JP2012207258A - Composition for forming layered to be plated, and method for producing laminate having metal film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a layer to be plated, which can be produced without using much energy, and which provides a film to be plated that has excellent resistance against alkaline solution, and excellent adhesiveness to a metal film to be deposited thereon.SOLUTION: The composition for forming the layer to be plated includes a compound expressed by formula (1), and a polymer having the dissociative functional group and the polymerizable group forming the interaction with the plating catalyst or the precursor thereof.

Description

  The present invention relates to a composition for forming a layer to be plated, and a method for producing a laminate having a metal film using the composition.

2. Description of the Related Art Conventionally, a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
As a method for producing such a metal pattern material, a “subtractive method” is mainly used. In this subtractive method, a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal film formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image. In this method, the metal film is etched to form a metal pattern, and finally the resist is removed.

  In the metal pattern obtained by this method, the adhesion between the substrate and the metal pattern (metal film) is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, when the obtained metal pattern is used as a metal wiring, there is a problem that high frequency characteristics are deteriorated due to the unevenness of the substrate interface portion of the metal pattern. In addition, in order to process the surface of the substrate, it is necessary to treat the surface of the substrate with a strong acid such as chromic acid, and thus a complicated process is required to obtain a metal pattern with excellent adhesion to the substrate. There was a problem that.

  As a means for solving this problem, a method is known in which a polymer layer having high adhesion to the substrate is formed on the substrate, the polymer layer is plated, and the resulting metal film is etched ( Patent Document 1). According to this method, the adhesion between the substrate and the metal film can be improved without roughening the surface of the substrate.

JP 2010-248464 A

When manufacturing a laminated body having a patterned metal film obtained from the prior art (Patent Document 1) and when applying the laminated body to a wiring board or the like, it is excellent in contact with various solutions. Solvent resistance, particularly alkali solution resistance is required.
On the other hand, in the case of the layer to be plated used in the prior art, the characteristics are not necessarily sufficient. For example, when an alkaline degreasing solution or an alkaline electroless plating solution is used during electroless plating, the layer to be plated is damaged by the solution, resulting in a decrease in the adhesion of the metal film, For example, the surface state of the electroless plating film) may be reduced, or the high definition of a wiring pattern using the metal film may be impaired.

Further, in recent years, in order to meet the demand for downsizing and high functionality of electronic devices, further high integration of fine wiring such as printed wiring boards is progressing.
Accordingly, it is required to produce a metal wiring having lower energy, better productivity, and better adhesion to the substrate.

  In view of the above circumstances, the present invention can be manufactured without requiring a large amount of energy, and can provide a film to be plated that is excellent in alkali solution resistance and excellent in adhesion of a metal film formed thereon. It aims at providing the manufacturing method of the laminated body which has a composition for to-be-plated layer formation, and the metal film enforced using this composition.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using an acrylamide monomer having a predetermined structure. That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A composition for forming a layer to be plated, comprising a compound represented by formula (1) described later, and a polymer having a dissociative functional group and a polymerizable group that form an interaction with the plating catalyst or its precursor. .
(2) The composition for forming a plated layer according to (1), wherein log P of the compound is −0.3 or more.

(3) After contacting the composition for forming a layer to be plated according to claim 1 or 2 on a substrate, energy is applied to the composition for forming a layer to be plated on the substrate, A layer forming step of forming a layer to be plated on the substrate;
A catalyst application step of applying a plating catalyst or a precursor thereof to the layer to be plated;
A method for producing a laminate having a metal film comprising: a plating process for performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal film on the layer to be plated.
(4) A wiring board including a laminate having a metal film obtained by the manufacturing method according to (3).

  According to the present invention, formation of a layer to be plated that can be produced without requiring a large amount of energy, can be obtained, can be obtained a film to be plated that is excellent in alkali solution resistance and excellent in adhesion of a metal film formed thereon. The composition for manufacturing, and the manufacturing method of the laminated body which has a metal film enforced using this composition can be provided.

(A)-(D) are typical sectional drawings from the board | substrate to a laminated body which show each manufacturing process in order in the manufacturing method of the laminated body which has a laminated body and patterned metal film of this invention, respectively. (A)-(D) are typical sectional drawings which show one mode of an etching process of a layered product of the present invention in order. (A)-(E) are typical sectional drawing which shows the other aspect of the etching process of the laminated body of this invention in order. (A)-(H) is typical sectional drawing which shows the manufacturing process of a multilayer wiring board in order.

Below, the composition for to-be-plated layer formation of this invention and the manufacturing method of the laminated body which has a metal film are demonstrated.
First, the feature point compared with the prior art of this invention is explained in full detail.
In the present invention, the use of a compound represented by the formula (1) (hereinafter also referred to as an acrylamide monomer) is mentioned. By using an acrylamide monomer, the crosslink density in the formed layer to be formed is controlled, and the crosslink structure is constituted by a compound having an amide group which is difficult to hydrolyze, thereby improving the solvent resistance.
That is, by using the acrylamide monomer in combination with a polymer having a predetermined functional group, it has been difficult to achieve with the alkali solution resistance of the layer to be plated and the adhesion of the metal layer formed on the layer to be plated. Coexistence can be achieved.

  First, the constituent components (the compound represented by the formula (1), the polymer, etc.) of the composition for forming a plating layer of the present invention will be described in detail, and then a method for producing a laminate having a metal film using the composition Will be described in detail.

<Compound represented by Formula (1)>
The composition for forming a layer to be plated of the present invention contains a compound represented by the formula (1).

In formula (1), R ¹ represents a hydrogen atom or an alkyl group. As an alkyl group, C1-C6 is preferable, for example, a methyl group, an ethyl group, etc. are mentioned. Among them, in view of polymerization rate (crosslinking rate), R ¹ is preferably a hydrogen atom.

R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.

  Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, which may be linear, branched, or cyclic. Especially, C1-C10 is preferable and C1-C6 is more preferable at a compatible point with the polymer which has a dissociative functional group and a polymeric group. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group.

  Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Especially, C6-C12 is preferable and C6-C8 is more preferable at a compatible point with the polymer which has a dissociative functional group and a polymeric group.

R ² and R ³ may be directly bonded to form a ring. R ² and R ³ may form a ring via an oxygen atom. In the case of forming a ring, the total carbon number of R ² and R ³ is preferably 4 to 10 and more preferably 4 to 6 in terms of compatibility with a polymer having a dissociable functional group and a polymerizable group.

  The molecular weight of the compound is not particularly limited, but is preferably 70 to 300, more preferably 70 to 200, from the viewpoint of compatibility with the polymer described later and solubility in a solution.

  Two or more of the compounds may be contained in the composition for forming a layer to be plated.

(Preferred embodiment of the compound represented by the formula (1))
A preferred embodiment of the compound represented by formula (1) is that the log P of the compound is −0.3 or more. If logP is the said range, it is preferable at the point of adhesiveness with a plating metal.
Of these, log P is preferably −0.3 to 3.0, more preferably −0.2 to 2.0, and more preferably 0.3 to 1.0 in terms of adhesion to the plated metal. Is particularly preferred.

  In addition, logP means the common logarithm of partition coefficient P (Partition Coefficient), and is an index showing the degree of distribution of the chemical substance between the octanol phase and the water phase, and is defined as the following calculation formula 1. The

  From the above calculation formula 1, it means that the higher the value of logP, the higher the hydrophobicity of the chemical substance, and the lower the value of logP, the higher the hydrophilicity of the chemical substance. For example, a chemical substance having a log P value of 0 or less is more easily dissolved in the aqueous phase than the octanol phase, and a chemical substance having a log P value of 1 is less soluble in the octanol phase than the solubility in the aqueous phase. It can be said that it has 10 times the solubility.

Log P values of many compounds are reported, and many values are listed in a database available from Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., and can be referred to. When there is no measured log P value, it is most convenient to calculate with the program “CLOGP” available from Daylight CIS. This program outputs the value of “calculated logP (ClogP)” calculated by the Hansch, Leo fragment approach together with the measured logP value, if any.
In the present invention, if there is an actual measured value of logP, the ClogP value calculated by the program attached to ChemDraw Pro Ver12.0 is used when there is no measured value.

<Polymer>
The polymer used in the present invention has a polymerizable group and a dissociative functional group that interacts with the plating catalyst or a precursor thereof (hereinafter, an appropriately interacting group).
Hereinafter, the functional groups contained in the polymer and the characteristics thereof will be described in detail.

(Polymerizable group)
A polymerizable group is a functional group capable of forming a chemical bond between polymers or between a polymer and a substrate (or an adhesion auxiliary layer described later) by applying energy, such as a radical polymerizable group or a cationic polymerization. Sex groups 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. Of these, methacrylic acid ester groups, acrylic acid ester groups, vinyl groups, styryl groups, acrylamide groups, and methacrylamide groups are preferable, and methacrylic acid ester groups, acrylic acid ester groups, and styryl groups are particularly preferable.

(Interactive group)
The polymer has a dissociative functional group that interacts with a plating catalyst or a precursor thereof described later. By having this group, a plating catalyst or a precursor thereof described later can be adsorbed efficiently.
The dissociative functional group is, for example, a functional group that dissociates hydrogen ions or metal ions (for example, alkali metal ions, alkaline earth metal ions, etc.). Specific examples include a carboxyl group and a phosphate group.
Among them, ionic dissociable groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, boronic acid groups, or salts thereof (ion) due to their high polarity and high adsorption ability to plating catalysts or their precursors. Polar group) is preferred, and a carboxyl group is more preferred.
Two or more of these functional groups as interactive groups may be contained in the polymer.

The weight average molecular weight of the polymer is not particularly limited, but is preferably from 5,000 to 700,000, more preferably from 8,000 to 200,000. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
Further, the degree of polymerization of the polymer is not particularly limited, but it is preferable to use a polymer of 10-mer or more, and more preferably a polymer of 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 polymer, 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 property represented by the following formula (b) Examples thereof include a copolymer containing a unit having a 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 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 bromine atom.
R ² is preferably a hydrogen atom, a methyl group, or a methyl group substituted with 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 or a substituted or unsubstituted divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), -O —, —S—, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, alkylene Oxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.).
As a substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, or a butylene group, or these groups are substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like Those are preferred.
As the substituted or unsubstituted aromatic hydrocarbon group, an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom or the like is preferable.

  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 X, Y, and Z mentioned above.
L ¹ is preferably an aliphatic hydrocarbon group (for example, an aliphatic hydrocarbon group), and among them, one having a total carbon number of 1 to 9 is 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.

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, and those groups substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, etc., The group which combined these is mentioned.

  In said formula (b), W represents the dissociative functional group which interacts with a plating catalyst or a precursor. The definition of this functional group is the same as the above-mentioned definition.

  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.

  Moreover, as a suitable aspect of the interactive group unit represented by Formula (b), the unit represented by the following formula (e) or Formula (f) is mentioned.

In the above formula (e), W, 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.

In the formula (f), W and R ⁵ are the same as the definitions of each group in the unit represented by the formula (b).

It is preferable that the said polymeric group unit is contained by 5-50 mol% with respect to all the units in a polymer, More preferably, it is 5-40 mol%. If it is less than 5 mol%, the reactivity (curability, polymerizability) may be lowered, and if it exceeds 50 mol%, gelation tends to occur during synthesis and synthesis is difficult.
Moreover, it is preferable that the said interactive group unit is contained by 5-95 mol% with respect to all the units in a polymer from a adsorptive viewpoint with respect to a plating catalyst or its precursor, More preferably, it is 10-85. Mol%.

(Other units)
The polymer may have other functional groups in addition to the polymerizable group and the interactive group as long as the effects of the present invention are not impaired. For example, a non-dissociable functional group that interacts with a plating catalyst or a precursor thereof can be used.
Non-dissociative functional groups include, for example, amino groups, amide groups, imide groups, urea groups, tertiary amino groups, ammonium groups, amidino groups, triazine rings, triazole rings, benzotriazole groups, imidazole groups, and benzimidazole groups. 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 A nitrogen-containing functional group such as a group containing, a nitro group, a nitroso group, an azo group, a diazo group, an azide group, a cyano group, and a cyanate group (R—O—CN); an ether group, a phenolic hydroxyl group, a carbonate group, a carbonyl group, An ester group, a group containing an N-oxide structure, a group containing an S-oxide structure, Oxygen-containing functional groups such as groups containing a roxy structure; thiophene groups, thiol groups, thiourea groups, thiocyanuric acid groups, benzthiazole groups, mercaptotriazine groups, thioether groups, thioxy groups, sulfoxide groups, sulfone groups, sulfite groups, sulfoximines A sulfur-containing functional group such as a group containing a structure, a group containing a sulfoxynium salt structure or a group containing a sulfonate structure; a phosphorus-containing functional group such as a phosphoramide group, a phosphine group or a group containing a phosphate ester structure; Examples thereof include groups containing halogen atoms such as chlorine and bromine, and these salts can also be used in functional groups that can take a salt structure.
Among these, an ether group or a cyano group is preferable because of its high adsorption ability to a plating catalyst or a precursor thereof.

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.

  In addition, the said polymer may contain the unit which has a non-dissociative functional group represented by a following formula (g).

In formula (g), 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 (g), 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 (g), 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 (g), V represents a non-dissociable functional group.

  When the unit represented by the formula (g) is contained in the polymer, the content is 10 to 70 mol% with respect to all the units in the polymer from the point of adsorptivity such as a plating catalyst. Is more preferable, it is 20-60 mol%, More preferably, it is 25-50 mol%.

  Specific examples of the polymer include those having a radical polymerizable group and a functional group that interacts with a plating catalyst or a precursor thereof, paragraphs [0106] to [0112] of JP-A-2009-007540. Can be used. As the polymer having a radical polymerizable group and an ionic polar group, the polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 can be used. Examples of the polymer having a radical polymerizable group, a functional group that interacts with a plating catalyst or a precursor thereof, and an ionic polar group include polymers described in paragraphs [0030] to [0108] of US2010-080964. Can be used.

(Polymer synthesis method)
The method for synthesizing the polymer is not particularly limited, and the monomer used may be a commercially available product or one synthesized by combining known synthesis methods. For example, the polymer can be synthesized with reference to the method described in paragraphs [0120] to [0164] of Japanese Patent Publication No. 2009-7762.

<Other optional components in the composition for forming a layer to be plated>
(solvent)
The composition for forming a layer to be plated may contain a solvent as necessary.
The solvent that can be used is not particularly limited. For example, water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, alcohol solvents such as 1-methoxy-2-propanol, acids such as acetic acid, acetone, and methyl ethyl ketone. , Ketone solvents such as cyclohexanone, amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propyronitrile, ester solvents such as methyl acetate and ethyl acetate, dimethyl carbonate and diethyl carbonate Other examples include carbonate solvents such as ether solvents, glycol solvents, amine solvents, thiol solvents, and halogen solvents.
Among these, alcohol solvents, amide solvents, ketone solvents, nitrile solvents, carbonate solvents are preferable, specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, Dimethyl carbonate and 1-methoxy-2-propanol are preferred.

(Polymerization initiator)
A polymerization initiator may be contained in the composition for forming a layer to be plated of the present invention. By including a polymerization initiator, a bond between the polymer, between the polymer and the substrate, and between the polymer and the compound represented by the formula (1) is further formed, and as a result, a metal having better adhesion. A membrane can be obtained.
The polymerization initiator to be used is not particularly limited, and examples thereof include a thermal polymerization initiator, a photopolymerization initiator (radical polymerization initiator, anionic polymerization initiator, and cationic polymerization initiator), and further, a polymerization initiation ability in the side chain. A polymer having a functional group having a crosslinkable group and a crosslinkable group (polymerization initiating polymer) can be used.

(monomer)
The composition for forming a layer to be plated of the present invention may contain a monomer other than the compound represented by the above formula (1). By including the monomer, the crosslinking density in the layer to be plated can be appropriately controlled.
The monomer to be used is not particularly limited, and examples thereof include compounds having an ethylenically unsaturated bond as compounds having addition polymerizability, and compounds having an epoxy group as compounds having ring-opening polymerizability.

Specific examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof, such as acryloyl group, methacryloyl group, ethacryloyl group, allyl group. And compounds containing vinyl ether groups, vinyl thioether groups, and the like.
Further, from the viewpoint of molecular mobility during the cross-linking reaction that affects the reactivity, the molecular weight of the monomer used is preferably 70 to 1000, more preferably 100 to 700.

(Other additives)
In the composition for forming a layer to be plated of the present invention, other additives (for example, a sensitizer, a curing agent, a polymerization inhibitor, an antioxidant, an antistatic agent, an ultraviolet absorber, a filler, particles, a flame retardant, Surfactants, lubricants, plasticizers, etc.) may be added as necessary.

<Composition for plating layer formation>
The composition for forming a plated layer of the present invention includes a compound represented by the above formula (1) and a polymer having the polymerizable group.
Although content of the compound represented by Formula (1) in the composition for to-be-plated layer forming is not restrict | limited in particular, 1-80 mass% is preferable with respect to the composition whole quantity, and 5-50 mass% is more preferable. . If it is in the said range, it is excellent in the handleability of a composition and excellent in the adhesiveness of the metal film obtained.

  Although content of the polymer in the composition for to-be-plated layer forming is not restrict | limited in particular, 10-99 mass% is preferable with respect to the composition whole quantity, and 20-85 mass% is more preferable. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.

  Mass ratio of mass (mass A) of the compound represented by the formula (1) and the total mass of the mass A of the compound and the mass of the polymer (mass B) in the composition for forming a plating layer {mass A / (Mass A + mass B)} is not particularly limited, but is preferably 0.02 to 0.50, and more preferably 0.05 to 0.30 in terms of appropriately controlling the crosslinking density. .

  When a solvent is contained in the composition for forming a layer to be plated, the content of the solvent is preferably 50 to 99% by mass and more preferably 70 to 97% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.

  When a polymerization initiator is contained in the composition for forming a layer to be plated, the content of the polymerization initiator is preferably 0.01 to 1% by mass with respect to the total amount of the composition, and 0.1 to 0. More preferably, it is 5 mass%. If it is in the said range, it is excellent in the handleability of a composition and excellent in the adhesiveness of the metal film obtained.

  When a composition other than the compound represented by Formula (1) is contained in the composition for forming a layer to be plated (particularly a polyfunctional monomer), the content thereof is 0.01 to It is preferably 5% by mass, more preferably 0.1-1% by mass. If it is in the said range, it is excellent in the handleability of a composition and excellent in the adhesiveness of the metal film obtained.

<Method for producing laminate having metal film>
By using the above-described composition for forming a layer to be plated, a laminate having a metal film can be manufactured. The manufacturing method mainly includes the following three steps.
(Plating layer forming step) After contacting the composition for forming a layer to be plated on a substrate, energy is applied to the composition for forming a layer to be plated on the substrate to form a layer to be plated on the substrate. Step of applying (catalyst applying step) Step of applying a plating catalyst or precursor thereof to the layer to be plated (plating step) Plating treatment is applied to the layer of plating to which the plating catalyst or precursor thereof has been applied. The process of forming a metal film on the material The material used in each process and the operating method thereof will be described in detail below.

<Plating layer forming process>
In the plating layer forming step, after contacting the composition for forming a layer to be plated on the substrate, energy is applied to the composition for forming a layer to be plated on the substrate to form the layer to be plated on the substrate. It is a process to do.
The to-be-plated layer formed by this process adsorbs (adheres) the plating catalyst or its precursor in a catalyst application process described later according to the function of the interactive group contained in the polymer. That is, the layer to be plated functions as a good receiving layer for the plating catalyst or its precursor. Moreover, a polymeric group is utilized for the chemical bond with the coupling | bonding of polymers and a board | substrate (or adhesion assistance layer mentioned later). As a result, excellent adhesion appears between the metal film (plating film) formed on the surface of the layer to be plated and the substrate. Moreover, the alkali solution resistance of a to-be-plated layer improves because the compound represented by Formula (1) chemically bonds with a polymer.
More specifically, in this step, a substrate 10 is prepared as shown in FIG. 1A, and a layer 12 to be plated is formed on the substrate 10 as shown in FIG. As will be described later, the substrate 10 may have a close adhesion auxiliary layer on its surface. In this case, the layer to be plated 12 is formed on the close adhesion auxiliary layer.
First, the materials (substrate, adhesion auxiliary layer, etc.) used in this step will be described in detail, and then the procedure of the step will be described in detail.

(substrate)
As a substrate used in the present invention, any conventionally known substrate (for example, an insulating substrate) can be used, and a substrate that can withstand the processing conditions described later is preferable. Moreover, it is preferable that the surface has a function which can be chemically bonded with the polymer mentioned later. Specifically, the substrate itself can form a chemical bond with the polymer by applying energy (for example, exposure), or an intermediate layer on the substrate that can form a chemical bond with the layer to be plated by applying energy. (For example, an adhesion auxiliary layer described later) may be provided.

  The material of the substrate is not particularly limited. For example, polymer material, metal material (for example, metal alloy, metal-containing material, pure metal, or the like), other materials (for example, paper, plastic are laminated) Paper), combinations thereof, or the like, or the like.

As the polymer material, a thermoplastic resin, a thermosetting resin, or the like can be used, and conventionally known general-purpose plastics or engineering plastics can be used.
Examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, a polyolefin resin, and an isocyanate resin.
Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, ABS resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, and polymethyl methacrylate. , Polyether ether ketone, polyamide, polylactic acid, cycloolefin copolymer (COP), liquid crystal polymer (LCP), and the like.

  Specific examples of the metal material are appropriately selected from a mixture of aluminum, zinc, copper and the like, an alloy, and an alloy thereof.

  Also, base paper (non-coated paper), fine paper, art paper, coated paper, cast coated paper, baryta paper, wallpaper, backing paper, synthetic resin, emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin fat-added paper Paperboard, cellulose fiber paper, cellulose ester, acetylcellulose, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyolefin coated paper (especially paper coated on both sides with polyethylene), etc. Craft paper can also be used. Synthetic paper (polyolefin-based or polystyrene-based synthetic paper), cloth, or the like can also be used.

Moreover, the board | substrate may have metal wiring in the inside or one side or both surfaces. The metal wiring may be formed in a pattern with respect to the surface of the substrate or may be formed on the entire surface. Typically, those formed by a subtractive method using an etching process and those formed by a semi-additive method using electrolytic plating may be used, and those formed by any method may be used.
Examples of the material constituting the metal wiring include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc, and gallium.
As a substrate having such a metal wiring, for example, a double-sided or single-sided copper-clad laminate (CCL) or a copper film of this copper-clad laminate is used as a pattern, and these are flexible substrates. It may be a rigid substrate.
For example, an insulating substrate having a metal wiring layer and an insulating layer in this order on the surface may be used as the substrate of the present invention. In that case, two or more metal wiring layers and insulating layers may be alternately laminated.

In addition, the laminate of the present invention can be applied to semiconductor packages, various electric wiring boards, and the like. When using for such a use, it is preferable to use the board | substrate (insulating board | substrate) which has the layer (insulating resin layer) of insulating resin on the surface.
As the insulating resin, a known material can be used.
Further, for example, an insulating substrate having a metal wiring layer and an insulating layer on the surface thereof in this order may be used as the substrate of the present invention. In that case, two or more metal wiring layers and insulating layers may be alternately laminated.

(Adhesion auxiliary layer)
The adhesion auxiliary layer is an arbitrary layer that may be provided on the surface of the substrate, and plays a role of assisting adhesion between the substrate and a layer to be plated described later. The adhesion auxiliary layer is preferably one that forms a chemical bond with the polymer when energy is applied (for example, exposure) to the polymer. In addition, the adhesion auxiliary layer may contain a polymerization initiator.

The thickness of the adhesion auxiliary layer needs to be appropriately selected depending on the surface smoothness of the substrate, etc., but is generally preferably 0.01 to 100 μm, more preferably 0.05 to 20 μm, particularly 0.05 to 10 μm. Is preferred.
In addition, the surface smoothness of the adhesion auxiliary layer is such that the surface roughness Rz measured by JIS B 0601 (1994), 10-point average height method is 3 μm or less from the viewpoint of improving the physical properties of the formed metal film. And Rz is more preferably 1 μm or less.

  The material for the adhesion auxiliary layer is not particularly limited, and is preferably a resin having good adhesion to the substrate. When the substrate is made of an electrically insulating resin, it is preferable to use a resin having a close thermal property such as a glass transition point, an elastic modulus, and a linear expansion coefficient. Specifically, for example, it is preferable to use the same type of insulating resin as the insulating resin constituting the substrate in terms of adhesion.

In the present invention, the insulating resin used for the adhesion assisting layer means a resin having an insulating property that can be used for a known insulating film, 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. For example, examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, a polyolefin resin, and an isocyanate resin. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin.
The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more.
In addition, a resin containing a cyano group may be used. Specifically, an ABS resin or a “unit having a cyano group in a side chain” described in JP 2010-84196 [0039] to [0063] is included. "Polymer" may be used.

  The method for forming the adhesion auxiliary layer is not particularly limited, and a method of laminating a resin to be used on a substrate or a method in which a necessary component is dissolved in a soluble solvent, and coating and drying on the substrate surface by a method such as coating. The method etc. are mentioned.

(Procedure for forming the layer to be plated)
The method for bringing the composition for forming a layer to be plated into contact with the substrate (or on the adhesion auxiliary layer) is not particularly limited, and the method for laminating the composition for forming a layer to be plated directly on the substrate or the formation of the layer to be plated When the composition for use is a liquid containing a solvent, a method of coating the composition on a substrate can be mentioned. From the viewpoint of easily controlling the thickness of the obtained layer to be plated, a method of applying the composition on the substrate is preferable.
The coating method is not particularly limited, and specific examples include a double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, curtain coater, die coater, spin coater, dip coater, screen printing, and gravure roll coating. Known methods such as a construction method, extrusion coating method, microcontact printing, and roll coating method can be used.
From the viewpoint of handleability and production efficiency, an embodiment in which a composition for forming a layer to be plated is applied and dried on a substrate (or an adhesion auxiliary layer) to remove a solvent contained therein to form a composition layer containing a polymer. Is preferred.

When the composition for forming a layer to be plated is brought into contact with the substrate, the coating amount is 0.01 g / m ^{2 in} terms of solid content from the viewpoint of sufficient interaction formation with a plating catalyst or a precursor thereof described later. preferably 10 g / m ^2, especially 0.1g / m ² ~5g / m ² is preferred.
In addition, when forming a to-be-plated layer in this process, you may leave at 20-40 degreeC for 0.5 to 2 hours between application | coating and drying, and you may remove the remaining solvent.

(Granting energy)
The method for applying energy to the composition for forming a layer to be plated on the substrate is not particularly limited. For example, light (ultraviolet light, visible light, X-ray, etc.), plasma (oxygen, nitrogen, carbon dioxide, argon, etc.), heat, electricity Known methods such as moisture curing and chemical curing (for example, chemically decomposing the surface with an oxidizing liquid (potassium permanganate solution) or the like) can be used. In particular, exposure treatment or heat treatment is preferred.
Further, the atmosphere for imparting energy is not particularly limited, and it may be carried out in an atmosphere in which substitution with an inert gas such as nitrogen, helium, argon or carbon dioxide is performed and the oxygen concentration is suppressed to 600 ppm or less, preferably 400 ppm or less. .

In the case of exposure, for example, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, Deep-UV light, xenon lamp, chemical lamp, carbon arc lamp, light irradiation with visible light, etc., scanning exposure with infrared laser, There are high-intensity flash exposures such as xenon discharge lamps, infrared lamp exposures, etc., and there are ozone-less types that generate less ozone. In addition, examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, and high-density energy beam (laser beam) can be used. Especially, it is preferable to expose with the exposure wavelength of 250 nm-450 nm.
The exposure energy may be about 10~8000mJ / cm ^2, preferably in the range of 100~6000mJ / cm ^2, particularly preferably 2000 mJ / cm ² ultra 5000 mJ / cm ² or less.

  In the case of curing by heat, a general thermal heat roller, laminator, hot stamp, electric heating plate, thermal head, laser, blower dryer, oven, hot plate, infrared dryer, heating drum, or the like can be used.

Although the thickness of the to-be-plated layer obtained is not restrict | limited in particular, 0.01-10 micrometers is preferable from the point of the adhesiveness to the board | substrate of a metal film, and 0.05-5 micrometers is more preferable.
The dry film is preferably 0.01 to 20 g / m ² in thickness, especially 0.05~6g / m ² preferred.
Furthermore, the surface roughness (Ra) of the layer to be plated is preferably 0.001 to 0.3 [mu] m, more preferably 0.01 to 0.15 [mu] m, from the viewpoint of wiring shape and adhesion strength. In addition, the surface roughness (Ra) was measured using Surfcom 3000A (manufactured by Tokyo Seimitsu Co., Ltd.) based on Ra described in JIS B 0601 (Revision of 201010120) by non-contact interference method.

  In addition, it is preferable that content of the polymer in a to-be-plated layer is 2 mass%-99 mass% with respect to the to-be-plated layer whole quantity, More preferably, it is the range of 10 mass%-85 mass%.

  In addition, when energy is applied, energy may be applied in a pattern, and then a non-energy-irradiated portion may be removed by a known development process to form a patterned plating layer.

<Catalyst application step>
In a catalyst provision process, a plating catalyst or its precursor is provided to the to-be-plated layer obtained at the said layer formation process.
In this step, the polymer-derived interactive group adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. More specifically, a plating catalyst or a precursor thereof is applied in the layer to be plated and on the surface of the layer to be plated.
Here, as a plating catalyst or its precursor, what functions as a catalyst or an electrode of a plating process in the plating process mentioned later is mentioned. Therefore, although a plating catalyst or its precursor is determined by the kind of plating process in a plating process, it is preferable that it is an electroless-plating catalyst or its precursor.
First, the material (electroless plating catalyst or its precursor etc.) used at this process is explained in full detail, and the procedure of this process is explained in full detail after that.

(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 used as an electroless plating catalyst after being applied to the layer to be plated and before being immersed in the electroless plating bath, by separately changing to a zero-valent metal by a reduction reaction. 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.

The metal ion that is the electroless plating catalyst precursor is preferably applied to the layer to be plated 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.

(Plating catalyst solution)
As described above, the plating catalyst as described above or a precursor thereof is preferably applied to the layer to be plated as a dispersion or solution (plating 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 layer to be plated is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the interactive group.

  The organic solvent used for the preparation of the dispersion or solution is not particularly limited as long as it is a solvent that can penetrate into the layer to be plated. 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.

(Procedure for applying catalyst)
The method for applying the plating catalyst or its precursor to the layer to be plated is not particularly limited.
For example, a dispersion in which a metal is dispersed in an appropriate dispersion medium or a solution containing a dissociated metal ion by dissolving a metal salt in an appropriate solvent is prepared, and the dispersion or solution (plating catalyst solution) is plated. The method of apply | coating on a layer, the method of immersing the board | substrate with which the to-be-plated layer was formed in the dispersion liquid or solution, etc. are mentioned.
The contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.
The temperature of the plating catalyst solution at the time of contact is preferably about 10 to 60 ° C, more preferably about 10 to 40 ° C.

The amount of adsorption of the plating catalyst or precursor of the layer to be plated varies depending on the type of plating bath used, the type of catalyst metal, the type of interactive base of the layer to be plated, the method of use, etc. 5 to 1000 mg / m ² is preferable, 10 to 800 mg / m ² is more preferable, and 15 to 600 mg / m ² is particularly preferable.

<Plating process>
A plating process is a process of performing a plating process with respect to the to-be-plated layer which the plating catalyst obtained by the catalyst provision process or its precursor adsorb | sucked, and forming a metal film on a to-be-plated layer. More specifically, as shown in FIG. 1C, in this step, the metal film 14 is formed on the layer 12 to be plated, and the laminate 16 is obtained.
Examples of the plating treatment performed in this step include electroless plating and electrolytic plating. In the above step, the plating treatment is selected depending on the function of the plating catalyst or its precursor that forms an interaction with the layer to be plated. be able to.
Especially, it is preferable to perform electroless plating from the point of the formation of the hybrid structure which expresses in a to-be-plated layer, and the adhesive improvement of a metal film. Moreover, in order to obtain the metal film 14 with a desired film thickness, it is a more preferable aspect that electrolytic plating is further performed after the 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. In addition, as an electroless-plating bath, the case where an alkaline electroless-plating bath (pH is preferable about 9-14) is preferable from the point of availability.
In addition, when the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the layer to be plated, the substrate is washed with water to remove excess. After removing the 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.
When dipping, keep the concentration of the electroless plating catalyst or its precursor near the surface of the layer to be plated in contact with the electroless plating catalyst or its precursor, and soak it with stirring or shaking. Is preferred.

  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.

  As the types of metals used in the electroless plating bath, for example, copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known. Among them, copper and gold are particularly preferable from the viewpoint of conductivity. preferable. 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 to be 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.

(Electrolytic plating (electroplating))
In this step, when the plating catalyst or its precursor applied in the above step has a function as an electrode, electrolytic plating can be performed on the layer to be plated to which the catalyst or its precursor is applied. it can.
Further, after the above-described electroless plating, the formed metal film may be used as an electrode, and further electrolytic plating may be 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 electrolytic plating, a conventionally known method can be used. Examples of the metal used for electrolytic plating include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is more preferable. preferable.

Moreover, the film thickness of the metal film obtained by electrolytic plating 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.

<Laminated body>
By passing through the said process, as shown in FIG.1 (C), the laminated body 16 (laminated body with a metal film) provided with the board | substrate 10, the to-be-plated layer 12, and the metal film 14 in this order can be obtained. it can.
The obtained laminate 16 can be used in various fields, for example, electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile. It can be used in a wide range of industrial fields such as precision equipment, wood, building materials, civil engineering, furniture, printing and musical instruments.
More specifically, printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc. Office equipment, OA equipment, washing machine, refrigerator, vacuum cleaner, microwave oven, lighting equipment, game machine, iron, kotatsu and other household appliances, TV, VTR, video camera, radio cassette, tape recorder, mini-disc, CD player, speaker , AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, semiconductor chips, various electrical wiring Board, FPC, COF, TAB, 2-layer CCL (Copper Clad Lami ate) material, an electrical wiring material, a multilayer wiring board, a motherboard, antennas, electromagnetic wave shielding film, electrical and electronic parts such as a watch, and are used for applications such as communications equipment.

  In particular, since the smoothness at the interface between the metal film and the layer to be plated has been improved, for example, ornaments (eyeglass frames, automobile ornaments, jewelry, play enclosures, western dishes, water fittings, lighting fixtures, etc.) The present invention can be applied to various applications such as applications (for example, for wiring boards and printed wiring boards) that need to ensure high frequency transmission.

<Optional process: Pattern formation process>
As needed, you may implement the process of etching a metal film in pattern shape with respect to the laminated body obtained above, and forming a patterned metal film.
More specifically, as shown in FIG. 1D, in this step, a patterned metal film 18 is formed on the plated layer 12 by removing unnecessary portions of the metal film 14. . In this step, a metal film having a desired pattern can be generated by removing unnecessary portions of the metal film formed over the entire substrate surface by etching.
Any method can be used to form this pattern. Specifically, a generally known subtractive method (a patterned mask is provided on a metal film and an unformed region of the mask is etched). After that, the mask is removed to form a patterned metal film), a semi-additive method (a plating process is performed so that a patterned mask is provided on the metal film, and a metal film is formed in a non-mask formation region) , Removing the mask, and performing an etching process to form a patterned metal film).

Specifically, the subtractive method provides a resist layer on the formed metal film, forms the same pattern as the metal film pattern part by pattern exposure and development, and removes the metal film with an etching solution using the resist pattern as a mask. In this method, a patterned metal film is formed.
Any material can be used as the 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.

More specifically, FIG. 2 shows an aspect of an etching process using a subtractive method.
First, by performing the plating step, the substrate 10, the metal wiring 20, the insulating resin layer 22, the adhesion auxiliary layer 24, the layer to be plated 12, and the metal film 14 shown in FIG. A laminate comprising: is prepared. In FIG. 2A, metal wiring 20 is provided on the surface of the substrate 10 and inside thereof. The insulating resin layer 22, the adhesion auxiliary layer 24, and the metal wiring 20 are constituent members that are added as necessary. In FIG. 2A, the metal film 14 is provided on one side of the substrate 10, but it may be provided on both sides.
Next, as shown in FIG. 2B, a patterned mask 26 is provided on the metal film 14.
Thereafter, as shown in FIG. 2C, the metal film 14 in the region where the mask is not provided is removed by an etching process (for example, dry etching or wet etching) to obtain a patterned metal film 18. Finally, the mask 26 is removed to obtain the laminate of the present invention (see FIG. 2D).

Specifically, the semi-additive method is to provide a resist layer on the formed metal film, form the same pattern as the non-metal film pattern part by pattern exposure and development, perform electroplating using the resist pattern as a mask, This is a method of forming a patterned metal film by performing quick etching after removing the resist pattern and removing the metal film in a pattern.
The resist, the etching solution, etc. can use the same material as the subtractive method. Moreover, the above-described method can be used as the electrolytic plating method.

More specifically, FIG. 3 shows an aspect of an etching process using a semi-additive method.
First, a laminate including the substrate 10, the metal wiring 20, the insulating resin layer 22, the adhesion auxiliary layer 24, the layer to be plated 12, and the metal film 14 shown in FIG. 3A is prepared.
Next, as shown in FIG. 3B, a patterned mask 26 is provided on the metal film 14.
Next, as shown in FIG. 3C, electrolytic plating is performed to form a metal film in a region where the mask 26 is not provided, thereby obtaining the metal film 14b.
Thereafter, as shown in FIG. 3D, the mask 26 is removed, an etching process (for example, dry etching, wet etching) is performed, and the laminate including the patterned metal film 18 as shown in FIG. Get.

  Note that the layer to be plated may be removed together with a known means (for example, dry etching) simultaneously with the removal of the metal film.

Further, when the etching process is performed by the semi-additive method, the process may be performed in order to obtain a multilayer wiring board as shown in FIG.
As shown in FIG. 4A, first, a laminate including a substrate 10, a metal wiring 20, an insulating resin layer 22, an adhesion auxiliary layer 24, a layer to be plated 12, and a metal film 14 is prepared. To do.
Next, as shown in FIG. 4B, the metal film 14, the plated layer 12, the adhesion auxiliary layer 24, and the insulating resin layer 22 are penetrated to reach the metal wiring 20 by laser processing or drill processing. A via hole is formed. If necessary, desmear treatment is then performed.
Further, as shown in FIG. 4C, a plating catalyst is applied to the formed via hole wall surface, and electroless plating and / or electrolytic plating is performed to obtain a metal film 28 in contact with the metal wiring 20. .
Further, as shown in FIG. 4D, a mask 26 having a predetermined pattern is provided on the metal film 28, and electrolytic plating is performed to obtain the metal film 30 (see FIG. 4E).
Thereafter, after removing the mask 26 (see FIG. 4F), an etching process (for example, dry etching or wet etching) is performed to obtain a patterned metal film 32 (see FIG. 4G). Thereafter, if necessary, the plated layer 12 and the adhesion auxiliary layer 24 may be removed by plasma treatment or the like (see FIG. 4H).

The laminate having the patterned metal film obtained above can be used for various applications. Especially, it can utilize suitably as a wiring board. Moreover, when using with a wiring board, you may provide an insulating layer on a laminated body as needed.
The wiring board including the laminate of the present invention and the insulating layer can form wiring with excellent adhesion to a smooth substrate, has high frequency characteristics, and even between fine wiring, Excellent insulation reliability.
A known material can be used for the insulating layer, and examples thereof include a known interlayer insulating film and a solder resist.

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

(Synthesis Example 1: Polymer 1)
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 M1 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. There, monomer M1: 14.3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.0 g, acrylic acid (manufactured by Tokyo Chemical Industry) 6.5 g, V-65 (manufactured by Wako Pure Chemical Industries) 0.4 g of N, An 8 g solution of N-dimethylacetamide was added dropwise over 4 hours.
After completion of the dropwise addition, the reaction solution 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 performed with water, and the solid matter was taken out to obtain 12.5 g of polymer 1.

The obtained polymer 1 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 (5H min), and a peak corresponding to the polymerizable group containing unit is 8.1 to 7.8 ppm (1 H min). 8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2-3.9 ppm (2H min), 3.5-3.3 ppm (2H min), 2.5- A broad peak was observed at 0.7 ppm (6H min), and a peak corresponding to a carboxylic acid-containing unit was observed broadly at 2.5-0.7 ppm (3H min), a polymerizable group-containing unit: a nitrile group-containing unit: It was found that the carboxylic acid group unit = 30: 21: 49 (mol%).

(Synthesis Example 2: Polymer 2)
In a 500 mL three-necked flask, 22 g of N, N-dimethylacetamide was placed and heated to 60 ° C. under a nitrogen stream. Thereto, the monomer M1: 29.6 g obtained above, acrylic acid (manufactured by Tokyo Chemical Industry) 15 g, V-65 (manufactured by Wako Pure Chemical Industries) 0.59 g N, N-dimethylacetamide 38 g solution over 6 hours. It was dripped. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 37 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) 0.18g and DBU118g were added to said reaction solution, and reaction was performed at room temperature for 12 hours. Thereafter, 116 g of a 70% by mass aqueous methanesulfonic acid 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 20 g of polymer 2 (weight average molecular weight 42,000) having the following structural formula was obtained. When the acid value of the obtained polymer 2 was measured using a potentiometric automatic titrator (manufactured by Kyoto Electronics Industry Co., Ltd.) and a 0.1 M sodium hydroxide aqueous solution as the titrant, the acid value of the polymer 2 was It was 5.7 mmol / g.

The obtained polymer 2 was dissolved in acetone and measured using an KBr crystal with an IR measuring device (manufactured by Horiba, Ltd.). As a result of IR measurement, no peak was observed in the vicinity of 2240 cm ⁻¹ , and it was found that cyano group was not contained in polymer 2. Further, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to the polymerizable group-containing unit are 7.8-8.1 ppm (1H min), 5.8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2- Broadly observed at 3.9 ppm (2H min), 3.3-3.5 ppm (2H min), 2.5-0.7 ppm (6H min), and a peak corresponding to a carboxylic acid group unit is 2.5- It was observed broadly at 0.7 ppm (3H min), and it was found that the polymerizable group-containing unit: carboxylic acid group unit = 33: 67 (mol ratio).

<Preparation of composition for forming layer to be plated>
Into a 100 ml beaker containing a magnetic stirrer, water, propylene glycol monomethyl ether, various acrylamide monomers, polymers 1-2, IRGACURE2959 (CIBA) were added according to Table 1, prepared, compositions 1-9, and comparative composition Items 1 to 6 were obtained.
Hereinafter, the content of each component is expressed as mass% with respect to the total amount of the composition. In Table 1, “initiator” means IRGACURE 2959 (CIBA).

<Examples 1 to 10 and Comparative Examples 1 to 6>
[Preparation of layer to be plated]
A substrate surface obtained by vacuum laminating GX-13 (Ajinomoto Fine Techno) on an FR-4 substrate (Hitachi Chemical, glass epoxy resin substrate) was treated with a 5% sodium hydroxide solution at 60 ° C. for 5 minutes.

Then, the to-be-plated layer was obtained according to the procedure of the following (exposure process) or (heating process).
(Exposure process)
The composition for forming a layer to be plated shown in Table 1 was dropped on the substrate surface on which GX-13 was laminated, and spin-coated at 3000 rpm for 20 seconds. In order to volatilize the solvent, it was dried in an oven at 150 ° C. for 15 minutes. Thereafter, the substrate was irradiated with UV (wavelength: 254 nm) under vacuum to cure the plated layer. The thickness of the obtained plated layer was 150 nm.
In addition, the exposure amount (J / cm < ² >) of UV irradiation was adjusted according to the composition to be used like Table 2 mentioned later.
(Heating process)
The composition for forming a layer to be plated shown in Table 1 was dropped on the substrate surface on which GX-13 was laminated, and spin-coated at 3000 rpm for 20 seconds. Thereafter, the substrate was heat-treated at 150 ° C. for 15 minutes and at 180 ° C. for 60 minutes to cure the layer to be plated. The thickness of the obtained plated layer was 140 nm.

[Catalyst application and electroless plating]
The obtained substrate with the layer to be plated was immersed in a cleaner conditioner solution ACL-009 (Uemura Kogyo) at 50 ° C. for 5 minutes and washed twice with pure water. Then, it was immersed in Pd catalyst provision liquid MAT-2 (Uemura Kogyo) at 30 ° C. for 5 minutes and washed twice with pure water.
Next, the substrate subjected to the above treatment was immersed in a reducing agent MAB (Uemura Industries) at 36 ° C. for 5 minutes and washed twice with pure water. Then, it was immersed for 5 minutes at room temperature in the activation treatment liquid MEL-3 (Uemura Kogyo), and immersed in electroless plating solution sulcup PEA (Uemura Kogyo) for 30 minutes without washing. The obtained metal film (electroless plating film) had a thickness of about 0.8 μm.

[Electrolytic plating]
As the electrolytic plating solution, a mixed solution of water 1283 g, copper sulfate pentahydrate 135 g, 98% concentrated sulfuric acid 342 g, 36% concentrated hydrochloric acid 0.25 g, ET-901M (Rohm and Haas) 39.6 g was used, and the holder was attached. The substrate and the copper plate were connected to a power source and subjected to electrolytic copper plating at 3 A / dm ^{2 for} 45 minutes to obtain a copper plating film (metal film) of about 21 μm.

<Evaluation>
(Peel strength measurement)
The laminates having the metal films obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were heated at 100 ° C. for 30 minutes, and further heated at 180 ° C. for 1 hour. The obtained sample was spaced by 10 mm, a 130 mm cut was made in parallel, and the end was cut by a cutter and started up by 10 mm. The peeled edge was grasped and the peel strength of the metal film was measured using an autograph (SHIMAZU) (tensile speed 50 mm / min). The results are shown in Table 2.

(Alkaline solution resistance)
As an alkaline solution, NaOH (40 g), Cleaner Securigant 902 (Atotech) (40 mL), and Cleaner Additive 902 (Atotech) (3 mL) are mixed, and water is added so that the liquid volume becomes 1 L. Thus, an alkaline aqueous solution was prepared.
The board | substrate with a to-be-plated layer obtained by the said [preparation of to-be-plated layer] in Examples 1-10 and Comparative Examples 1-6 was immersed in the said alkaline solution for 20 minutes at 60 degreeC.
The thickness of the plated layer before and after immersion was measured and evaluated according to the following criteria. In addition, the following thickness ratio is calculated | required by (thickness of the to-be-plated layer after immersion / thickness of the to-be-plated layer before immersion). Practically, “◎” and “◯” are preferable. The results are shown in Table 2.
“◎”: When the thickness ratio is 0.8 or more “◯”: When the thickness ratio is 0.6 or more and less than 0.8 “Δ”: The thickness ratio is 0.3 or more and less than 0.6 When “x” is present: When the thickness ratio is less than 0.3

  The thickness of the layer to be plated after the immersion and the thickness of the layer to be plated before immersion are measured by measuring SEM (scanning electron microscope) cross section at 10 or more arbitrary locations on the layer to be plated. Is an average value obtained by averaging.

(Electroless plating after alkali solution resistance)
Of the above electroless plating conditions in Examples 1 to 10 and Comparative Examples 1 to 6, “immersion in cleaner conditioner solution ACL-009 (Uemura Kogyo) at 50 ° C. for 5 minutes” is the test condition for the above (alkali solution resistance). It changed and electroless plating was performed. According to the following evaluation criteria, the surface state of the obtained electroless plating film was visually determined. Practically, “◯” is preferable. The results are shown in Table 2. In addition, unevenness means the part from which the thickness of a plating film differs and a color differs.
"○": When plating is uniform "△": When plating is uneven in part "X": When plating is uneven in most

As shown in Table 2, in Examples 1 to 10 using the compositions 1 to 9 corresponding to the composition for forming a plated layer of the present invention, excellent peel strength and alkaline solution resistance, and It was confirmed that the electroless plating property after the alkaline solution resistance test was excellent.
From the comparison between Example 1 and Example 7, the mass of the mass of the compound represented by the formula (1) (mass A) and the total mass of the mass A of the compound and the mass of the polymer (mass B). It was confirmed that when the ratio {mass A / (mass A + mass B)} is in a predetermined range (0.05 to 0.30), the alkaline solution resistance is more excellent.
Moreover, it was confirmed from the comparison with Example 1 and Example 8 that the direction with much energy provision in an exposure process shows the more excellent alkaline solution tolerance.
Furthermore, it was confirmed that by using an acrylamide monomer exhibiting a predetermined log P, a more excellent alkaline solution resistance was exhibited.

  On the other hand, in Comparative Examples 1 to 6 using Comparative Compositions 1 to 6 that do not correspond to the composition for forming a layer to be plated of the present invention, electroless plating properties after peel strength, alkali solution resistance, or alkali solution resistance test It was confirmed to be inferior.

<Example 11>
The substrate subjected to electrolytic copper plating obtained in Example 1 was heat-treated at 180 ° C./1 hour, and then a dry resist film (manufactured by Hitachi Chemical Co., Ltd .; RY3315, film) was formed on the metal film surface of the substrate. 15 μm thick) was laminated at 70 ° C. and 0.2 MPa with a vacuum laminator (manufactured by Meiki Seisakusho: MVLP-600). Next, a glass mask capable of forming a comb-type wiring (compliant with JPCA-BU01-2007) as defined in JPCA-ET01 is closely attached to the substrate laminated with the dry resist film, and the resist is exposed to light of 70 mJ with an exposure machine having a central wavelength of 405 nm. Irradiated with energy. Development was performed by spraying a 1% Na ₂ CO ₃ aqueous solution onto the exposed substrate at a spray pressure of 0.2 MPa. Thereafter, the substrate was washed with water and dried to form a subtractive resist pattern on the copper plating film.
Etching was performed by immersing the substrate on which the resist pattern was formed in an FeCl ₃ / HCl aqueous solution (etching solution) at a temperature of 40 ° C. to remove the copper plating film present in the region where the resist pattern was not formed. Thereafter, the resist pattern is swelled and peeled off by spraying a 3% NaOH aqueous solution onto the substrate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to form a comb-like wiring (pattern shape). Copper plating film) was obtained. The obtained wiring was L / S = 20 μm / 75 μm.

Furthermore, a solder resist (PFR800; manufactured by Taiyo Ink Mfg. Co., Ltd.) is vacuum-laminated on a laminate having a patterned copper plating film under conditions of 110 ° C. and 0.2 MPa, and an exposure machine having a center wavelength of 365 nm. The light energy of 420 mJ was irradiated.
Next, the laminate was subjected to a heat treatment at 80 ° C./10 minutes, and then developed by applying a NaHCO ₃ : 10% aqueous solution to the laminate surface at a spray pressure of 2 kg / m ² and dried. Thereafter, the laminate was irradiated again with light energy of 1000 mJ with an exposure machine having a center wavelength of 365 nm. Finally, a heat treatment at 150 ° C./1 hr was performed to obtain a wiring board coated with a solder resist.

<Example 12>
Instead of the entire surface exposure in forming the plated layer in Example 1, pattern exposure by laser irradiation was performed, and then the unexposed portion was developed and removed with 1% sodium bicarbonate water to obtain a patterned plated layer. . The obtained patterned plating layer is subjected to [application of catalyst and electroless plating] and “electrolytic plating” performed in Example 1, and a patterned copper plating film on the plating layer. Got.

10: Substrate 12: Plated layers 14, 14b: Metal film 16: Laminate 18: Patterned metal film 20: Metal wiring 22: Insulating resin layer 24: Adhesion auxiliary layer 26: Mask 28, 30: Metal film 32: Patterned metal film

Claims (4)

A composition for forming a layer to be plated, comprising a compound represented by the formula (1) and a polymer having a dissociative functional group and a polymerizable group that form an interaction with a plating catalyst or a precursor thereof.
(In the formula (1), R ¹ is .R ² and ^{R 3} represents a hydrogen atom or an alkyl group each independently represent a hydrogen atom or a hydrocarbon group. In addition, R ² and R ³ (It may be directly bonded to form a ring, or may be formed through an oxygen atom.)   The composition for forming a plated layer according to claim 1, wherein log P of the compound is −0.3 or more. After contacting the composition for forming a layer to be plated according to claim 1 or 2 on a substrate, energy is applied to the composition for forming a layer to be plated on the substrate, and A plated layer forming step for forming a plated layer;
A catalyst application step of applying a plating catalyst or a precursor thereof to the layer to be plated;
A method for producing a laminate having a metal film comprising: a plating process for performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied, and forming a metal film on the layer to be plated.   The wiring board containing the laminated body which has a metal film obtained from the manufacturing method of Claim 3.