polymerizable compound and the binder polymer which are essential components. Good.
(Filler)
For example, a filler can be added in order to reinforce properties such as mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, and electrical properties of the resin layer A.
Fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, Examples include calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is particularly preferred from the viewpoint of reducing the linear expansion coefficient.

The filler preferably has an average particle size of 5 μm or less. When the average particle diameter exceeds 5 μm, it is difficult to stably form a fine pattern when a fine pattern is formed using a conductive film.
When adding a filler, it is preferable to add in the range of 1-200 mass% with respect to a resin composition, More preferably, it adds in the range of 10-80 mass%. When this addition amount is less than 1% by mass, there is no effect of enhancing the above properties, and when it exceeds 200% by mass, properties such as strength specific to the resin are lowered.
The filler may be surface-treated with a surface treatment agent such as a silane coupling agent in order to improve the moisture resistance of the resin.

(Radical generator)
A radical generator may be added to the resin layer A for the purpose of further enhancing the adhesion with the resin layer B. As the radical generator to be used, either a photopolymerization initiator or a thermal polymerization initiator can be used. In particular, a photopolymerization initiator that can be easily cured simultaneously with the curing of the resin layer B is used. It is preferable. As the photopolymerization initiator that can be used, a polymerization initiator that can be used in the resin layer B described later can be used.

In the present invention, the resin composition for forming the resin layer A may appropriately contain a solvent.
Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, acetate esters such as propylene glycol monomethyl ether acetate, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, methyl Examples include glycol derivatives such as cellosolve acetate and ethyl cellosolve acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethers such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, and the like. .
These organic solvents may be used alone or as a mixed solvent of two or more.

As a method for forming the resin layer A, a composition for forming the resin layer A, that is, a resin composition containing a radical polymerizable compound and a thermoplastic resin and various components added as desired is applied. Examples of the liquid include a method in which knife coating, roll coating, curtain coating, spin coating, bar coating, dip coating, and the like are uniformly applied to the surface of the organic resin substrate described above and dried and cured.
As heating temperature at the time of drying, 20-100 degreeC is preferable, More preferably, it is 50-80 degreeC. The heating time is 1 second to 50 hours, more preferably 100 seconds to 3 hours.

  The thickness of the resin layer A in the present invention is preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.2 to 5 μm, from the viewpoint of adhesion strength.

<(B) Resin composition resin containing a resin having a functional group interacting with an electroless plating catalyst or a precursor thereof and a compound having a radical polymerizable group, and capable of adsorbing the electroless plating catalyst or the precursor thereof Step of forming layer>
(A) The surface of the resin layer A formed by the step further includes (b) a resin having a functional group that interacts with the electroless plating catalyst or its precursor and a radical polymerizable compound, and electroless plating. A resin composition resin layer (resin layer B) capable of adsorbing the catalyst or its precursor is formed. In order to ensure adhesion with the resin layer A, the resin layer B contains a radical generator in addition to a resin having a functional group that interacts with the electroless plating catalyst or its precursor and a radical polymerizable compound. Is preferred.
Hereinafter, a resin composition resin layer (resin) containing a resin having a functional group that interacts with an electroless plating catalyst or a precursor thereof and a radical polymerizable compound and capable of adsorbing the electroless plating catalyst or the precursor thereof This step of forming the layer B) may be referred to as a resin layer B forming step or (b) step.

(Resin composition having a functional group that interacts with the electroless plating catalyst or its precursor)
The resin layer B is a layer serving as a basis for forming a conductive layer formed in an electroless plating process to be described later, and is a functional group that can form an interaction with an electroless plating catalyst or a precursor thereof (hereinafter referred to as an interaction as appropriate). A resin having a functional group).
Examples of such interactive groups include carboxyl groups, hydroxyl groups, substituted or unsubstituted amino groups, sulfonic acid groups, phosphonic acid groups, amide groups, and other polar groups or salts thereof; cyano groups; imidazole groups and pyridine groups. A nitrogen-containing heterocyclic group which may have a substituent, and functional groups such as an ether group, and the resin layer B can be formed using a resin having such an interactive group. . Specific examples include polyacrylic acid, polymethacrylic acid, polyacrylonitrile, and ABS.

The resin composition having a functional group that interacts with the electroless plating catalyst or its precursor contains a radical polymerizable compound from the viewpoint of increasing sensitivity when light is used to develop adhesion, It is preferable to contain a radical generator.
The resin having a functional group that interacts with the electroless plating catalyst or its precursor and the radical polymerizable compound may serve as the same molecule. Specifically, it interacts with the electroless plating catalyst or its precursor. When the resin having a functional group has a polymerizable group in the molecule, the same molecule serves as the radical polymerizable compound, and does not need to contain another radical polymerizable compound. Among such embodiments, an acrylic resin containing a functional group that adsorbs the electroless plating catalyst or its precursor and a radical polymerizable group in the molecule is more preferable. In addition, a general radical polymerizable compound as contained in the resin layer A is added to the acrylic resin containing in the molecule a functional group that adsorbs the electroless plating catalyst or its precursor and a radical polymerizable group. You can also.
(Radically polymerizable compound)
The resin composition constituting the resin layer B contains a radical polymerizable compound.
The radically polymerizable compound used here can be the same as that used in the resin layer A. Moreover, preferable content is also the same. However, when a resin having a functional group capable of forming an interaction with an electroless plating catalyst or a precursor thereof has a polymerizable group as described later, these general radical polymerizable compounds may not be added.

(Acrylic resin containing functional group and radical polymerizable group in the molecule that adsorbs electroless plating catalyst or its precursor)
Examples of the acrylic resin having a radical polymerizable double bond include a compound containing a carboxylic acid (carboxylate) described in JP-A No. 2003-118043 and a formula (1) shown in JP-A No. 2009-77540. The copolymer etc. which contain the unit represented and the unit which has a cyano group represented by following formula (2) can be used.

(In the above formulas (1) and (2), R ^{1 to} R ⁵ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z are each independently Represents a single bond or a substituted or unsubstituted divalent organic group, ester group, amide group or ether group, and L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group Represents a group.)
The content of such a resin in the entire composition forming the resin layer B is preferably 50 to 100% by mass, and more preferably 60 to 95% by mass.

(Radical generator)
When exposure or heating with a wavelength of 300 nm or more is used as the energy imparting means in the present invention, the resin layer B may contain a radical generator from the viewpoint of improving curability and adhesion with the resin layer A. preferable. The radical generator used in the present invention may be either a thermal radical generator (thermal polymerization initiator) or a photo radical generator (photopolymerization initiator), but imparts energy in a pattern. Considering the suitability of the process and the simple production of the apparatus, it is preferable to use a photo radical generator.
1. Thermal radical generator As the thermal radical generator that can be used for the resin layer B, a peroxide initiator such as benzoyl peroxide, azobisisobutyronitrile, and an azo initiator can be used. .

2. Photoradical generators Photoradical generators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, Examples thereof include f) ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, (k) pyridinium compounds, and the like. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones In the present invention, (a) aromatic ketones preferred as a photo radical generator include those described in “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. Fouassier, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117, such as benzophenone, 1,1-diethoxymethyl-phenyl-ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, thioxanthone, Examples include 2-ethoxy-thioxanthone, 4-phenoxy-4′phenoxy-benzophenone, and the compounds shown below.

Among these, particularly preferred examples of (a) aromatic ketones are listed below.
The α-thiobenzophenone compound described in JP-B-47-6416 and the benzoin ether compound described in JP-B-47-3981 include, for example, the following compounds.

  Examples of the α-substituted benzoin compound described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, and the following compounds, for example.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-81345 include the following compounds.

  The α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, for example, the following compounds may be mentioned.

  P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  Examples of the acylphosphine sulfide described in JP-B-2-9597 include the following compounds.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

(B) Onium Salt Compound In the present invention, preferable examples of the (b) onium salt compound as a photoradical generator include compounds represented by the following general formulas (1) to (3).

In general formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In general formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of the (b) onium salt compound that can be suitably used in the present invention include paragraph numbers [0030] to [0033] of JP-A No. 2001-133969 and paragraph numbers of JP-A No. 2001-305734. Examples include [0048] to [0052] and those described in paragraph numbers [0015] to [0046] of JP-A-2001-343742.

(C) Organic peroxide In the present invention, (c) the organic peroxide preferable as a structure having photopolymerization initiating ability includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. . Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl peroxylaurate, and tertiary butyl peroxide. Oxycarbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3 ', 4,4' -Tetra- (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogendiphthalate), carbonyldi (t-hexylperoxydihydrogendiphthalate) Etc.

(D) Thio compound In the present invention, the (d) thio compound preferable as a photoradical generator includes a compound having a structure represented by the following general formula (4).

In the general formula (4), R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, and R ²⁷ represents a hydrogen atom or an alkyl group. R ²⁶ and R ²⁷ represent a group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may be bonded to each other and contain a hetero atom selected from oxygen, sulfur and nitrogen atoms.
Specific examples of the thio compound represented by the general formula (4) include compounds having a functional group shown in Table 1 below.

(E) Hexaarylbiimidazole compound In the present invention, preferred (e) hexaarylbiimidazole compounds as photoradical generators include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, for example, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazo 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

(F) Ketooxime ester compound In the present invention, preferred as a photoradical generator, (f) ketoxime ester compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one , 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

(G) Borate Compound In the present invention, examples of the (g) borate compound that is preferable as a photoradical generator include compounds represented by the following general formula (5).

In general formula (5), R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Represents an alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, and R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are bonded to form a cyclic structure. May be. However, at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group. (Z ⁵ ) ⁺ represents an alkali metal cation or a quaternary ammonium cation.

In the general formula (5), the alkyl group represented by R ^{28 to} R ³¹ includes linear, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. In addition, examples of the substituted alkyl group include the above alkyl groups, halogen atoms (eg, —Cl, —Br, etc.), cyano groups, nitro groups, aryl groups (preferably phenyl groups), hydroxy groups, —COOR. ³² (wherein R ³² represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —OCOR ³³ or —OR ³⁴ (wherein R ³³ and R ³⁴ represent 1 to 1 carbon atoms) 14 alkyl groups or aryl groups), and those having the following formula as substituents.

In the formula, R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group.

  Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. And the compounds shown below.

(H) Azinium compound In the present invention, (h) azinium salt compounds that are preferred as photo radical generators are disclosed in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, Examples thereof include compounds having an N—O bond described in Japanese Utility Model Laid-Open Nos. 63-143537 and 46-42363.

(I) Active ester compound In the present invention, (i) an active ester compound preferable as a photoradical generator is an imide sulfonate compound described in JP-B-62-2223, JP-B-63-14340, JP-A-59. The active sulfonates described in -174831 can be mentioned.

(J) Compound having carbon halogen bond In the present invention, the compound described in the following general formulas (6) and (7) is preferable as the compound (j) having a carbon halogen bond, which is preferable as a photoradical generator. it can.

In the general formula (6), X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ . Here, ^R38 represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³⁷ represents -C (X ²⁾ _3, alkyl group, substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

In general formula (7), R ³⁹ represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group, or a cyano group. . X ³ represents a halogen atom. n represents an integer of 1 to 3.

  Specific examples of the compounds represented by the general formulas (6) and (7) include the following compounds.

(K) Pyridinium Compound In the present invention, examples of the (k) pyridium compound preferable as a photoradical generator include compounds represented by the following general formula (8).

In general formula (8), preferably, R ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, a halogen atom or a monovalent organic residue, at least one of which is represented by the following general formula (9 ). Further, R ⁵ and R ^6, R ⁵ and R ^10, R ⁶ and R ^7, R ⁷ and R ^8, R ⁸ and R ^9, R ⁹ and R ¹⁰ are bonded to each other may form a ring. Furthermore, X represents a counter anion. m represents an integer of 1 to 4.

In general formula (9), R ¹² and R ¹³ are each independently a hydrogen atom, halogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group or substituted alkynyl group. R ¹¹ represents a hydrogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group Represents an amino group or a substituted amino group. R ¹² and R ¹³ , R ¹¹ and R ¹² , and R ¹¹ and R ¹³ may be bonded to each other to form a ring. L represents a divalent linking group containing a hetero atom.

Among these photoradical generators, heat-resistant photopolymerization initiators are preferable, and specifically, aromatic ketones are preferable.
Among these aromatic ketones, aromatic ketones having the following structure are more preferable.

  When the photopolymerization initiating group represented by the general formula (I) is linked to a polymer chain to form a polymer photopolymerization initiator, the linking group is preferably linked to a phenyl ring. Alternatively, the phenyl group and the polymer chain may be directly bonded.

  When the photopolymerization initiating groups represented by the general formula (II) and the general formula (III) are linked to a polymer chain to form a polymer initiator, the linking group is linked to a phenyl ring or —OH. Is preferred. Alternatively, the phenyl group or —OH may be directly bonded to the polymer chain.

  When the photopolymerization initiating group represented by the general formula (IV) is linked to a polymer chain to form a polymer initiator, the linking group is preferably linked to a phenyl ring. Alternatively, the phenyl group and the polymer chain may be directly bonded.

  Examples of the linking group include a divalent or trivalent linking group. Specifically, —O—, —OCO—, —CO—, —OCONH—, —S—, —CONH—, —OCOO—, —N = and the like can be mentioned. Of these, -O- and -OCO- are preferably used.

The photo radical generator may be a low molecule or a polymer.
Specific examples of the low molecular photoradical generator include acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine, and thioxanthone. A known radical generator can be used. Usually, sulfonium salts and iodonium salts used as photoacid generators also act as radical generators upon irradiation with light, and these may be used in the present invention.

  A sensitizer may be used in addition to the photo radical generator for the purpose of increasing sensitivity. Specific examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives. As the polymer photoradical generator, a polymer compound having an active carbonyl group in the side chain described in JP-A-9-77891 and JP-A-10-45927 can be used.

  The amount of the radical generator to be contained in the composition for forming the resin layer B is selected depending on the purpose, but is generally 0 to the total solid content contained in the composition for forming the resin layer B. About 40 mass% can be contained, it is preferable that it is 0.1-40 mass%, and it is more preferable that it is about 1-20 mass%.

(Formation of resin layer B)
As a method for forming the resin layer B, the substrate on which the resin layer A is formed may be immersed in a liquid composition containing a polymerizable compound, but handling properties, production efficiency, etc. If it considers, it is preferable to form by apply | coating a liquid composition.
Examples of the solvent used in the composition for forming the resin layer B include water, methanol, ethanol, propanol, alcohol solvents such as ethylene glycol, glycerin, and propylene glycol monomethyl ether, acids such as acetic acid, acetone, and cyclohexanone. Examples thereof include ketone solvents, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and acetonitrile.
The surfactant that can be added to the solvent as needed may be any that dissolves in the solvent. Examples of such surfactants include an anionic interface such as sodium n-dodecylbenzenesulfonate. Activators, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate ( Examples of commercially available products include non-ionic surfactants such as trade name “Tween 20” and polyoxyethylene lauryl ether.
In the case of forming a coating method, the coating amount is preferably from 0.1g ^{/ m 2} ~10g ^/ m 2 in terms of solid content, especially 0.5g ^{/ m 2} ~5g ^/ m 2 preferred.
The film thickness of the formed resin layer B is preferably in the range of 0.1 μm to 10 μm, more preferably 0.5 μm to 5 μm, from the viewpoint of plating.

(Energy provision)
By applying energy after the formation of the resin layer B, the radical generator contained in the resin layer B decomposes to generate radicals, which not only cure the resin layer B based on this, but also the action of the radicals. By reacting with the radical polymerizable compound contained in the resin layer A, the resin layer B adheres to the resin layer A with high strength. As a result, the resin layer B is firmly attached to the organic resin substrate via the resin layer A. Will adhere to.
Examples of the energy application method for improving the adhesion include heating and exposure to actinic rays.
Examples of the heating include a method of heating the laminated body of the organic resin substrate, the resin layer A, and the resin layer B with a contact or non-contact heat source, a method of conveying or arranging in the heating zone, and the like.
Examples of the contact heating include a method of contacting with a heating roll having a built-in heater, and examples of the non-contact heating include heating by an infrared heater, blowing of warm air, and placement in a high temperature atmosphere.
As heating conditions, it is preferable that it is about 5 to 60 minutes at 50 to 100 degreeC. Moreover, it is preferable that heating is performed from the resin layer B surface side from a viewpoint of adhesive improvement sensitivity and the thermal stability of an organic resin substrate.
In addition, when the resin layer B does not contain an initiator, a monomer or the like, it is necessary to increase the exposure amount and the heating temperature time.

When energy is applied by exposure to actinic rays, commonly used mercury lamps, metal halide lamps, xenon lamps, chemical lamps, carbon arc lamps, etc., light emitting diodes (LEDs), semiconductor lasers may be used. Alternatively, a light source such as a fluorescent lamp may be used. Further, a light source such as a hot cathode tube, a cold cathode tube, an electron beam or an X-ray, an electromagnetic wave, or the like can be used.
In the present invention, it is preferable to use a mercury lamp, LED, or semiconductor laser as the light source. The LED or semiconductor laser is characterized by its small size. In particular, LEDs have the advantages of long life, low calorific value, low power consumption, no generation of ozone, and immediate use when turned on.
A pattern can also be formed by light beam scanning exposure or pattern exposure using a mask.
Using these means, the resin layer B can be formed in a pattern on the entire surface of the resin layer A or in a desired region. It is preferable to use light for energy application from the viewpoint of ease of pattern formation during pattern formation and simple apparatus. In particular, when an exposure light source having a wavelength of 300 nm or less is used, a radical generator is not required, and good adhesion between the resin layer A and the resin layer B can be ensured.

According to the method of the present invention, since the energy application is preferably performed from the resin layer B side containing the radical generator, a compound capable of generating an initiation species in the vicinity of the exposed surface, particularly when applying light energy. It is considered that higher sensitivity can be achieved because it exists at a high density.
The energy required for improving the adhesion between the resin layer B and the organic resin substrate is appropriately selected according to the purpose through the resin layer A. However, in the embodiment of the present invention, a highly sensitive reaction is possible. , adhesion improving long 200mJ ^/ cm ² ~500mJ ^/ cm 2, about the surface of the resin layer B can be achieved.

  After completion of energy application, for the purpose of removing the unreacted low molecular weight polymerizable compound remaining in the resin layer B, washing with a solvent, for example, washing with water or alkaline water is preferably performed. In addition, when providing energy provision to pattern shape, it is necessary to wash | clean for the purpose of removing an unapplied part (residual compound etc. of the non-formation area | region of the resin layer B).

<(C) The process of providing an electroless plating catalyst or its precursor to the layer (resin layer B) which can adsorb | suck an electroless plating catalyst or its precursor>
An electroless plating catalyst or a precursor thereof is applied to the resin layer B thus formed, and then electroless plating is performed to form a conductive film. After the formation of the resin layer B, the electroless plating catalyst or a precursor thereof is brought into contact, whereby the electroless plating catalyst or the precursor thereof is adsorbed by the interaction to the interactive group present in the resin layer B.
(Electroless plating catalyst)
The electroless plating catalyst used in this step [(c) step] is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a method for fixing the zero-valent metal on the graft pattern (interactive region), for example, a functional group (interactive group) that interacts with the electroless plating catalyst (precursor) on the graft pattern, A technique is used in which a metal colloid whose charge is adjusted so as to interact is applied to the interactive region. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here. By interacting the metal colloid thus adjusted in charge with the interactive group of the graft pattern, Metal colloid (electroless plating catalyst) can be selectively adsorbed on the graft pattern.

(Electroless plating catalyst precursor)
The electroless plating catalyst precursor used in the step (c) can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion that is the electroless plating catalyst is applied to the base material, and before being immersed in the electroless plating bath, it may be changed to a zero-valent metal by a separate reduction reaction and used as an electroless plating catalyst. The precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

In fact, the metal ions that are electroless plating precursors are imparted to the graft pattern in the state of a metal salt and allowed to interact. The metal salt used is not particularly limited as long as it is dissolved in an appropriate solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ), M (OAc) _n (M represents an n-valent metal atom, and Ac represents an acetyl group). As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method for applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor onto a graft pattern, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is added with an appropriate solvent. A solution containing dissolved and dissociated metal ions is prepared, and the solution is applied to the surface of the substrate on which the graft pattern exists, or the substrate having the graft pattern is immersed in the solution. Contacting a solution containing a metal ion to adsorb a metal ion to the interacting group of the graft pattern forming region using an ion-ion interaction or a bipolar-ion interaction; or The interaction region can be impregnated with metal ions. From the viewpoint of sufficient adsorption or impregnation, the metal ion concentration or metal salt concentration of the solution to be contacted is preferably in the range of 1 to 50% by mass, and in the range of 10 to 30% by mass. Is more preferable.

(Organic solvent)
The plating catalyst liquid in the present invention contains an organic solvent. By containing this organic solvent, the permeability of the plating catalyst or its precursor metal to the resin layer B is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the interactive group of the resin increase B. Can do.
The solvent used in the preparation of the plating catalyst solution in this step is not particularly limited as long as it is a solvent that can penetrate the resin layer B, but water is generally used as the main solvent (dispersion medium) of the plating catalyst solution. Therefore, the water-soluble organic solvent described in detail below is preferable. However, in general, even a “non-aqueous” organic solvent is not limited to a water-soluble organic solvent as long as water is a main component, and is not limited to a water-soluble organic solvent as long as it dissolves in the solvent content range described below. Aqueous "organic solvents can also be used.

(Water-soluble organic solvent)
The water-soluble organic solvent used in the plating catalyst solution of the present invention is not particularly limited as long as it is a solvent that dissolves 1% by mass or more in water. Examples thereof include water-soluble organic solvents such as ketone solvents, ester solvents, alcohol solvents, ether solvents, amine solvents, thiol solvents, and halogen solvents.

Examples of the ketone solvent include acetone, 4-hydroxy-4-methyl-2-pentanone, γ-butyrolactone, and hydroxyacetone.
As ester solvents, ethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methyl cellosolve acetate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, glycolic acid Examples include methyl and ethyl glycolate.

  Examples of alcohol solvents include ethanol, isopropyl alcohol, normal propyl alcohol, 3-acetyl-1-propanol, 2- (allyloxy) ethanol, 2-aminoethanol, 2-amino-2-methyl-1-propanol, (±) 2-amino-1-propanol, 3-amino-1-propanol, 2-dimethylaminoethanol, 2,3-epoxy-1-propanol, ethylene glycol, 2-fluoroethanol, diacetone alcohol, 2-methylcyclohexanol 4-hydroxy-4-methyl-2-pentanone, glycerin, 2,2 ′, 2 ″ -nitrilotriethanol, 2-pyridinemethanol, 2,2,3,3-tetrafluoro-1-propanol, 2- ( 2-Aminoethoxy) ethanol, 2- [2- (benzyloxy) eth Si] ethanol, 2,3-butanediol, 2-butoxyethanol, 2,2′-thiodiethanol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-2 1,4-pentanediol, 1,3-propanediol, diglycerin, 2,2′-methyliminodiethanol, 1,2-pentanediol and the like.

  Examples of ether solvents include bis (2-ethoxyethyl) ether, bis [2- (2-hydroxyethoxy) ethyl] ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxy). Ethoxy) ethyl] ether, bis (2-methoxyethyl) ether, 2- (2-butoxyethoxy) ethanol, 2- [2- (2-chloroethoxy) ethoxy] ethanol, 2-ethoxyethanol, 2- (2- Ethoxyethoxy) ethanol, 2-isobutoxyethanol, 2- (2-isobutoxyethoxy) ethanol, 2-isopropoxyethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, 2- (2-methoxyethoxy ) Ethanol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol, tripropylene glycol monomethyl ether , Methoxyacetic acid, and 2-methoxy ethanol.

Examples of the glycol solvent include diethylene glycol, triethylene glycol, ethylene glycol, hexaethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
Examples of the amine solvent include N-methyl-2-pyrrolidone and N, N-dimethylformamide.
Examples of thiol solvents include mercaptoacetic acid and 2-mercaptoethanol.
Examples of the halogen solvent include 3-bromobenzyl alcohol, 2-chloroethanol, 3-chloro-1,2-propanediol and the like.
In addition, various organic solvents described in the following table can be used as the water-soluble organic solvent.

As other usable organic solvents, specifically, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl), propylene glycol diacetate, Triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve and the like can be used. In particular, acetone, dimethyl carbonate, and dimethyl cellosolve are also preferably used in combination from the viewpoint of compatibility with the plating catalyst or a precursor thereof and the hydrophobic cured product layer.
Other solvents that can be used in combination include diacetone alcohol, methyl cellosolve, ethyl cellosolve, ethylene glycol tertiary butyl ether, tetrahydrofuran, 1,4-dioxane, and n-methyl-2-pyrrolidone.
In addition, about the water-insoluble solvent contained in the example solvent mentioned above, it is permissible if it is mixed up to the solubility limit in water. For example, dimethyl carbonate can be mixed with water up to 12.5%, triacetin up to 7.2%, and cyclohexanone up to 9%.

  Among the water-soluble organic solvents described above, as one of the preferred embodiments, an organic solvent system that does not contain alcohol is a liquid storability as a catalyst solution from the viewpoint that there is less concern about oxidation by the catalyst metal. From the viewpoint, ketone solvents, ester solvents, and ether solvents are preferable. More specifically, acetone, dimethyl carbonate, ethylene glycol dimethyl ether, 2- (2-ethoxyethoxy) ethyl acetate, 1-acetoxy-2-methoxyethane, bis (2-ethoxyethyl) ether (also known as diethylene glycol diethyl ether) 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, bis (2-methoxyethyl) ether (other name: diethylene glycol dimethyl ether) and the like are preferable.

The content of the solvent is preferably 0.5% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass with respect to the total amount of the plating catalyst solution. It is particularly preferred.
Moreover, in the case of the water-soluble organic solvent which is a preferable embodiment, from the viewpoint of permeability to the object to be plated, which will be described later, 0.1% by mass to 40% by mass is preferable with respect to the total amount of the plating catalyst solution, and 5% by mass to 40 mass% is more preferable.
Although the content of the solvent is within the above range, the plating catalyst or its precursor permeates into the exposed substrate region (resin layer B non-formed region), and undesirable dissolution and erosion of the substrate are suppressed. Since the permeability and adsorbability of the catalyst solution into the resin layer B having catalyst acceptability are maintained, the plating metal is deposited not only on the surface layer but also inside the surface layer of the resin layer B. Good adhesion between the material and the metal interface is maintained.

The plating catalyst liquid according to the present invention may contain other additives depending on the purpose within a range not impairing the effects of the present invention, in addition to the plating catalyst or a precursor thereof and water as a main solvent.
Examples of other additives include those shown below.
For example, acids (organic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid and citric acid), swelling agents (such as organic compounds such as ketones, aldehydes, ethers and esters), and surfactants (anionic and cationic) , Zwitterionic, nonionic and low molecular or polymeric).

  The water that is an essential component of the plating catalyst solution in the present invention and is the main solvent preferably contains no impurities. From such a viewpoint, RO water, deionized water, distilled water, purified water, and the like are used. It is preferable to use deionized water or distilled water.

In order to adsorb the metal that is the plating catalyst or the metal salt that is the plating precursor to the resin layer B, the catalyst solution according to the present invention is prepared, and the catalyst solution is formed into the resin layer B]. What is necessary is just to apply | coat to the board | substrate surface or to immerse this board | substrate in a catalyst liquid.
The immersion time is preferably about 1 minute to 24 hours, and more preferably about 5 minutes to 1 hour.
In this way, the electroless plating catalyst or its precursor is adsorbed on the resin layer B in the step (c).

<(D) Step of performing electroless plating to form an electroless plating film>
After the electroless plating catalyst (precursor) is adsorbed on the resin layer B, electroless plating is performed, whereby a high-density metal film is formed on the resin layer B obtained in the previous step (b). A membrane is obtained. As a result, the formed conductive film has excellent conductivity and high adhesion to the resin layer B.

(Electroless plating)
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating in this step is performed by, for example, washing the substrate provided with the electroless plating catalyst in a pattern to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. . As the electroless plating bath to be used, a generally known electroless plating bath can be used.

  In addition, when the substrate to which the electroless plating catalyst is applied in a pattern is immersed in the electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the graft pattern, the substrate is washed with excess water. After removing the electroless plating catalyst precursor (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used in this embodiment, a generally known electroless plating bath can be used as described above.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath, and copper and gold are particularly preferable from the viewpoint of conductivity.
In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless plating bath contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, and sodium succinate as complexing agents. It is included. In addition, the palladium electroless plating bath contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

The film thickness of the metal film thus formed can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, etc. Is preferably 0.5 μm or more, more preferably 3 μm or more.
Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.
Thus, a conductive film is formed by electroless plating in the step (d). In this conductive film, an electroless plating catalyst or a precursor thereof that forms a conductive film is firmly adsorbed with an interactive group in the resin constituting the resin layer B, and the resin layer B is an adjacent resin layer. Since it is chemically bonded to the organic resin substrate via A, the formed conductive film has excellent adhesion to the organic resin substrate.

(Electroplating)
In the method for forming a conductive film of the present invention, an electroplating treatment can be further performed as desired after the electroless plating step (d).
That is, when a conductive film is formed using electroless plating, electroplating can be further performed using the formed metal film as an electrode. As a result, a metal film having an arbitrary thickness can be easily formed on the metal film pattern having excellent adhesion to the substrate. By adding this step, the conductive film (metal film) can be formed with a thickness according to the purpose, so that a conductive pattern having desired characteristics can be formed.
A conventionally known method can be used as the electroplating method in the present invention. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is preferable. More preferred.

The film thickness of the metal film obtained by electroplating varies depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath, the dipping time, or the current density. In addition, from the viewpoint of conductivity, the film thickness when used for general electric wiring or the like is preferably 0.3 μm or more, and more preferably 3 μm or more.
According to the method for forming a conductive film of the present invention, a conductive film having excellent adhesion to the substrate is chemically bonded to the entire surface of the organic resin substrate via the resin layer B and the resin layer A. For this reason, the adhesion strength of the conductive film shows a practically sufficient value even when the smoothness of the insulating substrate is high.

<Method for manufacturing printed wiring board>
As described above, the wiring of the printed wiring board can be easily formed by patterning the conductive film obtained by the conductive film forming method of the present invention by a known method. The wiring obtained by the method for producing a printed wiring board of the present invention also has an advantage of excellent adhesion to a smooth organic resin substrate.
Hereinafter, a patterning method for forming the wiring of the printed wiring board will be described.

(Etching process)
This step is a step of etching the conductive film (plating film) formed by the conductive film forming method of the present invention into a pattern.
In the method for producing a printed wiring board of the present invention, when the conductive film is formed on the entire surface of the substrate surface by the conductive film formation method, the “electroless plating catalyst application step: (c) step”, “ Electroless plating process: (d) process "and" electroplating process "carried out in this order are performed in this order, then this process is performed, and unnecessary portions of the plating film are removed by etching. A conductive layer to be a metal wiring portion can be formed.
Any method can be used for this etching step, and specifically, generally known subtractive methods and semi-additive methods are used.

  With the subtractive method, a dry film resist layer is provided on the formed plating film, the same pattern as the metal pattern part is formed by pattern exposure and development, the plating film is removed with an etching solution using the dry film resist pattern as a mask, This is a method of forming a metal pattern. Any material can be used as the dry film resist, and negative, positive, liquid, and film-like ones can be used. Moreover, as an etching method, any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, a wet etching apparatus or the like is simple and preferable. As an etching solution, for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.

  The semi-additive method is to provide a dry film resist layer on the formed plating film, form the same pattern as the non-metallic pattern part by pattern exposure and development, and perform electroplating using the dry film resist pattern as a mask. In this method, quick etching is performed after removing the dry film resist pattern, and the plating film is removed in a pattern to form a metal pattern. The dry film resist, etching solution, etc. can use the same material as the subtractive method. As the electroplating technique, the technique described above can be used.

  In addition, if the resin layer B is cured and applied with a pattern to develop a pattern, a resin layer B having a pattern-receiving property is formed on the surface of the resin layer A, and electroless plating is performed thereon. The conductive film (conductive pattern) on the pattern can be formed without an etching step.

<Printed wiring board>
A printed wiring board is obtained through the above steps.
As described above, the printed wiring board obtained by the manufacturing method of the present invention has a plating film having a desired film thickness formed by a plating process, and therefore an organic resin substrate for printed wiring or an interlayer made of an organic resin. The wiring has excellent adhesion and conductivity to the insulating film (intermediate layer), and is excellent in thermal reliability and electrical characteristics.
In particular, as will be described later, the use of an intermediate layer with small surface irregularities and high smoothness can further reduce electrical loss during high-frequency power transmission.

  The printed wiring board obtained by the production method of the present invention is provided with a plating film on an organic resin substrate having a surface irregularity (Rz) of 500 nm or less (more preferably 100 nm or less) through a resin layer A and a resin layer B. As described above, it is characterized by excellent adhesion, and the adhesion is preferably 0.6 kN / m or more.

The unevenness on the surface of the organic resin substrate can be measured by cutting the substrate perpendicular to the substrate surface and observing the cross section with an SEM.
According to the method for manufacturing a printed wiring board of the present invention, a multilayer printed wiring board is formed by build-up with an electric circuit board made of an organic resin layer or formed on a substrate including an organic resin layer or an insulating layer. You can also

<Conductive film material>
According to the manufacturing method of the present invention, a thermoplastic resin layer containing a compound having a radical polymerizable group on an organic resin substrate, a resin layer containing an electroless plating catalyst or a precursor thereof, and a conductive film. A conductive film material having excellent adhesion between the base material and the conductive film can be obtained. The conductive film material obtained by the manufacturing method of the present invention is formed by forming a conductive film having excellent adhesion on a smooth organic resin substrate, and is useful for manufacturing printed wiring boards and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to these.

[Synthesis Example 1: Synthesis of specific polymerizable polymer]
A 500 ml three-necked flask was charged with 14 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. The following monomer: 42 g, V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.32 g of an N, N-dimethylacetamide 14 g solution was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 141 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature (20 ° C.).

  4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.28g and DBU60.9g were added to said reaction solution, and reaction was performed at room temperature for 4 hours. Then, 60.4 g of 70 mass% methanesulfonic acid aqueous solution was added to the reaction liquid. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was taken out to obtain 30 g of a specific polymerizable polymer (weight average molecular weight 74,000).

[Synthesis Example 2: Synthesis of polymer for resin layer B]
A 500 ml three-necked flask was charged with 48 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. Thereto, the following monomer M: 49.6 g, 2-cyanoethyl acrylate (manufactured by Tokyo Chemical Industry) 60.1 g, acrylic acid (manufactured by Tokyo Chemical Industry) 64.6 g, V-65 (manufactured by Wako Pure Chemical Industries) 2.4 g of N, A 48 g solution of N-dimethylacetamide was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 240 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature (20 ° C.).

  To the above reaction solution, 0.41 g of 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry) and 182.2 g of triethylamine were added and reacted at room temperature for 4 hours. Then, 272 g of 70 mass% methanesulfonic acid aqueous solution was added to the reaction liquid. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 100 g of polymer for resin layer B (weight average molecular weight 18,000) was obtained. The acid value of this resin layer B polymer was 3.9 mmol / g.

[Example 1]
[Preparation of resin layer A]
A resin composition for forming the resin layer A is prepared on a glass epoxy substrate, applied by spin coating (conditions: 5 seconds at 250 rpm, and then 20 seconds at 750 rpm), and dried to a thickness of 1.2 μm. A substrate provided with the resin layer A was obtained.

(Resin composition for forming resin layer A)
・ ABS resin (manufactured by Aldrich, thermoplastic resin) 9g
Specific polymerizable polymer (obtained in Synthesis Example 1) 1g
・ Cyclohexane 91g

[Application of acrylic resin composition layer (resin layer B)]
On the surface of the thermoplastic resin layer (resin layer A) obtained as described above, an acrylic resin composition 1 having the following composition was applied by a spin coater and dried at 50 ° C. for 5 minutes to obtain a 1 μm-thick resin layer (none An acrylic resin layer containing a functional group that adsorbs an electroplating catalyst or its precursor and a radical polymerizable group in the molecule) was applied.

<Acrylic resin composition 1>
-Resin layer B polymer (obtained in Synthesis Example 2, Mw: 74,000) 10 parts by mass-Water 90 parts by mass-Acetonitrile (manufactured by Wako Pure Chemical Industries) 90 parts by mass

[Energy application (formation of resin layer B and bond formation between resin layer A and resin layer B)]
A UV exposure machine (model number: manufactured by Mitsunaga Electric, model number: UVF-502S, lamp: UXM-) is applied to the surface of the resin layer B in the laminate of the organic resin substrate, the resin layer A, and the resin layer B thus obtained. 501MD), and exposure was performed for 300 seconds with an irradiation power of 10 mW / cm ² (measurement of irradiation power with an UV integrated light meter UIT150—light receiving sensor UVD-S254 manufactured by USHIO INC.).
The substrate after the exposure was immersed in a 1% by mass Na ₂ CO ₃ aqueous solution for 5 minutes, and then washed with distilled water. (The polymer of Synthesis Example 2 contains acid groups and can be washed with water)
This obtained the board | substrate which has the whole surface resin layer B (plating reception layer).

[Application of electroless plating catalyst: step (c)]
The obtained laminate was immersed in a 10% by mass aqueous solution of silver nitrate for 10 minutes, and then immersed in distilled water and washed.
[Formation of electroless plating layer: step (d)]
Thereafter, the laminate having the electroless plating catalyst adsorbed was subjected to electroless plating at 30 ° C. for 10 minutes in an electroless plating bath having the following composition to obtain a laminate having the conductor film of Example 1. The thickness of the obtained electroless copper plating film was 0.1 μm. For the preparation of the plating solution, OPC Copper T manufactured by Okuno Pharmaceutical Co., Ltd. was used.

(Composition of electroless plating bath)
・ Distilled water 926g
・ OPC T1 66ml
・ OPC T3 110ml
・ Formaldehyde (35%) 10.7g
Electroless plating bath pH: 12.5

(Electrolytic plating)
Subsequently, in order to measure the peel strength, electrolytic plating was performed for 20 minutes at a current density of 3 A / dm ² in an electrolytic plating bath having the following composition to form an electrolytic copper plating layer having a thickness of 8 μm, and at 90 ° C. for 60 minutes. After baking.
<Composition of electrolytic plating bath>
・ Distilled water 500g
・ Copper sulfate 38g
・ 95 g concentrated sulfuric acid
-Hydrochloric acid 1mL
・ Kappa-Gream PCM (Meltex Co., Ltd.) 3mL

[Performance evaluation 1: Adhesion evaluation]
When a cross-cut test (JIS-K5600) was performed on the plating film obtained in Example 1, no peeling of 1 out of 100 was observed (0/100).
Next, five reciprocating heat cycle tests were performed between 0 ° C. and 110 ° C. for the plated film obtained in Example 1. After the test, a cross-cut test (JIS-K5600) was performed on the plated film, and one of 100 peels was not observed (0/100)

[Example 2]
After obtaining a patterned resin layer B using a photomask at the time of exposure in Example 1, only electroless plating was performed. As a result, a conductive film was formed in the region where the resin layer B was formed. Two conductive patterns were obtained.

[Performance evaluation 2: Evaluation of adhesion]
When a cross-cut test (JIS-K5600) was performed on the conductive pattern obtained in Example 2, one peeling out of 100 was not observed (0/100).
Next, the plating film obtained in Example 1 was subjected to a 5-reciprocal heat cycle test (between 0 ° C. and 110 ° C. After the test, a cross-cut test (JIS-K5600) was performed on the plating film. However, one peeling out of 100 eyes was not observed (0/100).

Example 3
A plating film 3 was obtained in the same manner as in Example 1 except that the acrylic resin composition 1 used in Example 1 was changed to the acrylic resin composition 2 shown below and the exposure time was changed to 200 seconds.

<Acrylic resin composition 2>
-Polymer for resin layer B (obtained in Synthesis Example 2, Mw: 74,000) 10 parts by mass-IRG907 (radical generator: manufactured by Ciba Specialty Chemicals) 1 part by mass ethylene diacrylate (radical polymerizable compound) 5 90 parts by mass of water, 90 parts by mass of water, acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.)

[Performance evaluation 3: Evaluation of adhesion]
When a cross-cut test (JIS-K5600) was performed on the conductive film (metal film) obtained in Example 3, one of 100 peels was not observed (0/100).
Next, the plating film obtained in Example 3 was subjected to a 5 reciprocating heat cycle test (between 0 ° C. and 110 ° C. After the test, a cross cut test (JIS-K5600) was performed on the plating film. However, one peeling out of 100 eyes was not observed (0/100).
As is clear from Examples 1 to 3, it can be seen that the conductive film obtained by the production method of the present invention is excellent in adhesion to the substrate even under severe conditions such as a heat cycle test.

Claims (8)

  (A) a step of forming a resin layer (resin layer A) comprising a compound having a radical polymerizable group and a thermoplastic resin on an organic resin substrate; (b) an electroless plating catalyst or a precursor thereof. Forming a resin layer (resin layer B) capable of adsorbing an electroless plating catalyst or a precursor thereof containing a resin having a functional group that interacts with the body and a compound having a radical polymerizable group; A step of applying an electroless plating catalyst or a precursor thereof to a layer (resin layer B) capable of adsorbing an electroplating catalyst or a precursor thereof; and (d) electroless plating to form an electroless plating film. A method for forming a conductive film.   The method for forming a conductive film according to claim 1, wherein the resin layer B further contains a radical generator.   The method for forming a conductive film according to claim 1, wherein the compound having a radical polymerizable group has a weight average molecular weight of 5,000 or more and 200,000 or less. The resin layer (resin layer B) capable of adsorbing the electroless plating catalyst or its precursor contains a resin having a functional group that interacts with the electroless plating catalyst or its precursor formed on the resin layer A. 4. The resin layer according to claim 1, which is a resin layer formed by applying energy to the resin composition layer and chemically bonding the resin composition layer with the adjacent resin layer A. 5. Of forming the conductive film.   The thermoplastic resin is made of polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ABS resin, acrylonitrile / styrene copolymer, acrylic resin, polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene terephthalate, and polyethylene terephthalate. The method for forming a conductive film according to claim 1, wherein the conductive film is one or more selected from the group.   The functional group that adsorbs the electroless plating catalyst or its precursor is a cyano group, a substituted or unsubstituted amino group, or a substituted or unsubstituted nitrogen-containing heterocyclic group. The formation method of the electrically conductive film as described in any one of.   The manufacturing method of the printed wiring board containing the formation method of the electrically conductive film of any one of Claims 1-6. On the organic resin substrate,
A thermoplastic resin layer containing a compound having a radical polymerizable group;
A resin layer containing an electroless plating catalyst or a precursor thereof;
A conductive film;
In this order.