JP2012097296A - Method of forming metal film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of forming a metal film, by which the metal film exhibiting excellent adhesiveness to a substrate even when exposed to environment of high temperatures and high humidities can be easily formed, without need of a large amount of energy.SOLUTION: The method of forming the metal film includes steps of: (1) forming a first resin layer containing a resin with a cyano group and having a cyano group content of 7.4 mmol/g or more on the substrate; (2) forming a resin composition layer on the first resin layer, wherein the resin composition layer contains a resin having a polymerizable group and a functional group that interacts with a plating catalyst or a precursor thereof, and a polymerization initiator; (3) forming a second resin layer by applying energy to the resin composition layer and by curing the layer; (4) applying the plating catalyst or the precursor to the second resin layer; and (5) forming a metal film on the second resin layer by performing plating.

Description

  The present invention relates to a metal film 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 image is peeled off.

  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 was also a problem that a complicated process was required.

  As a means for solving this problem, a method for solving the above problem by using a polymer having a cyano group in the side chain as a primer layer has been proposed (Patent Document 1).

JP 2010-84196 A

On the other hand, in recent years, a semiconductor element provided with a metal wiring board is assumed to be used under more severe high temperature and high humidity conditions, and a metal film exhibiting sufficient adhesion even when exposed to such an environment. Development was desired.
The present inventors have used the primer layer specifically disclosed in the example of Patent Document 1 to adhere the metal film after being exposed to more severe high-temperature and high-humidity conditions as required recently. The sex was examined. As a result, it has been found that the adhesion of the formed metal film is remarkably deteriorated and is not always satisfactory in practical use.

Moreover, in patent document 1, after apply | coating the polymer which has a functional group and a polymeric group which interact with an electroless-plating catalyst or its precursor, a polymer layer is formed, UV exposure of short wavelength lights, such as 254 nm, The adhesion between the polymer layer and the primer layer is improved.
On the other hand, in order to perform such short wavelength UV exposure, a large apparatus is required, resulting in an increase in manufacturing cost. Furthermore, UV exposure has a problem in terms of work safety, and development of a mode in which a desired effect can be obtained by low energy irradiation using longer wavelength light has been demanded.

This invention is made | formed in view of the said situation, and makes it a subject to achieve the following objectives.
An object of the present invention is to provide a metal film forming method that can be produced without requiring a large amount of energy and can easily form a metal film that exhibits excellent adhesion to a substrate even when exposed to a high temperature and high humidity environment. It is to provide.

As a result of intensive studies on the cause of the deterioration of the adhesion of the metal film in the above prior art, the inventors have found that the adhesion between the primer layer and the polymer layer existing between the substrate and the metal film is high and high. It was found that it deteriorates in a wet environment.
Based on the above findings, the present inventors have found that the above object can be achieved by the following means.

<1> forming a first resin layer containing a cyano group-containing resin and having a cyano group content of 7.4 mmol / g or more on the substrate;
A step (2) of forming on the first resin layer a resin composition layer containing a polymerization group and a resin having a polymerizable group and a functional group that interacts with a plating catalyst or a precursor thereof;
(3) forming a second resin layer by applying energy to the resin composition layer and curing the resin composition layer;
A step (4) of applying a plating catalyst or a precursor thereof to the second resin layer;
Performing a plating step to form a metal film on the second resin layer (5);
A metal film forming method comprising:

<2> In the resin composition layer, the polymerization initiator is contained in a range of 1 to 20% by mass with respect to the resin having a polymerizable group and a functional group that interacts with a plating catalyst or a precursor thereof. <1> The metal film formation method according to <1>.
<3> The metal film forming method according to <1> or <2>, wherein the polymerization initiator has an absorption peak wavelength in a range of 250 to 400 nm.

<4> The metal film forming method according to <1>, wherein the following step (6) is performed instead of the step (3).
Step (6): Applying pattern energy to the resin composition layer, curing the resin composition layer in the energy application region, and then developing and removing the non-energy application region to form a pattern-like second resin layer Process

<5> The metal film forming method according to any one of <1> to <4>, wherein the resin having a cyano group is a resin having a unit represented by the formula (1) described later.
<6> The resin having a cyano group is acrylonitrile-butadiene copolymer or polyacrylonitrile, and the resin having a functional group that interacts with the polymerizable group and the plating catalyst or its precursor is represented by the formula (A) described later. The metal film formation method in any one of <1>-<5> which is a copolymer containing the unit represented by Formula (B) and Formula (C).
<7> The metal film forming method according to any one of <1> to <6>, wherein the energy is applied by irradiating light having a wavelength of 300 nm or more.

  According to the present invention, there is provided a metal film forming method capable of easily forming a metal film that can be manufactured without requiring a large amount of energy and exhibits excellent adhesion to a substrate even when exposed to a high temperature and high humidity environment. Can be provided.

Below, the metal film formation method of this invention is demonstrated.
The feature of the present invention is that the first resin layer containing a predetermined amount or more of cyano groups is used, and the polymerization initiator is formed on the resin composition layer formed on the first resin layer. Is included. By taking such an embodiment, it is possible to obtain a metal film that exhibits excellent adhesion even when exposed to a high temperature and high humidity environment.

The metal film forming method of the present invention has the following five steps.
Step (1): Step of forming a first resin layer containing a cyano group-containing resin and having a cyano group content of 7.4 mmol / g or more on the substrate (2): On the first resin layer Step (3) of forming a resin composition layer containing a polymerization group and a resin having a polymerizable group and a functional group that interacts with a plating catalyst or a precursor thereof, and applying energy to the resin composition layer Step (4) for curing and forming a second resin layer: Step (5) for applying a plating catalyst or a precursor thereof to the second resin layer: Plating is performed on the second resin layer. Step of Forming Metal Film The procedure of each step and the materials used will be described in detail below.

<Step (1): First resin layer forming step>
In the step (1), a first resin layer containing a cyano group-containing resin (hereinafter, appropriately referred to as a cyano group-containing resin) and having a cyano group content of 7.4 mmol / g or more is formed on the substrate. . By including a predetermined amount of cyano group in the first resin layer, the wettability to the substrate and the affinity to the substrate are improved, and as a result, the first resin layer having excellent adhesion to the substrate. (Primer layer) can be formed. Moreover, since the 1st resin layer shows the outstanding compatibility also with the 2nd resin layer formed on it, the 2nd resin layer also shows the outstanding adhesiveness.
Below, the material used at this process and the procedure of a process are explained in full detail.

(Cyano group-containing resin)
First, the cyano group-containing resin contained in the first resin layer will be described.
The structure / kind of the cyano group-containing resin is not particularly limited as long as the cyano group content of the first resin layer satisfies the above range. Examples thereof include NBR (acrylonitrile butadiene rubber), PAN (polyacrylonitrile), AS (acrylonitrile styrene) and the like.
Especially, resin which has a cyano group in a side chain is preferable, and it is more preferable that it is resin which has a unit (repeating unit) represented by following formula (1).

In the above formula (1), R ^a represents a hydrogen atom or a substituted or unsubstituted alkyl group. When R ^a is a substituted or unsubstituted alkyl group, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the substituted alkyl group include a methoxy group and a hydroxy group. , A methyl group, an ethyl group, a propyl group, and a butyl group substituted with a chlorine atom, a bromine atom, or a fluorine atom.
R ^a is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.

In the formula (1), L ^a represents a single bond, or a substituted or unsubstituted divalent organic group. The organic group represented by L ^a, for example, a substituted or unsubstituted aliphatic hydrocarbon group (preferably having from 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably 6 carbon atoms 12), - O -, - S -, - SO 2 -, - N (R) - (R: alkyl group), - CO -, - NH -, - COO -, - CONH-, or a combination thereof Groups (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).
Examples of the substituted or unsubstituted aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, or a butylene group, or a group that includes a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, or a fluorine atom. Substituted ones are preferred.
As the substituted or unsubstituted aromatic hydrocarbon group, an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like is preferable.
Among these, as La, ^a single bond is more preferable.

  The cyano group-containing resin may contain two or more units represented by the formula (1).

Other units (repeating units) contained in the cyano group-containing resin are not particularly limited. For example, a unit derived from a linear or cyclic olefin compound (for example, ethylene or propylene) or a unit derived from a conjugated diene compound A unit derived from an aromatic vinyl compound having no polar group, a unit derived from a (meth) acrylate monomer having no polar group, or a unit derived from a (meth) acrylamide monomer having no polar group is preferred.
Specific examples include units derived from monomers as shown below. In the following formulae, R represents a hydrogen atom or a methyl group, and X represents O or NH.

Among these, from the viewpoint of cost and film property control, preferred examples of other units include units derived from conjugated diene compounds and units derived from aromatic vinyl compounds.
Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, α-chlorostyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-amino. Examples include ethyl styrene, vinyl pyridine, N, N-diethyl-p-aminostyrene and the like.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, Examples include 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and the like.

  The content of the cyano group in the cyano group-containing resin is not particularly limited as long as the first resin layer falls within the above-described range, but it is usually preferably 7.4 mmol / g or more. The upper limit is not particularly limited, but is preferably 20 mmol / g or less, more preferably 18 mmol / g or less, and most preferably 13 mmol / g or less from the viewpoint of electrical insulation. The lower limit is not particularly limited as long as it is within the above-described range, but is preferably 7.5 mmol / g or more and more preferably 8 mmol / g or more in terms of more excellent heat resistance.

  When the unit represented by the formula (1) is included in the cyano group-containing resin, the content thereof is preferably in the range of 10 to 100 mol% with respect to all units (repeating units) in the resin. More preferably, it is 30-100 mol%.

The weight average molecular weight of the cyano group-containing resin is not particularly limited, but is preferably 1000 or more and 700,000 or less, and more preferably 2000 or more and 200,000 or less. In particular, it is preferably 10,000 or more from the viewpoint of adhesion to the substrate.
The degree of polymerization of the cyano group-containing resin is not particularly limited, but it is preferable to use a 10-mer or more, more preferably a 20-mer or more. Moreover, 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.

(Method for forming first resin layer)
The first resin layer can be formed by applying a known layer forming method, for example, a method of laminating the above-described cyano group-containing resin on a substrate, a composition containing a cyano group-containing resin (hereinafter referred to as a first layer). No. 1 resin layer composition) is applied on a substrate.
From the viewpoint of work, the above coating method is preferable. As a coating method, a known method can be used, and examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. For example, when a volatile component is not blended in the first resin layer composition, a die coating method, a spin coating method, or a screen printing method is preferable. In the case of the 1st composition for resin layers which mix | blended volatile components, such as a solvent, it hardens | cures after removing a volatile component by heating etc. before hardening.

In the application method, a solvent may be added to the first resin layer composition. Examples of the solvent that can be used include water, methanol, ethanol, propanol, ethylene glycol, glycerin, alcohol solvents such as propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, formamide, Amide solvents such as dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, tetrahydrofuran (THF) , Ether solvents such as 1,4-dioxane, acetal solvents such as 1,3-dioxolane, and the like.
Among these, amide solvents, ketone solvents, nitrile solvents, carbonate solvents, ether solvents, and acetal solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N -Methylpyrrolidone, dimethyl carbonate, THF, 1,3-dioxolane are preferred.
Moreover, when apply | coating the 1st composition for resin layers, the solvent whose boiling point is 50-150 degreeC is preferable from handling ease. In addition, these solvents may be used alone or in combination.

  Moreover, you may add additives, such as surfactant and a plasticizer, to the 1st composition for resin layers.

When the first resin layer composition is applied on the substrate and dried to form the first resin layer, the drying conditions are in the range of 50 ° C. to 220 ° C. for 1 minute to 5 hours. Is preferable, and it is more preferable that it is the range of 50 to 180 degreeC.
The coating amount of the first resin layer composition is preferably 0.1 to 10 g / m ^{2 in} terms of solid content, particularly 0.5, in terms of adhesion to the substrate and obtaining a uniform coating film. ˜5 g / m ² is preferred.
The first resin layer may be formed by a printing method (for example, gravure printing method, screen printing method, flexographic printing method, ink jet printing method, imprinting method) or a developing method (for example, wet etching, dry etching, ablation). Further, it may be formed into a pattern using a method such as curing and plasticizing with light (negative type / positive type).

(substrate)
The substrate used in this step is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), metal plate (for example, Aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polyvinyl acetal, polyimide, epoxy, (Bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), paper or plastic film on which a metal as described above is laminated or vapor-deposited.

  Moreover, the laminated body obtained by the metal film forming method of the present invention can be applied to semiconductor packages, various electric wiring boards and the like. When used for such applications, the following substrate containing an insulating resin, specifically, a substrate made of an insulating resin, or a substrate having a layer made of an insulating resin on an appropriate support surface Is preferably used.

When obtaining a substrate made of an insulating resin or a layer made of an insulating resin, a known insulating resin composition is used. In addition to the main resin, various additives can be used in combination with the insulating resin composition depending on the purpose. For example, for the purpose of increasing the strength of the insulating layer, a polyfunctional acrylate monomer is added, or for the purpose of increasing the strength of the insulating layer and improving electrical characteristics, inorganic or organic particles are added. You can also
In addition, the “insulating resin” in the present invention means a resin having an insulating property that can be used for a known insulating film or insulating layer, and is not a perfect insulator. In addition, any resin having insulating properties according to the purpose can be applied to the present invention.

Specific examples of the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. Examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, and a bismaleimide. Examples thereof include resins, polyolefin resins, isocyanate resins and the like.
Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.

  Further, the insulating resin composition may be filled with a filler (for example, silica, alumina, clay, talc, etc.), a colorant, a flame retardant, an adhesion imparting agent, a silane coupling agent, an antioxidant, if necessary. You may add 1 type, or 2 or more types of various additives, such as a ultraviolet absorber.

(First resin layer)
The first resin layer formed in this step contains the cyano group-containing resin described above.
The content of the cyano group-containing resin in the first resin layer is not particularly limited, but is 50 to 100% by mass with respect to the total amount of the first resin layer in terms of better adhesion to the second resin layer. Is preferable, and 75-100 mass% is more preferable.

The amount of cyano group (cyano group content) contained in the first resin layer is 7.4 mmol / g or more. By being in the above range, the above effect can be obtained. The upper limit is not particularly limited, but is preferably 20 mmol / g or less, more preferably 18 mmol / g or less, and most preferably 13 mmol / g or less from the viewpoint of electrical insulation. Among these, from the viewpoints of adhesion, electrical insulation, elastic modulus and the like, the content of the cyano group is preferably 7.5 to 18 mmol / g, and more preferably 8.0 to 13 mmol / g.
When the content of the cyano group is less than 7.4 mmol / g, the adhesion with the second resin layer described later is inferior, and as a result, the adhesion between the metal film provided on the surface and the substrate is inferior.
The cyano group content can be measured using a known measuring instrument (for example, NMR).

The first resin layer may contain other resins in addition to the cyano group-containing resin.
Examples of the other resin include epoxy resin, phenol resin, polyimide resin, polyester resin, bismaleimide resin, polyolefin resin, isocyanate resin, butadiene-styrene copolymer resin, and the like.

  The thickness of the first resin layer is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.1 to 6 μm, from the viewpoint of adhesion to the second resin layer described later and stress relaxation. Most preferred is ˜6 μm.

<Step (2): resin composition layer forming step>
In step (2), on the first resin layer obtained in step (1), a resin having a polymerizable group, a functional group that interacts with the plating catalyst or its precursor, and a polymerization initiator. A resin composition layer is formed.
First, materials (resin and polymerization initiator) used in this step will be described, and then the procedure of this step will be described.

(Resin having a polymerizable group and a functional group that interacts with the plating catalyst or its precursor)
The resin used in this step (hereinafter referred to as “resin A” as appropriate) has a polymerizable group and a functional group that interacts with the plating catalyst or its precursor (hereinafter referred to as “interactive group” as appropriate).

(Polymerizable group)
The polymerizable group is a functional group capable of forming a bond between the resins A or between the resin A and the first resin layer by applying energy in the step (3) to be described later. Group, cationically polymerizable group and the like. Of these, a radical polymerizable group is preferable from the viewpoint of reactivity. Examples of the radical polymerizable group include unsaturated carboxylic acid ester groups such as acrylic acid ester groups, methacrylic acid ester groups, itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, styryl groups, Examples thereof include a vinyl group, an acrylamide group, and a methacrylamide group. Among these, a methacrylic acid ester group (methacryloyl group), an acrylic acid ester group (acryloyl group), a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and an acryloyl group, a methacryloyl group, and a styryl group are particularly preferable.

(Interactive group)
The interactive group is a functional group that interacts with a plating catalyst or a precursor thereof described later, a functional group that can form an electrostatic interaction with a metal ion, or a nitrogen-containing function that can form a coordination with a metal ion. Groups, sulfur-containing functional groups, oxygen-containing functional groups and the like can be used.
Examples of interactive groups include non-dissociable functional groups (functional groups that do not generate protons by dissociation).
More specifically, as an interactive group, amino group, amide group, imide group, urea group, tertiary amino group, ammonium group, amidino group, triazine ring, triazole ring, benzotriazole group, imidazole group, benzimidazole Group, quinoline group, pyridine group, pyrimidine group, pyrazine group, nazoline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, isocyanuric structure Nitro group, nitroso group, azo group, diazo group, azide group, cyano group, nitrogenate functional group such as cyanate group (R—O—CN); ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, Carbonate group, carbonyl group, ester group, group containing N-oxide structure, S Oxygen-containing functional groups such as a group containing an oxide structure and a group containing an N-hydroxy structure; Sulfur-containing functional groups such as sulfone group, sulfite group, group containing sulfoxyimine structure, group containing sulfoxynium salt structure, sulfonic acid group, group containing sulfonic acid ester structure; Phosphate group, phosphoramide group, phosphine group And a phosphorus-containing functional group such as a group containing a phosphate ester structure; a group containing a halogen atom such as chlorine and bromine, and the like. In a functional group capable of taking a salt structure, a salt thereof can also be used.
Among them, an ionic polar group (for example, a carboxyl group), an ether group, or a cyano group is particularly preferable because of its high polarity and high adsorption ability to a plating catalyst or a precursor thereof. Further preferred.
In addition, a functional group derived from a compound having an inclusion ability can also be used as the interactive group. For example, a functional group containing a cyclodextrin, a crown ether, a cyclic polyamine or the like as a partial structure can be introduced.
Two or more of these functional groups as the interactive group may be contained in the resin.

In addition, as said ether group, the polyoxyalkylene group represented by the following formula | equation (X) is preferable.
Formula (X) *-(YO) _n -R ^c
In formula (X), Y represents an alkylene group, and R ^c represents an alkyl group. n represents a number from 1 to 30. * Represents a bonding position.
As an alkylene group, C1-C3 is preferable and, specifically, an ethylene group and a propylene group are mentioned preferably.
As an alkyl group, C1-C10 is preferable and a methyl group and an ethyl group are mentioned preferably specifically ,.
n represents the number of 1-30, Preferably it is 3-23. In addition, n represents an average value, and the numerical value can be measured by a known method (NMR) or the like.

The weight average molecular weight of the resin A is not particularly limited, but is preferably 1000 or more and 700,000 or less, and more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
Further, the degree of polymerization of the resin A is not particularly limited, but it is preferable to use a 10-mer or more, more preferably a 20-mer or more. Moreover, 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.

(Preferred embodiment 1)
As a first preferred embodiment of the resin A, a unit having a polymerizable group represented by the following formula (a) (hereinafter also referred to as a polymerizable group unit as appropriate) and an interaction represented by the following formula (b) Examples thereof include a copolymer containing a unit having a functional group (hereinafter also referred to as an interactive group unit as appropriate). In addition, a unit means a repeating unit.

In the above formula (a) and formula (b), R ^{1 to} R ⁵ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
When R ^{1 to} R ⁵ are a substituted or unsubstituted alkyl group, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, or a butyl group. Examples of the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, or a fluorine atom.
R ¹ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
R ² is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.

In the above formulas (a) and (b), X, Y, and Z each independently represent a single bond, a substituted or unsubstituted divalent organic group. As a definition of ^a divalent organic group, it is synonymous with the divalent organic group described by La in Formula (1) mentioned above.

  X, Y, and Z are preferably a single bond, an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or a substituted or unsubstituted aromatic hydrocarbon group. More preferred are a single bond, an ester group (—COO—), and an amide group (—CONH—).

In the above formulas (a) and (b), L ¹ and L ² each independently represent a single bond or a substituted or unsubstituted divalent organic group. As a definition of ^a divalent organic group, it is synonymous with the divalent organic group described by La in Formula (1) mentioned above.
L ¹ is preferably a single bond or a divalent organic group having a urethane bond or a urea bond, more preferably a divalent organic group having a urethane bond, and among them, those having 1 to 9 carbon atoms in total. preferable. Incidentally, the total number of carbon atoms of L ^1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^1.
More specifically, the structure of L ¹ is preferably a structure represented by the following formula (1-1) or formula (1-2).

In the above formulas (1-1) and (1-2), R ^a and R ^b each independently represent two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. It is a divalent organic group formed by using. Preferably, it is a substituted or unsubstituted methylene group, ethylene group, propylene group, or butylene group, or ethylene oxide group, diethylene oxide group, triethylene oxide group, tetraethylene oxide group, dipropylene oxide group, tripropylene oxide group, tetra A propylene oxide group is mentioned.

L ² is preferably a single bond, a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L ² is a single bond, or, preferably has a total carbon number of 1 to 15, particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L ^2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^2.
Specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, or a group in which these groups are substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like, or a combination thereof. Group.

  In said formula (b), W represents the functional group which interacts with a plating catalyst or its precursor. The definition of the functional group is as described above.

  A preferred embodiment of the polymerizable group unit represented by the above formula (a) includes a unit represented by the following formula (c).

In the formula (c), R ¹ , R ² , Z and L ¹ are the same as the definitions of each group in the unit represented by the formula (a). A represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).

  A preferred embodiment of the unit represented by the formula (c) is a unit represented by the formula (d).

In the formula (d), R ¹ , R ² , and L ¹ are the same as the definitions of each group in the unit represented by the formula (a). A and T each represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).

In the above formula (d), T is preferably an oxygen atom.
In the above formulas (c) and (d), L ¹ is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and a divalent organic group having a urethane bond. Are more preferable, and those having 1 to 9 carbon atoms are particularly preferable.

  Moreover, the unit represented by the following formula (e) is mentioned as one of the suitable aspects of the interactive group unit represented by Formula (b).

In the above formula (e), R ⁵ and L ² are the same as the definition of each group in the unit represented by the formula (b). Q represents an oxygen atom or NR ′ (R ′ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
L ² in the formula (e) is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these.
In particular, in the formula (e), it is preferable that the linking site with the interactive group in L ² is a divalent organic group having a linear, branched, or cyclic alkylene group. The valent organic group preferably has 1 to 10 carbon atoms in total.
As another preferred embodiment, the connecting portion between the interactive group in L ² in Formula (e) is preferably a divalent organic group having an aromatic group, among others, of the divalent The organic group preferably has 6 to 15 carbon atoms in total.

The polymerizable group unit is preferably contained in an amount of 5 to 50 mol%, more preferably 5 to 40 mol%, based on all units in the resin. If it is 5 mol% or less, the reactivity (curability, polymerizability) may be lowered, and if it is 50 mol% or more, gelation tends to occur during synthesis and synthesis is difficult.
The interactive group unit is preferably contained in an amount of 5 to 95 mol%, more preferably 10 to 95 mol%, with respect to all units in the resin, from the viewpoint of adsorptivity to a plating catalyst or the like. is there.

(Preferred embodiment 2)
As a 2nd preferable aspect of resin A, in addition to an interactive group and a polymeric group, resin which has an ionic polar group is mentioned, More specifically, following formula (A), formula (B And a copolymer containing a unit represented by the formula (C).

The unit represented by the formula (A) is the same as the unit represented by the above formula (a), and the explanation of each group is also the same.
R ^5, X and L ² in the unit represented by formula (B) is the same as R ^5, X and L ² in the unit represented by the above formula (b), same explanation of each group It is.
Wa in the formula (B) represents a functional group that interacts with the plating catalyst or its precursor, excluding an ionic polar group represented by V described later.

In formula (C), each R ⁶ independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. The definition of an alkyl group is synonymous with the alkyl group represented by R < ¹ > -R < ⁵ > mentioned above.
In formula (C), U represents a single bond or a substituted or unsubstituted divalent organic group. The definition of a bivalent organic group is synonymous with the divalent organic group represented by X, Y, and Z mentioned above.
In Formula (C), L ³ represents a single bond or a substituted or unsubstituted divalent organic group. Defining divalent organic group has the same meaning as divalent organic group represented by L ¹ and L ² as described above.
In formula (C), V represents an ionic polar group. Specific examples of the ionic polar group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group. Among these, a carboxylic acid group is preferable from the viewpoint of moderate acidity (does not decompose other functional groups).

In particular, in the unit represented by the formula (C), moderate acidity (does not decompose other functional groups), hydrophilicity in an alkaline aqueous solution, and hydrophobicity due to the cyclic structure when water is dried. Therefore, it is preferable that V is a carboxylic acid group and has a 4-membered to 8-membered ring structure at the connecting portion of L ³ with V. Here, examples of the 4- to 8-membered ring structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a phenyl group, and among them, a cyclohexyl group and a phenyl group are preferable.
The unit represented by the formula (C) is moderately acidic (does not decompose other functional groups), hydrophilic in an alkaline aqueous solution, and hydrophobic by a long-chain alkyl group structure when water is dried. From the viewpoint of ease, it is also preferred that V is a carboxylic acid group and the chain length of L ³ is 6 to 18 atoms. Here, the chain length of L ³ represents the distance between U and V in the formula (C), and it is preferable that the distance between U and V is preferably in the range of 6 to 18 atoms. To do. The chain length of L ³ is more preferably 6 to 14 atoms, still more preferably 6 to 12 atoms.

The preferred content of each unit in the second preferred embodiment of the resin A is as follows.
The unit represented by the formula (A) is contained in an amount of 5 to 50 mol% with respect to all units in the resin A in terms of reactivity (curability and polymerization) and suppression of gelation during synthesis. Preferably, it is 5-30 mol%.
The unit represented by the formula (B) is preferably contained in an amount of 5 to 80 mol%, more preferably 10 to 70 mol%, with respect to all units in the resin A, from the viewpoint of adsorptivity to the plating catalyst. It is.
The unit represented by the formula (C) is preferably contained in an amount of 10 to 70 mol%, more preferably 20 to 70%, based on all units in the resin A, from the viewpoints of developability with an aqueous solution and moisture-resistant adhesion. It is 60 mol%, and particularly preferably 30 to 50 mol%.

  In addition, as an ionic polar value in the 2nd preferable aspect of resin A (when an ionic polar group is a carboxylic acid group), 1.5-7.0 mmol / g is preferable and 1.7-5 0.0 mmol / g is more preferable, and 1.9 to 4.0 mmol / g is particularly preferable. When the ionic polarity value is within this range, it is possible to achieve both the development of the aqueous solution and the suppression of the decrease in the adhesion strength with time of wet heat.

(Resin synthesis method)
The method for synthesizing the resin A is not particularly limited, and the monomer used may be a commercially available product or a combination of known synthesis methods. For example, the resin A can be synthesized with reference to the method described in paragraphs [0120] to [0164] of Japanese Patent Publication No. 2009-7662.
More specifically, when the polymerizable group is a radical polymerizable group, the following method is preferably exemplified as a resin synthesis method.
i) a monomer having a radical polymerizable group, a method of copolymerizing a monomer having an interactive group, ii) a monomer having an interactive group and a monomer having a radical polymerizable group precursor are copolymerized and then a base A method of introducing a radical polymerizable group by a treatment such as iii) a method of introducing a radical polymerizable group by copolymerizing a monomer having an interactive group and a monomer having a reactive group for introducing a radical polymerizable group Is mentioned.
From the viewpoint of synthesis suitability, preferred methods are the methods ii) and iii). The kind of polymerization reaction at the time of synthesis is not particularly limited, and it is preferably performed by radical polymerization.

(Polymerization initiator)
The resin composition layer contains a polymerization initiator. When a polymerization initiator is included, an active species (for example, radical active species) is generated by energy application described below (particularly irradiation using long wavelength light, etc.), and a reaction between polymerizable groups or polymerizability. The reaction between the group and the first resin layer is further promoted. As a result, a metal film with high adhesion can be obtained.
When the polymerization initiator is not included, the second resin layer described later is not sufficiently formed, and as a result, the plating deposition does not proceed sufficiently, and the metal film cannot be formed.

  Examples of the polymerization initiator that can be used in the present invention include a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. From the viewpoint of excellent reactivity, a radical polymerization initiator is preferable. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. From the viewpoint of the production process in the step (3) described later, a photopolymerization initiator is preferable.

The polymerization initiator is preferably a compound that undergoes polymerization cleavage upon irradiation with low energy light. For example, polymerization having a molar extinction coefficient in a methanol solution at 365 nm of 50 to 10,000 (ml / g · cm). Preferably it is an initiator. Especially, it is more preferable that it is 270-10,000 (l / mol * cm). In addition, even when irradiated with long-wavelength light in other wavelength ranges (lights exceeding 365 nm), if the molar extinction coefficient in the wavelength range is within the above range, the reaction of the polymerizable group proceeds well, and is excellent. A metal film exhibiting excellent adhesion can be obtained.
Moreover, it is preferable that a polymerization initiator has an absorption peak wavelength in the range of 250-400 nm by the point from which the metal film excellent in adhesiveness is obtained by low energy irradiation.

Examples of the polymerization initiator include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f And ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, and the like.
Of these, α-aminoalkylphenone compounds, oxime / ester compounds, acylphosphine oxide compounds, and titanocene compounds are preferred because the effects of the present invention are more excellent. Specific examples of the α-aminoalkylphenone compounds include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butanone-1,2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropan-2-one and the like. Specific examples of the oxime ester compound include 1,2-octanedione, 1- {4- (phenylthio)-, 2- (O-benzoyloxime)}, ethanone, 1- {9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl}-, 1- (O-acetyloxime) and the like. Specific examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Specific examples of the titanocene compound include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl)- Phenyl) titanium. These may be used alone or in combination. Examples of commercially available α-aminoalkylphenone compounds include Irgacure 369 and Irgacure 907 manufactured by Ciba, and examples of oxime ester compounds include OXE-01 and OXE-02.

(Method for forming resin composition layer)
The resin composition layer can be formed by applying a known layer forming method, for example, a method of laminating the above-described resin A and a polymerization initiator on a substrate, or a composition containing the resin A and a polymerization initiator. Examples thereof include a method of applying (hereinafter referred to as composition A) on a substrate.
From the viewpoint of work, the above coating method is preferable. Examples of the application method include the methods exemplified in the first resin layer composition described above.

The composition A may contain a solvent, and the solvent to be used is not particularly limited as long as the resin A which is the main component of the composition A can be dissolved.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone and cyclohexanone, amides such as formamide and dimethylacetamide. Examples thereof include water-based solvents and water.
Moreover, the composition A may contain surfactant as needed.

When the composition A contains a solvent, the composition A may be applied and dried as necessary. Drying may be performed by natural drying to remove the solvent, but can also be performed by heating or exposing the coating film.
The coating amount of the resin composition layer is preferably 0.1 to 10 g / m ^{2 in} terms of solid content from the viewpoint of obtaining sufficient plating catalyst or its interaction with the precursor and a uniform coating film. In particular, 0.5 to 5 g / m ² is preferable.

(Resin composition layer)
Resin A and a polymerization initiator are contained in the resin composition layer obtained by the above procedure. A part of the solvent may be included.
The content of the resin A in the resin composition layer is appropriately selected according to the type of the resin A used. Especially, it is preferable that content of resin A is 0.1-99.9 mass% with respect to the resin composition layer whole quantity from the viewpoint of the coating-film property of a resin composition layer, and film | membrane physical property. More preferably, it is -50 mass%.
The content of the polymerization initiator in the resin composition layer is appropriately selected according to the type of resin A used. Especially, from the viewpoint of the reactivity and film properties of the resin A, the content of the polymerization initiator is preferably 0.1 to 20% by mass with respect to the resin A, and is 1 to 10% by mass. Is more preferable.

In the resin composition layer, other resins than the resin A may be contained. Other resin types are the same as other resins that may be included in the first resin layer described above.
The resin composition layer may contain other additives (surfactants) and the like as necessary.

  The thickness of the resin composition layer is appropriately adjusted so that a second resin layer described later has a predetermined thickness.

<Process (3): Curing process>
In the step (3), energy is imparted to the resin composition layer obtained in the step (2) and cured to form a second resin layer. The cured second resin layer forms a chemical bond with the first resin layer via the polymerizable group, and adhesion to the first resin layer is improved.

(Granting energy)
As the energy application method, radiation irradiation such as heating or exposure can be used. For example, light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible.
Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.
Specific examples generally used include direct image-like recording using a thermal recording head, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
The time required for energy application varies depending on the light source, but is usually between 10 seconds and 5 hours.

In addition, when performing energy provision by exposure, the exposure power is in the range of 50 to 30000 mJ / cm ² in order to sufficiently proceed the reaction between the polymerizable groups and to suppress the decomposition of the resin. Is preferable, and the range of 100 to 5000 mJ / cm ² is more preferable.

  The form of energy application is preferably performed by light irradiation (exposure) using long-wavelength light from the viewpoint of reducing the cost of the manufacturing process and suppressing decomposition of the resin. The long wavelength light specifically means light having a wavelength of 254 nm or more, and light having a wavelength of 254 to 460 nm is preferable. In particular, it is preferable to perform light irradiation with a wavelength of 300 nm or more.

  The thickness of the second resin layer is not particularly limited, but is preferably 0.1 to 1.5 μm, more preferably 0.3 to 1.2 μm from the viewpoint of forming sufficient interaction with the plating catalyst or its precursor. preferable.

<Process (4): Plating catalyst application process>
In step (4), a plating catalyst or a precursor thereof is applied to the second resin layer obtained in step (3).
In this step, the interactive group possessed by the resin constituting the second resin layer adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. More specifically, a plating catalyst or a precursor thereof is imparted through the interactive group in the second resin layer and on the surface of the second resin layer.
Here, examples of the plating catalyst or a precursor thereof include those that function as a plating catalyst or an electrode in the step (5) described later. Therefore, the plating catalyst or its precursor is determined by the type of plating in step (5).
In addition, it is preferable that the plating catalyst used in this process or its precursor is an electroless plating catalyst or its precursor.

(Electroless plating catalyst)
As the electroless plating catalyst used in this step, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal (Ni) having catalytic ability for autocatalytic reduction reaction. And those known as metals capable of electroless plating with a lower ionization tendency). Specific examples include Pd, Ag, Cu, Ni, Al, Fe, and Co. Of these, Ag and Pd are particularly preferable because of their high catalytic ability.
This electroless plating catalyst may be used as a metal colloid. Generally, 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 controlled by the surfactant or protective agent used here.

(Electroless plating catalyst precursor)
The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. The metal ions of the metals mentioned as the electroless plating catalyst are mainly 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 which is an electroless plating catalyst precursor may be converted into a zero-valent metal by a reduction reaction separately after being applied to the second resin layer and before immersion in the electroless plating bath. Then, the electroless plating catalyst 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.

It is preferable that the metal ion which is an electroless plating precursor is provided to the second resin layer using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable 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 represents an n-valent metal atom), and the like. 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. Among them, those capable of multidentate coordination are preferable, and in particular, functionalities capable of coordination. In view of the number of types of groups and catalytic ability, Ag ions and Pd ions are preferred.

  One preferred example of the electroless plating catalyst or precursor thereof used in the present invention is a palladium compound. This palladium compound acts as a plating catalyst (palladium) or a precursor thereof (palladium ions), which serves as an active nucleus during plating treatment and serves to precipitate a metal. The palladium compound is not particularly limited as long as it contains palladium and acts as a nucleus in the plating process, and examples thereof include a palladium (II) salt, a palladium (0) complex, and a palladium colloid.

Moreover, as an electroless-plating catalyst or its precursor, silver or silver ion is mentioned as another preferable example.
When silver ions are used, those obtained by dissociating silver compounds as shown below can be suitably used. Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples thereof include silver diethyldithiocarbamate and silver p-toluenesulfonate. Among these, silver nitrate is preferable from the viewpoint of water solubility.

  As a method for applying a metal that is an electroless plating catalyst or a metal salt that is an electroless plating precursor to the second resin layer, a dispersion in which a metal is dispersed in an appropriate dispersion medium or a metal salt is appropriately used. A solution containing dissolved and dissociated metal ions is prepared, and the dispersion or solution is applied onto the second resin layer, or the second resin layer is formed in the dispersion or solution. What is necessary is just to immerse the done substrate.

By contacting the electroless plating catalyst or a precursor thereof as described above, the interaction group of the second resin layer is caused to interact by an intermolecular force such as van der Waals force or by a lone electron pair. An electroless plating catalyst or a precursor thereof can be adsorbed by utilizing an interaction due to a coordinate bond.
From the viewpoint of sufficiently performing such adsorption, the metal concentration or metal ion concentration in the dispersion or solution is preferably in the range of 0.001 to 50% by mass, and 0.005 to 30% by mass. More preferably, it is the range.
Further, the contact time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.

(Other catalysts)
In the present invention, a zero-valent metal can be used as a catalyst used for performing direct electroplating without performing electroless plating on the second resin layer in the step (4). Examples of the zero-valent metal include Pd, Ag, Cu, Ni, Al, Fe, and Co. Among them, those capable of multidentate coordination are preferable, and in particular, adsorptive (adhesive) property to an interactive group, Pd, Ag, and Cu are preferable because of their high catalytic ability.

(Organic solvent and water)
As described above, the plating catalyst or the precursor thereof is applied to the second resin layer as a dispersion or a solution (catalyst solution).
An organic solvent or water is used for the dispersion or solution. By containing the organic solvent, the permeability of the plating catalyst or its precursor to the second resin layer is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the interactive group.

  In the dispersion or solution, water may be used, and it is preferable that this water does not contain impurities. From such a viewpoint, RO water, deionized water, distilled water, purified water, etc. are used. It is particularly preferable to use deionized water or distilled water.

  The organic solvent used for preparing the dispersion or solution is not particularly limited as long as it is a solvent that can penetrate into the second resin layer. Specifically, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol Diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve, and the like can be used.

  In particular, a water-soluble organic solvent is preferable from the viewpoint of compatibility with a plating catalyst or a precursor thereof and permeability to the second resin layer, and acetone, dimethyl carbonate, dimethyl cellosolve, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether are preferable. Diethylene glycol diethyl ether is preferred.

  Further, the dispersion or solution may contain other additives depending on the purpose. Examples of other additives include swelling agents and surfactants.

  Through the step (4) described above, an interaction can be formed between the interactive group in the second resin layer and the plating catalyst or its precursor.

<Process (5): Plating process>
In step (5), plating is performed on the second resin layer to which the plating catalyst or its precursor has been applied in step (4) to form a metal film on the second resin layer. The formed metal film has excellent conductivity and adhesion.
Examples of the type of plating performed in this step include electroless plating, electroplating, etc., and the function of the plating catalyst or its precursor that forms an interaction with the second resin layer in the above step (4). Can be selected.
That is, in this step, electroplating or electroless plating may be performed on the second resin layer provided with the plating catalyst or its precursor.
Among these, electroless plating is preferably performed from the viewpoint of improving the formability and adhesion of the hybrid structure that appears in the second resin layer. In order to obtain a metal film having a desired film thickness, it is a more preferable aspect that electroplating is further performed after electroless plating.
Hereinafter, the plating suitably performed in this process will be described.

(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, for example, by rinsing the substrate provided with the electroless plating catalyst to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. As the electroless plating bath used, a known electroless plating bath can be used.
Further, when the substrate to which the electroless plating catalyst precursor is applied is immersed in the electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the second resin layer, the substrate is washed with water. After removing an excess precursor (metal salt etc.), it is immersed in an electroless plating bath. In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a known electroless plating bath can be used as described above.

In addition, the reduction of the electroless plating catalyst precursor may be performed as a separate step before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above. Is possible. The catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and the concentration of the reducing agent with respect to the whole liquid is 0.1 to 50% by mass. Preferably, 1-30 mass% is more preferable. As the reducing agent, it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, or a reducing agent such as formaldehyde or hypophosphorous acid.
In soaking, the concentration of the electroless plating catalyst or its precursor in the vicinity of the surface of the second resin layer with which the electroless plating catalyst or its precursor contacts is kept constant while stirring or shaking. It is preferable to do.

  As a composition of a general electroless plating bath, in addition to a solvent (for example, water), 1. 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.

  The organic solvent used in the plating bath needs to be a solvent that can be used in water, and in this respect, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.

  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. Moreover, the optimal reducing agent and additive are selected according to the said metal.

The film thickness of the metal film formed by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. From the viewpoint, it is preferably 0.1 μm or more, and more preferably 0.2 to 2 μm.
However, when performing electroplating described later using a metal film formed by electroless plating as a conductive layer, it is preferable that a film of at least 0.1 μm or more is uniformly applied.
Further, the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.

  The metal film obtained by electroless plating obtained as described above has fine particles of a plating catalyst and a plating metal dispersed in the second resin layer at a high density by cross-sectional observation using a scanning electron microscope (SEM). Further, it is confirmed that the plating metal is deposited on the second resin layer. Since the interface between the second resin layer and the metal film is a hybrid state of the resin composite and the fine particles, the interface between the second resin layer (organic component) and the inorganic substance (plating catalyst metal or plating metal) is smooth. Even so, the adhesion is good.

(Electroplating)
In this step, when the plating catalyst or its precursor applied in the above step (4) has a function as an electrode, the second resin layer to which the catalyst or its precursor is applied is electrically Plating can be performed.
In addition, after the above electroless plating, the formed metal film may be used as an electrode, and electroplating may be further performed. As a result, a new metal film having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the substrate. As described above, by performing electroplating after electroless plating, the metal film can be formed to a thickness according to the purpose, which is suitable for applying the metal film to various applications.

  As a method of electroplating, a conventionally known method can be used. In addition, as a metal used for electroplating, copper, chromium, lead, nickel, gold | metal | money, silver, tin, zinc etc. are mentioned, From a conductive viewpoint, copper, gold | metal | money, silver is preferable and copper is more preferable.

Moreover, the film thickness of the metal film obtained by electroplating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like.
In addition, when applying to general electrical wiring etc., it is preferable that the film thickness of a metal film is 0.5 micrometer or more from a viewpoint of electroconductivity, and 1-30 micrometers is more preferable.
In addition, the thickness of the electrical wiring is reduced in order to maintain the aspect ratio as the line width of the electrical wiring is reduced, that is, as the size is reduced. Therefore, the layer thickness of the metal film formed by electroplating is not limited to the above and can be arbitrarily set.

<Surface metal film material>
By passing through each process of the metal film formation method of this invention, the surface metal film material provided with a board | substrate, a 1st resin layer, a 2nd resin layer, and a metal film in this order can be obtained.
The obtained surface metal film material can be applied to various uses such as an electromagnetic wave prevention film, a coating film, a two-layer CCL (Copper Clad Laminate) material, and an electric wiring material.

<Metal pattern material and manufacturing method thereof>
By performing the process of etching the metal film in the surface metal film material in a pattern shape, a metal pattern material having the pattern metal film on the surface can be manufactured. That is, a wiring (metal pattern) can be formed by patterning a metal film (plating film) in the surface metal film material.
This etching step (step (7)) will be described in detail below.

<Process (7): Etching process>
Step (7) is a step of etching the metal film (plated film) formed in step (5) into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the metal film formed on the entire substrate surface by etching.
Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.

  With the subtractive method, a dry film resist layer is provided on the formed metal film, the same pattern as the metal pattern part is formed by pattern exposure and development, the metal 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, wet etching is preferable from the viewpoint of simplicity of the apparatus. As an etching solution, for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.

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

On the other hand, a patterned second resin layer can be obtained by performing the following step (6) instead of the step (3). For the development removal in the step (6), a developer capable of dissolving and removing the resin composition layer is appropriately used.
Step (6): Applying pattern energy to the resin composition layer, curing the resin composition layer in the energy application region, and then developing and removing the non-energy application region to form a pattern-like second resin layer Step of Performing Steps (4) and (5) on the patterned second resin layer obtained in Step (6) can also produce a metal pattern material having a patterned metal film ( Full additive method).

<Application>
The obtained metal pattern material can be applied to various uses such as semiconductor chips, various electric wiring boards, FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, and the like. Especially, the use which provides an insulating layer on a metal pattern material and uses it as a wiring board is preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

Below, the synthesis method of the polymer used in a present Example is explained in full detail.
(Synthesis Example 1: Synthesis of specific polymer A)
A 500 ml three-necked flask was charged with 20 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. There, 20.7 g of monomer M having the following structure, 20.5 g of 2-cyanoethyl acrylate (manufactured by Tokyo Chemical Industry), 14.4 g of acrylic acid (manufactured by Tokyo Chemical Industry), 1.0 g of V-65 (manufactured by Wako Pure Chemical Industries) A 20 g solution of N, N-dimethylacetamide was added dropwise over 4 hours. After completion of dropping, the reaction solution was further stirred for 3 hours. Thereafter, 91 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature.

4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.17g and triethylamine 75.9g were added to said reaction solution, and reaction was performed at room temperature for 4 hours. Thereafter, 112 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, the solid was taken out, and 25 g of specific polymer A (weight average molecular weight: 34000) having the following structure was obtained. The acid value of this specific polymer A was 4.0 mmol / g.
In addition, the numerical value in the following structural formula represents the mol% of each unit.

(Synthesis Example 2: Synthesis of specific polymer B)
1 L of ethyl acetate and 159 g of 2-aminoethanol were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto, 150 g of 2-bromoisobutyric acid bromide was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.
Next, 47.4 g of raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask and cooled in an ice bath. Thereto, 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water and dried over magnesium sulfate, and ethyl acetate was further distilled off. Thereafter, the following monomer L was purified by column chromatography to obtain 20 g.

  A 500 mL three-necked flask was charged with 8 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. The monomer L obtained above: 14.3 g, 3.0 g of acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.5 g of acrylic acid (manufactured by Tokyo Chemical Industry), V-65 (manufactured by Wako Pure Chemical Industries) 4 g of N, N-dimethylacetamide 8 g solution was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 41 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. 4-hydroxy TEMPO (product made from Tokyo Chemical Industry) 0.09g and DBU54.8g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 54 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 12 g of specific polymer B (weight average molecular weight 53,000) was obtained. The acid value of the obtained specific polymer B was measured using a potentiometric automatic titrator (manufactured by Kyoto Denshi Kogyo Co., Ltd.) and a 0.1M sodium hydroxide aqueous solution as the titrant. Was 3.9 mmol / g.

The obtained polymer B was identified using an IR measuring machine (manufactured by Horiba, Ltd.). The measurement was performed by dissolving the polymer in acetone and using KBr crystals. As a result of IR measurement, a peak was observed in the vicinity of 2240 cm ⁻¹ , and it was found that acrylonitrile, which is a nitrile unit, was introduced into the polymer. Moreover, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Moreover, it melt | dissolved in heavy DMSO (dimethyl sulfoxide), and measured by NMR (AV-300) of Bruker 300MHz. 4. A peak corresponding to the nitrile group-containing unit is broadly observed at 2.5 to 0.7 ppm (5 H min), and a peak corresponding to the polymerizable group containing unit is 7.8 to 8.1 ppm (1 H min). 8-5.6 ppm (for 1H), 5.4-5.2 ppm (for 1H), 4.2-3.9 ppm (for 2H), 3.3-3.5 ppm (for 2H), 2.5- A broad peak was observed at 0.7 ppm (6 H min), and a peak corresponding to a carboxylic acid group unit was observed broad at 2.5-0.7 ppm (3 H min), and a polymerizable group-containing unit: a nitrile group-containing unit: The carboxylic acid group unit was found to be 25:28:47 (mol ratio).

<Example 1>
(Process 1)
Acrylonitrile-butadiene copolymer (NBR) resin [product name: Nipol 003 (cyano group content: 9.2 mmol / g), manufactured by Nippon Zeon Co., Ltd.] as a first resin layer on a polymethyl methacrylate resin (PMMA) substrate. Is applied by spin coating (condition: resin layer dried and film thickness 4 μm), and dried at 120 ° C. for 30 minutes to prepare a substrate A having a first resin layer (cyano group content 9.2 mmol / g). Obtained.

(Steps 2 and 3)
A resin composition A having the following composition containing the specific polymer A is applied to the substrate A by a spin coating method (condition: film thickness after drying: 1 μm) to form a resin composition layer, and a UV exposure machine (wavelength: 365 nm (wavelength: 365 nm ( Short wavelength side cut using soda glass) The resin composition layer was exposed with an exposure energy of 500 mJ / cm ² using Mitsunaga Electric Manufacturing Co., Ltd. model number: UVF-502S, lamp: UXM-501MD). .
The exposed substrate is dipped in a 1% by weight NaHCO ₃ aqueous solution for 10 minutes, and then washed with distilled water, and provided with a second resin layer (thickness: 1 μm) chemically bonded to the first resin layer. A substrate B was obtained.

(Resin composition A)
Water: 4.628 g, NaHCO ₃ : 0.31 g, specific polymer A: 1.742 g, ethanol: 18.51 g were mixed and stirred to dissolve the polymer, and then the water-insoluble photoinitiator (Irgacure 379): 0.174g was added and it stirred further, and the resin composition A was produced.

(Process 4)
Substrate B having the second resin layer was immersed in 1% by weight aqueous solution of silver nitrate for 10 minutes, and then immersed in acetone for cleaning.

(Process (5): Electroless plating and electroplating)
As described above, the substrate B having the second resin layer provided with the plating catalyst was subjected to electroless plating at 26 ° C. for 30 minutes using an electroless plating bath having the following composition. The thickness of the obtained electroless copper plating film was 0.3 μm.

(Composition of electroless plating bath)
・ 774g of distilled water
・ ATS Ad Copper IW-A (Okuno Pharmaceutical Co., Ltd.) 45mL
・ ATS Ad Copper IW-M (Okuno Pharmaceutical Co., Ltd.) 72mL
・ ATS Ad Copper IW-C (Okuno Pharmaceutical Co., Ltd.) 9mL
・ NaOH 1.98 g
・ 2,2'-bipyridyl

Subsequently, electroplating was performed for 20 minutes under the condition of 3 A / dm ² using an electroless copper plating film as a power feeding layer and using an electrolytic copper plating bath having the following composition. In this way, a metal film having an electrolytic copper plating film thickness of 18 μm was produced.

(Composition of electroplating bath)
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Copper Greeme PCM (Meltex Co., Ltd.) 3mL
・ Water 500g

<Example 2>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in step (1) of Example 1, NBR resin [product name: Nipol 1041 (cyano group content: 7.4 mmol / g), manufactured by Nippon Zeon Co., Ltd.] A metal film was prepared according to the same procedure as in Example 1 except that it was used.
In addition, cyano group content of the obtained 1st resin layer was 7.4 mmol / g.

<Example 3>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in step (1) of Example 1, NBR resin [product name: Nipol DN101L (cyano group content: 7.8 mmol / g), manufactured by Nippon Zeon Co., Ltd.] A metal film was prepared according to the same procedure as in Example 1 except that it was used.
In addition, cyano group content of the obtained 1st resin layer was 7.8 mmol / g.

<Example 4>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in step (1) of Example 1, SBR resin (product No: 182907, manufactured by Aldrich) and polyacrylonitrile (product No: 181315, cyano group content) A metal film was prepared according to the same procedure as in Example 1 except that a mixture (SBR: PAN = 1: 1 (weight ratio)) with 18.9 mmol / g, PAN (Aldrich) was used.
The cyano group content of the obtained first resin layer was 7.5 mmol / g.

<Example 5>
A metal film was prepared according to the same procedure as in Example 1 except that the specific polymer B was used instead of the specific polymer A used in the step (2) of Example 1.

<Example 6>
A metal film was prepared according to the same procedure as in Example 2, except that the specific polymer B was used instead of the specific polymer A used in the step (2) of Example 2.

<Example 7>
Instead of the resin composition A containing the specific polymer A used in the step (2) of Example 3, a resin composition B having the following composition containing the specific polymer B was used, and the same procedure as in Example 3 was followed. A metal film was prepared.
(Resin composition B)
Water: 4.628 g, NaHCO ₃ : 0.31 g, specific polymer B: 1.742 g, ethanol: 18.51 g were mixed and stirred to dissolve the polymer, and then the water-insoluble photoinitiator (Irgacure 379): 0.174g was added and it stirred further, and the resin composition B was produced.

<Example 8>
A metal film was prepared according to the same procedure as in Example 7, except that the resin composition B containing the specific polymer B used in the step (2) of Example 7 was changed to the resin composition B-1 described below. .
(Resin composition B-1)
Water: 4.628 g, NaHCO ₃ : 0.31 g, specific polymer B: 1.742 g, 1-methoxy-2-propanol: 18.51 g were mixed and stirred to dissolve the polymer, then water-insoluble photo initiation Agent (Irgacure OXE-02): 0.174 g was added and further stirred to prepare Resin Composition B-1.

<Example 9>
According to the same procedure as in Example 8, except that the water-insoluble photoinitiator (Irgacure OXE-02) contained in the resin composition B-1 used in Example 8 was changed to Irgacure OXE-01, a metal film was formed. Produced.

<Example 10>
A metal film was produced according to the same procedure as in Example 8, except that the exposure amount in step (3) of Example 8 was changed to 4000 mJ / cm ² .

<Example 11>
A metal film was produced according to the same procedure as in Example 8, except that the exposure amount in the step (3) of Example 8 was changed to 1000 mJ / cm ² .

<Example 12>
A metal film was produced according to the same procedure as in Example 8, except that the exposure amount in the step (3) of Example 8 was changed to 200 mJ / cm ² .

<Example 13>
A metal film was produced according to the same procedure as in Example 3, except that the drying conditions in Step (1) of Example 3 were changed to 150 ° C. and 30 minutes.

<Example 14>
A metal film was produced according to the same procedure as in Example 3 except that the drying conditions in Step (1) of Example 3 were changed to 180 ° C. and 30 minutes.

<Example 15>
Except that the water-insoluble photoinitiator (Irgacure OXE-02) contained in the resin composition B-1 used in Example 8 was changed to Irgacure 379 and the addition amount was changed to 5% by mass with respect to the polymer B, A metal film was prepared according to the same procedure as in Example 8.

<Example 16>
Except that the water-insoluble photoinitiator (Irgacure OXE-02) contained in the resin composition B-1 used in Example 8 was changed to Irgacure 379 and the addition amount was changed to 20% by mass with respect to the polymer B, A metal film was prepared according to the same procedure as in Example 8.

<Example 17>
The process up to the layer formation of the resin composition B in the step (2) of Example 7 is performed in the same procedure, and the exposure is performed with a light exposure of 3000 mJ / cm ² and pattern exposure through a photomask with a line and space of 300 μm. Changed. The substrate after the exposure was immersed in a 1% by mass aqueous NaHCO ₃ solution for 10 minutes, and then washed with distilled water. Thus, a substrate having a patterned second resin layer (layer to be plated) was obtained.
The substrate having the second resin layer was immersed in 1% by weight aqueous solution of silver nitrate for 10 minutes, and then immersed in water for cleaning.
A sample in which pattern plating is formed by performing electroless plating for 30 minutes at 30 ° C. using an electroless plating bath having the following composition on a substrate having a plating layer provided with a plating catalyst as described above. Got. The thickness of the obtained electroless copper plating film was 1 μm.
(Composition of electroless plating bath)
・ 463g of distilled water
・ OPC Copper T1 (Okuno Pharmaceutical Co., Ltd.) 33g
・ OPC Copper T3 (Okuno Pharmaceutical Co., Ltd.) 55g
・ Formalin 5.35g

<Comparative Example 1>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in step (1) of Example 1, a styrene-butadiene copolymer (SBR) latex resin [Product name: Nipol LX430, manufactured by Nippon Zeon Co., Ltd.] was used. A metal film was produced according to the same procedure as in Example 1 except for the above. In addition, the cyano group is not contained in the obtained 1st resin layer.

<Comparative example 2>
Example 1 and Example 1 were used except that polystyrene (PS) resin [Product No: 189596, manufactured by Aldrich] was used instead of the acrylonitrile-butadiene copolymer (NBR) resin used in the step (1) of Example 1. A metal film was prepared according to the same procedure. In addition, the cyano group is not contained in the obtained 1st resin layer.

<Comparative Example 3>
The same procedure as in Example 1 except that SBR resin [Product No: 182907, manufactured by Aldrich] was used instead of the acrylonitrile-butadiene copolymer (NBR) resin used in Step (1) of Example 1. According to this, a metal film was prepared. In addition, the cyano group is not contained in the obtained 1st resin layer.

<Comparative example 4>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in step (1) of Example 1, an acrylonitrile-butadiene-styrene copolymer (ABS) resin [Product No: 430145 (cyano group content: 3.2 mmol) / G), manufactured by Aldrich Co.], a metal film was prepared according to the same procedure as in Example 1.
The cyano group content of the obtained first resin layer was 3.2 mmol / g.

<Comparative Example 5>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in step (1) of Example 1, NBR resin [product name: Nipol 1043 (cyano group content: 5.6 mmol / g), manufactured by Nippon Zeon Co., Ltd.] A metal film was prepared according to the same procedure as in Example 1 except that it was used.
The cyano group content of the obtained first resin layer was 5.6 mmol / g.

<Comparative Example 6>
A metal film was prepared according to the same procedure as in Example 1 except that an epoxy resin described later was used instead of the acrylonitrile-butadiene copolymer (NBR) resin used in Step (1) of Example 1.
The epoxy resin layer is composed of 12.3 parts by mass of jER806 (bisphenol F type epoxy resin: manufactured by Japan Epoxy Resin), 4.3 parts by mass of LA7052 (phenolite, curing agent: Dainippon Ink and Chemicals), YP50-35EK (phenoxy). Resin, manufactured by Toto Kasei Co., Ltd.) 20.9 parts by mass, 62.5 parts by mass of cyclohexanone, and 0.1 parts by mass of 2-ethyl-4-methylimidazole (curing accelerator) were mixed with a filter cloth (mesh # 200), and the prepared coating solution was applied by spin coating (condition: film thickness after drying: 6 μm).
In addition, the cyano group is not contained in the obtained 1st resin layer.

<Comparative Example 7>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in the step (1) of Example 1, NBR resin [product name: Nipol 1042 (cyano group content 6.1 mmol / g), manufactured by Nippon Zeon Co., Ltd.] A metal film was prepared according to the same procedure as in Example 1 except that it was used.
The cyano group content of the obtained first resin layer was 6.1 mmol / g.

<Comparative Example 8>
Instead of the acrylonitrile-butadiene copolymer (NBR) resin used in step (1) of Example 1, NBR resin (product name: Nipol 1042, manufactured by Nippon Zeon Co., Ltd.) and polyacrylonitrile (PAN) (manufactured by Aldrich) A metal film was prepared according to the same procedure as in Example 1 except that the mixture (NBR: PAN = 91: 9 (mass ratio)) was used.
In addition, cyano group content of the obtained 1st resin layer was 7.2 mmol / g.

<Comparative Example 9>
Instead of the resin composition A used in the step (2) of Comparative Example 8, the following resin composition A-3 was used, and an attempt was made to produce a metal film according to the same procedure as in Example 1. However, in this comparative example, no plating was deposited, and evaluation on a metal film described later could not be performed.
In addition, the polymerization initiator is not contained in resin composition A-3.
Further, the cyano group content of the obtained first resin layer was 7.2 mmol / g.
(Resin composition A-3)
Water: 4.628 g, NaHCO ₃ : 0.31 g, specific polymer A: 1.742 g, and ethanol: 18.51 g were mixed and stirred to dissolve the polymer, thereby preparing a resin composition A-3.

<Comparative Example 10>
Production of a metal film was attempted according to the same procedure as in Example 1 except that the above resin composition A-3 was used instead of the resin composition A used in the step (2) of Example 3. However, in this comparative example, no plating was deposited, and evaluation on a metal film described later could not be performed.
In addition, cyano group content of the obtained 1st resin layer was 7.8 mmol / g.

<Initial adhesion evaluation>
The substrate having the metal film after step (5) obtained in each example and comparative example was cut into a grid pattern of 1 mm in width and 100 squares according to JIS K5400-8.5 (JIS D0202), and cross A cut test was conducted.
The smaller the peeling of the metal film, the better the adhesion, and in the following evaluation, it is evaluated that practical adhesion is achieved if it is ○. The results are summarized in Table 1.
○: No peeling ×: There is peeling

<Evaluation of adhesion after environmental test>
The substrate having the metal film after the step (5) obtained in each example and comparative example was held at a temperature of 85 ° C. and a humidity of 85% for 336 hours, and then subjected to a cross-cut test in the same manner as the initial adhesion evaluation. It was. The results are summarized in Table 1.

In addition, the polymerization initiator (Irgacure 379, Irgacure OXE-02, Irgacure OXE-01) used in the Examples had an absorption peak wavelength in the range of 250 to 400 nm.
In the column of “Presence / absence of polymerization initiator in resin composition layer” in Table 1 below, the case where a polymerization initiator is included in the resin composition layer is “◯”, and the case where it is not included is “x”. . In the column “Adhesive strength after environmental test”, the number of remaining masses after the peel test is also described.

As shown in Table 1, in Examples 1 to 17 using the first resin layer having a predetermined cyano group content of 7.4 mmol / g or more, any of the initial adhesion force and the adhesion force after the environmental test Also in this item, excellent adhesion between the metal film and the substrate was shown.
On the other hand, in Comparative Examples 1 to 10 that do not satisfy the predetermined range, there is an aspect that shows excellent adhesion in initial adhesion, but when held in a high-temperature and high-humidity environment, the adhesion between the metal film and the substrate It was confirmed that it was inferior in sex.
In Comparative Example 8, the cyano group of the first resin layer is 7.2 mmol / g, which is equivalent to the primer layer obtained from the cyano group-containing polymer 2 described in the examples of JP 2010-084196 A Amount of cyano group. Therefore, when the primer layer obtained from the cyano group-containing polymer 2 is used, the comparative example 8 is inferior in adhesion after the environmental test as described above.
Moreover, in Comparative Examples 9 and 10 in which the resin composition layer did not contain a polymerization initiator, plating deposition did not proceed and a desired metal film could not be obtained.

Claims (6)

Forming a first resin layer containing a cyano group-containing resin and having a cyano group content of 7.4 mmol / g or more on the substrate;
On the first resin layer, a step (2) of forming a resin composition layer containing a polymerizable group and a resin having a functional group that interacts with a plating catalyst or a precursor thereof, and a polymerization initiator;
A step (3) of applying energy to the resin composition layer and curing to form a second resin layer;
Providing a plating catalyst or a precursor thereof to the second resin layer (4);
Performing plating (5) to form a metal film on the second resin layer;
A metal film forming method comprising:   The polymerization initiator is contained in the resin composition layer in a range of 1 to 20% by mass with respect to a resin having a functional group that interacts with the polymerizable group and the plating catalyst or a precursor thereof. Item 2. The metal film forming method according to Item 1.   The metal film formation method according to claim 1, wherein the polymerization initiator has an absorption peak wavelength in a range of 250 to 400 nm. The metal film forming method according to claim 1, wherein the following step (6) is performed instead of the step (3).
Step (6): pattern-like energy is imparted to the resin composition layer, the resin composition layer in the energy imparted region is cured, and then the resin composition layer in the non-energy imparted region is developed and removed. Forming the second resin layer The metal film formation method in any one of Claims 1-4 whose resin which has the said cyano group is resin which has a unit represented by following formula (1).

(In Formula (1), R ^a represents a hydrogen atom or a substituted or unsubstituted alkyl group. L ^a represents ^a single bond or a substituted or unsubstituted divalent organic group.) The resin having a cyano group is acrylonitrile-butadiene copolymer or polyacrylonitrile,
The resin having a functional group that interacts with the polymerizable group and the plating catalyst or a precursor thereof is a copolymer including units represented by the following formulas (A), (B), and (C). The metal film formation method in any one of Claims 1-5.

(In the above formula (A), formula (B) and formula (C), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. X, Y, Z , U, L ¹ , L ² and L ³ each independently represents a single bond or a substituted or unsubstituted divalent organic group In formula (B), Wa represents an ionic polar group. Except for a functional group that interacts with the plating catalyst or its precursor, except that in formula (C), V represents an ionic polar group.