JP2013041942A - Method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate having a metal layer excellent in adhesion to an inorganic substrate.SOLUTION: A method for manufacturing a laminate 18 having a metal layer 16 comprises the steps of: (1) forming a primer layer 12 on an inorganic substrate 10 using a composition for primer layer formation containing a hydrolyzate obtained by hydrolyzing a silane coupling agent having a prescribed functional group under a pH 1 to pH 8 condition and/or its condensate, and a resin; (2) forming a plated layer 14 on the primer layer 12; (3) applying a plating catalyst or its precursor to the plated layer 14; and (4) forming a metal layer 16 on the plated layer 14 by plating the plated layer 14, to which the plating catalyst or its precursor was applied.

Description

  The present invention relates to a method for manufacturing a laminate.

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.
A “subtractive method” is mainly used as a method for manufacturing such a metal wiring board. In this subtractive method, a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal layer 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 layer 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 layer 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 layer 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, there is a method of forming a polymer layer (layer to be plated) having high adhesion with the substrate on the substrate, plating the polymer layer, and etching the obtained metal layer. Known (Patent Document 1). According to this method, the adhesion between the substrate and the metal layer can be improved without roughening the surface of the substrate.
Patent Document 1 discloses that an adhesion auxiliary layer may be provided in order to improve the adhesion between the substrate and the polymer layer.

JP 2010-248464 A

In recent years, in order to meet the demand for miniaturization and higher functionality of electronic devices, further higher integration of fine wiring such as printed wiring boards is progressing. Along with this, further improvement in the adhesion of the wiring (metal pattern) to the substrate is required. In recent years, attempts have been made to use an inorganic substrate such as a glass substrate or a ceramic substrate as a substrate for a printed wiring board from the viewpoint of heat resistance and rigidity.
The inventors use the adhesion auxiliary layer specifically disclosed in the example of Patent Document 1, and use an inorganic substrate such as a glass substrate as the substrate, and adhere to the adhesion auxiliary layer and polymer on the inorganic substrate. After forming a layer and a metal layer and examining the adhesion of the metal layer, it is clear that the adhesion of the obtained metal layer (plating layer) does not necessarily reach the level required recently. Became.

  An object of this invention is to provide the manufacturing method of the laminated body which has a metal layer which is excellent in the adhesiveness with respect to an inorganic substrate in view of the said situation.

As a result of intensive studies on the cause of deterioration of the adhesion of the metal layer in the above-described conventional technology, the present inventors have found that the adhesion auxiliary layer (corresponding to the primer layer) and the adhesion between the adjacent inorganic substrate and the layer to be plated are However, I found that it was not always sufficient.
Based on the above findings, the present inventors have found that the above object can be achieved by the following means.

(1) A silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, an acryloyloxy group, a phenyl group, and a cyano group, under a pH of 1 to 8 A step (1) of forming a primer layer on an inorganic substrate using a composition for forming a primer layer containing a hydrolyzate obtained by hydrolysis and / or a condensate thereof, and a resin;
On the primer layer, a layer containing a polymer having a functional group and a polymerizable group that interacts with a plating catalyst or a precursor thereof is formed, and then energy is applied to the layer containing the polymer, A step (2) of forming a layer to be plated on the primer layer;
A step (3) of applying a plating catalyst or a precursor thereof to the layer to be plated;
Step (4) of performing a plating process on the layer to be plated to which a plating catalyst or a precursor thereof is applied and forming a metal layer on the layer to be plated, and a method for producing a laminate having a metal layer .

(2) The manufacturing method of the laminated body which has a metal layer as described in (1) whose range of the said pH is 1-4.
(3) The manufacturing method of the laminated body as described in (1) or (2) whose said resin contained in the said composition for primer layer formation is an elastomer.
(4) The manufacturing method of the laminated body which has a metal layer in any one of (1)-(3) whose Young's modulus of the said primer layer is 500 Mpa or less.

(5) The laminate having the metal layer according to any one of (1) to (4), wherein the resin contained in the primer layer forming composition has a unit represented by the following general formula (1). Body manufacturing method.
(6) The manufacturing method of the laminated body which has a metal layer in any one of (1)-(5) whose film thickness of the said primer layer is 4 micrometers or more.

(7) A laminate having a metal layer produced by the production method according to any one of (1) to (6).
(8) The manufacturing method of the laminated body which has a pattern-shaped metal layer provided with the pattern formation process which etches the metal layer in the laminated body as described in (7) in pattern shape, and forms a patterned metal layer.
(9) A printed wiring board including a laminate having a patterned metal layer obtained by the production method according to (8).

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated body which has a metal layer excellent in the adhesiveness with respect to an inorganic substrate can be provided.

(A)-(D) is a typical sectional view from an inorganic substrate to a layered product which shows each manufacturing process in a manufacturing method of a layered product which has a layered product and a patterned metal layer of the present invention in order, respectively.

Below, the manufacturing method of the laminated body which has a metal layer of this invention is demonstrated.
As a feature of the present invention, a hydrolyzate and / or a condensation product obtained by hydrolysis (hydrolysis reaction / condensation reaction) of a silane coupling agent having a predetermined functional group in the primer layer within a predetermined pH range. (Hereinafter, also referred to as a hydrolysis-condensation product as a general term for both). By using the hydrolyzed condensate and the resin in combination (preferably by reacting the hydrolyzed condensate and the resin), in particular, the adhesion between the inorganic substrate and the primer layer is improved. In particular, when the inorganic substrate is a substrate having a hydroxyl group on the surface (for example, a glass substrate), the hydroxyl group on the inorganic substrate reacts with a terminal group (silanol group) of the hydrolysis condensate (preferably reacted with a primer). In addition, the affinity of the interface between the inorganic substrate and the primer layer is improved, and as a result, the adhesion between the two is further improved. In addition, if the primer layer is within a predetermined Young's modulus range, stress that causes the adhesive force to deteriorate (stress due to difference in stress during thermal treatment, thermal expansion coefficient, shrinkage stress generated during polymerization of the plated layer, etc.) As a result, the function as a stress relaxation layer that relaxes is improved, and as a result, the adhesion of the metal layer is further improved.

The manufacturing method of the laminated body which has a metal layer of this invention has the process (1) which forms a primer layer (1st resin layer) on an inorganic substrate, and a to-be-plated layer (2nd on a formed primer layer). A step (2) of forming a resin layer), a step (3) of applying a plating catalyst or a precursor thereof to the layer to be plated, and a step of performing a plating process on the layer of plating to which the plating catalyst or precursor thereof has been applied. (4).
Below, the material used in each process and its procedure are explained in full detail. First, the step (1) will be described in detail.

[Step (1): Primer layer forming step]
In the step (1), a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, an acryloyl group, a phenyl group, and a cyano group is a pH 1-8 condition. This is a step of forming a primer layer on an inorganic substrate using a primer layer forming composition containing a hydrolyzate obtained by hydrolysis under the above and / or a condensate thereof and a resin.
More specifically, as shown in FIG. 1A, a primer layer 12 is formed on the inorganic substrate 10 in this step.

The primer layer formed at this process is arrange | positioned between an inorganic substrate and the to-be-plated layer mentioned later, and contributes to both adhesive improvement. Further, as described above, it also serves as a stress relaxation layer.
First, materials (inorganic substrate, hydrolyzate and / or its condensate, resin, primer layer forming composition, etc.) used in this step will be described in detail, and then the procedure of this step will be described in detail.

(Inorganic substrate)
The inorganic substrate is a member for supporting each layer to be described later, and any conventionally known inorganic substrate can be used. More specifically, examples of the inorganic substrate include substrates composed of metals such as titanium, gold, silver, copper, silicon, aluminum, and stainless steel, and inorganic materials such as ceramic, alumina, glass, quartz, mica, and silicon.
Among these, an inorganic substrate (for example, a glass substrate or a ceramic substrate) having a hydroxyl group on the surface is preferable because it is excellent in reactivity with a hydrolyzate of a silane coupling agent and / or a condensate thereof.

Moreover, the inorganic substrate may have a metal layer on one side or both sides separately from the metal layer formed in the step (4) described later. The metal layer may be formed in a pattern with respect to the surface of the inorganic 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 electroplating may be used, and those formed by any method may be used.
Examples of the material constituting the metal layer include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc, and gallium.
Moreover, you may have an insulating layer on the surface of an inorganic board | substrate.

(Hydrolyzate and / or condensate thereof)
The primer layer forming composition used in this step has at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, an acryloyloxy group, a phenyl group, and a cyano group. A hydrolyzate obtained by hydrolyzing a silane coupling agent under conditions of pH 1 to 8 and / or a condensate thereof (hydrolysis condensate) are included. By including the hydrolysis condensate in the primer layer, the adhesion between the inorganic substrate and the layer to be plated described later is improved, and as a result, the adhesion of the metal layer is improved.
First, the silane coupling agent used is described in detail, and then the method for preparing the hydrolysis condensate is described in detail.

(Silane coupling agent)
The silane coupling agent used has at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, an acryloyloxy group, a phenyl group, and a cyano group. Among these, an acryloyloxy group, a vinyl group, and an amino group are preferable because the adhesion of the layer to be plated is more excellent. In particular, when the resin has an unsaturated group, a cyano group, an epoxy group, etc., the acryloyloxy group reacts with the unsaturated group, cyano group, epoxy group, etc. to further improve the adhesion of the layer to be plated. A vinyl group is preferred.

  A preferred embodiment of the silane coupling agent includes a compound represented by the following general formula (2).

In the general formula (2), Z ^a represents an epoxy group, an amino group, a vinyl group, a mercapto group, acryloyloxy group, a phenyl group, or a cyano group.
Each R independently represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, etc., preferably having 1 to 12 carbon atoms), or an aromatic hydrocarbon group (for example, a phenyl group, a naphthyl group, etc.). . Of these, the hydrocarbon group is preferably a methyl group or an ethyl group.
When there are a plurality of R, they may be the same or different.

  W represents a hydrolyzable group. Specifically, an alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyloxy group (acetoxy) A methoxy group, an ethoxy group, and a chlorine atom are preferable in terms of good reactivity.

L ^b represents a single bond or a divalent organic group. As the divalent organic group, a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (for example, an arylene group, preferably). number 6-12), carbon - O -, - S -, - SO 2 -, - N (R) - (R: alkyl group), - CO -, - NH -, - COO -, - CONH-, Alternatively, a group in which these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, or the like) can be given. Among these, an alkylene group is preferable from the viewpoint of compound preparation.
In the case of a single bond, Z ^{a in the} general formula (2) is directly connected to Si.

  m represents an integer of 0 to 2, n represents an integer of 1 to 3, and satisfies the relationship of n + m = 3. Among these, m is preferably 0 to 1. n is preferably 2 to 3.

  Examples of the silane coupling agent used include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyl. Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-trimethoxysilylpropyl methacrylate, 3- (acryloxy) propyltri Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-methacryl Propyl methyl dimethoxy silane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl triethoxysilane, and vinyl trichlorosilane.

(Method for preparing hydrolysis condensate)
The hydrolysis condensate obtained using the silane coupling agent is obtained by hydrolysis (hydrolysis reaction and / or polycondensation reaction) under the conditions of pH 1-8. In particular, a pH range of 1 to 5 is preferable and 1 to 4 is more preferable in that the adhesion of the formed metal layer is more excellent. If it is in the said range, it will be excellent in the adhesiveness of the metal layer formed.
When the pH is outside the above range, the adhesion of the metal layer is poor.
When adjusting to the above pH range, a predetermined acidic component or alkaline component may be used as necessary. Examples of the acidic component used include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the alkali component include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and the like.

  If necessary, a silane coupling agent and a solvent may be mixed and the silane coupling agent may be hydrolyzed in the solvent. The kind of the solvent used is not particularly limited, and examples thereof include water, alcohol solvents (eg, methanol, ethanol, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.), amide solvents (eg, formamide, Dimethylacetamide, N-methylpyrrolidone, etc.), nitrile solvents (eg, acetonitrile, propyronitrile, etc.), ester solvents (eg, methyl acetate, ethyl acetate, etc.), carbonate solvents (eg, dimethyl carbonate, diethyl carbonate, etc.) In addition, ether solvents, glycol solvents, halogen solvents, and the like can be given.

  The reaction time for hydrolysis of the silane coupling agent is appropriately selected depending on conditions such as pH, but is usually preferably 1 minute or longer, more preferably 10 minutes or longer, and particularly preferably 30 minutes or longer. The upper limit is not particularly limited, but is preferably within 72 hours from the viewpoint of productivity and storage stability.

(resin)
The kind in particular of resin contained in the composition for primer layer formation is not restrict | limited, A well-known resin can be used. For example, thermosetting resins (for example, epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, isocyanate resins, etc.) and thermoplastic resins (for example, phenoxy resins, polyether sulfones, polysulfones, Polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, etc.).

  Especially, it is preferable that resin is an elastomer (elastomer component) at the point which the adhesiveness of a metal layer improves more by stress relaxation. Known materials can be used as the elastomer, such as acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-methyl methacrylate copolymer, methyl methacrylate-butadiene-acrylonitrile-styrene copolymer, methyl methacrylate-butadiene-styrene. Copolymer (MBS), acrylonitrile-styrene-butadiene copolymer, various synthetic rubbers such as acrylonitrile-butadiene rubber, linear polyurethane, styrene-butadiene rubber, chloroprene rubber and butadiene rubber, natural rubber, styrene-polybutadiene- Styrenic thermoplastic elastomers such as styrene synthetic rubber, olefinic thermoplastic elastomers such as polyethylene-EPDM synthetic rubber, and caprolact -Type, adipate-type and PTMG-type urethane-based thermoplastic elastomers, polybutylene terephthalate-polytetramethylene glycol multi-block polymer polyester-based thermoplastic elastomers, nylon-polyol block copolymers and nylon-polyester block copolymers Examples include thermoplastic elastomers, 1,2-polybutadiene thermoplastic elastomers, and vinyl chloride thermoplastic elastomers. These elastomer components can be used alone or in combination of two or more if the compatibility is good.

  As one preferred embodiment of the resin, it is preferable that the resin has a unit represented by the general formula (1) in that the adhesion of the metal layer is more excellent.

In the general 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 general 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.
In addition, resin may contain the unit represented by 2 or more types of General formula (1).

Other units (repeating units) contained in the resin are not particularly limited. For example, a unit derived from a linear or cyclic olefin compound (for example, ethylene or propylene), a unit derived from a conjugated diene compound, or a polar group A unit derived from an aromatic vinyl compound not having a polar group, a unit derived from a (meth) acrylate monomer having no polar group, a unit derived from a (meth) acrylamide monomer having no polar group, or the like is preferable.
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.

(Primer layer forming composition)
The primer layer forming composition used in this step contains the hydrolysis condensate and the resin.
Ratio of the amount (addition amount) of the silane coupling agent that is the starting material of the hydrolysis condensate in the composition for forming the primer layer to the amount of use (addition amount) with the resin (use of the silane coupling agent) The amount / amount used with the resin) is not particularly limited, but is preferably 0.01 to 1, and more preferably 0.01 to 0.1. If it is in the said range, adhesiveness with an inorganic board | substrate can be strengthened, utilizing the characteristic of primer resin.

The content of the hydrolysis condensate in the primer layer forming composition is not particularly limited, but is preferably 0.01 to 50% by mass, and preferably 0.01 to 10% by mass with respect to the total amount of the composition.
The content of the resin in the primer layer forming composition is not particularly limited, but is preferably 0.1 to 99.9% by mass, and more preferably 1 to 99.9% by mass with respect to the total amount of the composition.

  The composition for primer layer formation may contain the solvent as needed. The kind in particular of solvent used is not restrict | limited, For example, the solvent etc. which may be used in the case of the hydrolysis of the silane coupling agent mentioned above are mentioned.

The method for preparing the primer layer forming composition is not particularly limited. For example, the silane coupling agent and the resin are mixed in a solvent, adjusted to a predetermined pH, and the hydrolysis reaction of the silane coupling agent proceeds. And a method for preparing a primer layer forming composition having a hydrolysis-condensation product and a resin. Alternatively, a composition for forming a primer layer may be prepared by once preparing a hydrolysis-condensation product and mixing it with a resin.
The time for performing the hydrolysis of the silane coupling agent is not particularly limited, but is preferably 1 minute or more, more preferably 10 minutes or more, and 30 minutes in terms of excellent productivity of the metal layer and excellent productivity. The above is more preferable. Moreover, although it does not restrict | limit especially as an upper limit, from a viewpoint of subsequent storage stability, within 72 hours are preferable and within 24 hours are more preferable. In addition, when performing a hydrolysis by stirring a silane coupling agent in a solution, it is preferable if stirring time is in the said time.

  In addition, the composition for primer layer formation may contain the other additive (For example, a hardening accelerator, a vulcanizing agent, antioxidant, a plasticizer etc.) as needed.

(Procedure of step (1))
The method for forming the primer layer on the inorganic substrate using the primer layer forming composition described above is not particularly limited. For example, the primer layer forming composition is applied on the inorganic substrate to form the primer layer. (Hereinafter, also referred to as a coating method) and a method of laminating a primer layer forming composition on an inorganic substrate. Of these, the coating method is preferable because the control of the film thickness is ready.
As a coating method used in the coating method, a known method (for example, spin coating, dip coating, double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, etc.) is used. it can.

In addition, after apply | coating the composition for primer layer formation on an inorganic board | substrate, you may heat-process as needed. By performing the heat treatment, removal of the solvent contained in the composition and promotion of a crosslinking reaction between the resins are promoted.
The conditions for the heat treatment are not particularly limited, but are preferably 20 to 300 ° C, more preferably 50 to 220 ° C, and preferably 1 minute to 2 hours, and more preferably 1 minute to 30 minutes.

  The thickness of the primer layer formed by the above process is not particularly limited, but is preferably 0.6 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, from the viewpoint of further relaxing the plating stress and the thermal stress of the resin layer. 4 μm or more is particularly preferable. The upper limit is not particularly limited, but is preferably 30 μm or less and more preferably 10 μm or less from the viewpoint of further relaxing the plating stress and the thermal stress of the resin layer.

  The Young's modulus of the primer layer is not particularly limited, but is preferably 2000 MPa or less, more preferably 500 MPa or less, and more preferably 0.01 to 500 MPa from the viewpoint that the plating stress and the thermal stress of the resin layer are relaxed and the adhesion of the metal layer is more excellent. Is more preferable, and 0.1 to 250 MPa is particularly preferable.

[Step (2): Plated layer forming step]
Step (2) has a functional group (hereinafter also referred to as an interactive group as appropriate) and a polymerizable group that form an interaction with the plating catalyst or its precursor on the primer layer formed in step (1). This is a step of forming a layer containing a polymer, and then applying energy to the layer containing the polymer on the primer layer to form a layer to be plated on the primer layer.

The to-be-plated layer formed by this process adsorbs (attaches) the plating catalyst or its precursor in the process (3) described later, depending on 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 coupling | bonding of polymers and chemical coupling | bonding with a primer layer by the hardening process by energy provision. As a result, excellent adhesion is exhibited between the metal layer (plating layer) formed on the surface of the layer to be plated and the inorganic substrate.
More specifically, as shown in FIG. 1B, in this step, a layer 14 to be plated is formed on the primer layer 12.
First, materials (polymer, composition for forming a layer to be plated, etc.) used in this step will be described in detail, and then the procedure of the step will be described in detail.

(polymer)
The polymer used in this step has a polymerizable group and an interactive group.

  The polymerizable group is a functional group capable of forming a chemical bond between polymers or between the polymer and the primer layer by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Of these, a radical polymerizable group is preferable from the viewpoint of reactivity. Examples of radical polymerizable groups include acrylic acid ester groups (acryloyloxy groups), methacrylic acid ester groups (methacryloyloxy groups), itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, and the like. Examples include unsaturated carboxylic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups. Of these, a methacryloyloxy group, an acryloyloxy group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacryloyloxy group, an acryloyloxy group, and a styryl group are particularly preferable.

An interactive group is a functional group that interacts with a plating catalyst or a precursor thereof, a functional group that can form an electrostatic interaction with the plating catalyst or a precursor thereof, or a coordination group with a plating catalyst or a precursor thereof. Nitrogen-containing functional groups, sulfur-containing functional groups, oxygen-containing functional groups and the like that can be formed 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, a group containing an N-hydroxy structure; a thiophene group, a thiol group, a thiourea group, a thiocyanuric acid group, a benzthiazole group, a mercaptotriazine group, a thioether group, a thioxy group, a sulfoxide group, 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, since the polarity is high and the adsorption ability to a plating catalyst or a precursor thereof is high, an ionic polar group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group, an ether group, or A cyano group is particularly preferable, and a carboxyl group or a cyano group is more preferable.
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 1000 or more and 700,000 or less, more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
The degree of polymerization of the polymer is not particularly limited, but is preferably a 10-mer or more, and 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 of polymer)
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 formulas (a) and (b), R ^{1 to} R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. ). The substituent is not particularly limited, and examples thereof include 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. As the divalent organic group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted A divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, for example, a phenylene group), —O—, —S—, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like) can be given.

  As X, Y, and Z, a single bond, an ester group (—COO—), an amide group (—) can be used because the polymer can be easily synthesized and the functions of the plated layer (catalyst adsorption, hydrolysis resistance) are excellent. CONH-), an ether group (-O-), a substituted or unsubstituted divalent aromatic hydrocarbon group, and the like are preferable, and a single bond, an ester group (-COO-), 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 a divalent organic compound having an aliphatic hydrocarbon group, a urethane bond, or a urea bond in that the polymer is easily synthesized and the functions of the plated layer (catalyst adsorption, hydrolysis resistance) are excellent. A group (for example, an aliphatic hydrocarbon group) is preferable, and a group having 1 to 9 carbon atoms is particularly 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 easy to synthesize a polymer and has excellent functions (catalyst adsorbability, hydrolysis resistance) of the layer to be plated. From the viewpoint of L ² , a single bond, a divalent aliphatic hydrocarbon group, or a divalent aroma is used. It is preferably a group hydrocarbon group or a combination thereof. Among these, L ² is preferably a single bond or an aliphatic hydrocarbon group having 1 to 15 carbon atoms in total, and 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.

  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 the same as the definition of the interactive group described above.

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 10-95. Mol%.

(Preferred embodiment 2 of polymer)
As a 2nd preferable aspect of a polymer, the copolymer containing the unit represented by a following formula (A), a formula (B), and a formula (C) is mentioned.

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 a plating catalyst or a precursor thereof excluding a hydrophilic group represented by V described later or a precursor group thereof. Of these, a cyano group and an ether group are preferable.

In formula (C), each R ⁶ independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
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. U is a single bond, an ester group (—COO—), an amide group (—CONH—), an ether in that the polymer can be easily synthesized and the functions of the layer to be plated (catalytic adsorption, hydrolysis resistance) are excellent. The group (—O—) or a substituted or unsubstituted divalent aromatic hydrocarbon group is preferred.
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. L ³ is a single bond, a divalent aliphatic hydrocarbon group or a divalent aromatic in that the polymer is easily synthesized and the functions of the layer to be plated (catalyst adsorption, hydrolysis resistance) are excellent. It is preferably a hydrocarbon group or a group obtained by combining these.

In the formula (C), V represents a hydrophilic group or a precursor group thereof. The hydrophilic group is not particularly limited as long as it is a hydrophilic group, and examples thereof include a hydroxyl group and a carboxylic acid group. The precursor group of the hydrophilic group means a group that generates a hydrophilic group by a predetermined treatment (for example, treatment with acid or alkali). For example, carboxy protected with THP (2-tetrahydropyranyl group). Group and the like.
The hydrophilic group is preferably an ionic polar group because the layer to be plated is easily wetted with various aqueous treatment solutions and plating solutions. 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).

The preferred content of each unit in the second preferred embodiment of the polymer 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 polymer from the viewpoint of reactivity (curability and polymerization) and suppression of gelation during synthesis. It is preferably 5 to 30 mol%.
The unit represented by the formula (B) is preferably contained in an amount of 5 to 75 mol%, more preferably 10 to 10%, based on the entire unit in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor. 70 mol%.
The unit represented by the formula (C) is preferably contained in an amount of 10 to 70 mol%, more preferably 20 to 60 mol% with respect to all units in the polymer, from the viewpoint of developability with an aqueous solution and moisture-resistant adhesion. It is mol%, Especially preferably, it is 30-50 mol%.

Specific examples of the polymer include, for example, the polymers described in paragraphs [0106] to [0112] of JP2009-007540A, and the paragraphs [0065] to [0070] of JP2006-135271A. Examples thereof include polymers described in paragraphs [0030] to [0108] of US2010-080964.
The polymer can be produced by known methods (eg, the methods in the literature listed above).

(Procedure of step (2))
First, a method for forming a layer containing the polymer (layer to be plated precursor layer) on the primer layer is not particularly limited, and a known method can be used. For example, a method of applying a composition for forming a layer to be plated containing the polymer on the primer layer (application method), and a method of directly laminating the polymer on the primer layer can also be mentioned. Of these, the coating method is preferable because the film thickness of the layer to be plated can be easily controlled. About the aspect of the composition for to-be-plated layer forming, it mentions later.

In the case of the coating method, the method for coating the composition for forming a layer to be plated on the primer layer is not particularly limited, and a known method (for example, spin coating, die coating, dip coating, lamination, etc.) can be used.
From the viewpoint of handleability and production efficiency, a composition for forming a layer to be plated is applied on the primer layer, and if necessary, a drying treatment is performed to remove the remaining solvent, and a layer containing a polymer (layer to be plated) A mode of forming the forming composition layer) is preferred.
The conditions for the drying treatment are not particularly limited, but are 1 to 30 minutes (preferably 1 to 10 minutes) at room temperature to 220 ° C. (preferably 50 to 120 ° C.) in terms of more excellent productivity and adhesion of the metal layer. ) It is preferable to implement.
The coating amount of the composition for forming a layer to be plated is preferably 0.1 to 10 g / m ^{2 in} terms of solid content, particularly 0.5 to 0.5 from the viewpoint of sufficient interaction formation with the plating catalyst or its precursor. 5 g / m ² is preferred.

The method for applying energy to the layer containing the polymer on the primer layer (composition layer for plating layer formation) is not particularly limited. For example, it is preferable to use a heat treatment or an exposure process, and the exposure process is preferable from the viewpoint that the process is completed in a short time. By applying energy to the layer containing the polymer, the polymerizable group in the polymer is activated, cross-linking between the polymers and bonding between the polymer and the primer layer occur, and the curing of the layer proceeds.
For the exposure process, light irradiation with a UV lamp, visible light, or the like is used. 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. Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
The exposure time varies depending on the reactivity of the polymer and the light source, but is usually between 10 seconds and 5 hours. The exposure energy may be about 10 to 8000 mJ, and is preferably in the range of 50 to 3000 mJ.

  In addition, when using heat processing as energy provision, a ventilation dryer, oven, an infrared dryer, a heating drum, etc. can be used.

  Although the thickness of a to-be-plated layer is not restrict | limited in particular, 0.01-10 micrometers is preferable from the point of the adhesiveness of a metal layer, 0.1-5 micrometers is more preferable, and 0.1-1.0 micrometer is especially preferable.

(Composition for plating layer formation)
The composition for forming a layer to be plated contains the polymer.
Although content of the polymer in the composition for to-be-plated layer forming is not restrict | limited in particular, 2-50 mass% is preferable with respect to the composition whole quantity, and 3-10 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.

The composition for forming a layer to be plated may contain a solvent. By containing the solvent, the handleability is improved.
Solvents that can be used are not particularly limited, for example, alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, 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, carbonate solvents such as dimethyl carbonate and diethyl carbonate, and others In addition, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents and the like can be mentioned.
Among these, amide solvents, ketone solvents, nitrile solvents, and carbonate solvents are preferable, and specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, and dimethyl carbonate are preferable. .

  Although content of the solvent in the composition for to-be-plated layer forming is not restrict | limited in particular, 50-98 mass% is preferable with respect to the composition whole quantity, and 90-97 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.

[Step (3): Catalyst application step]
Step (3) is a step of applying a plating catalyst or a precursor thereof to the layer to be plated obtained in step (2).
In this step, the polymer-derived interactive group adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. More specifically, the plating catalyst or its precursor is adsorbed in the layer to be plated and on the surface of the layer to be plated.
First, materials (plating catalyst or its precursor etc.) used at this process are explained in full detail, and the procedure of this process is explained in full detail after that.

(Plating catalyst or its precursor)
The plating catalyst or its precursor functions as a catalyst or electrode for plating treatment in the plating step described later. Therefore, the type of plating catalyst or precursor used is appropriately determined depending on the type of plating treatment.
Hereinafter, mainly electroless plating or a precursor thereof will be described in detail as a plating catalyst or a precursor thereof.

As the electroless plating catalyst, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal having a catalytic ability for autocatalytic reduction reaction (which tends to be more ionized than Ni). And those known as metals capable of low electroless plating). More specifically, Pd, Ag, Cu, Ni, Al, Fe, Co, etc. are mentioned. Of these, Ag and Pd are particularly preferable because of their high catalytic ability.
As the electroless plating catalyst, metal colloid (metal particles) may be used. Generally, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent.

  Any electroless plating catalyst precursor 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 that 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 solution, by separately changing to a zero-valent metal by a reduction reaction. The electroless plating catalyst precursor may be immersed in an electroless plating solution and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating solution.

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.

  In this step, zero-valent metals other than those described above can also be used as a catalyst used for direct electroplating without electroless plating.

The plating catalyst or a precursor thereof is preferably used in the form of a dispersion or solution in which these are dispersed or dissolved in a solvent (hereinafter also referred to as a plating catalyst solution as appropriate).
As the solvent used in the plating catalyst solution, an organic solvent and / or water is used. When the plating catalyst solution contains an organic solvent, the permeability of the plating catalyst solution 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 plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the plating 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.

(Procedure of step (3))
The method for applying the plating catalyst or its precursor to the layer to be plated is not particularly limited.
For example, the above plating catalyst solution (a dispersion in which a metal is dispersed in an appropriate dispersion medium or a solution containing a metal salt dissolved in an appropriate solvent and dissociated metal ions) is prepared, and the plating catalyst solution is applied to the layer to be plated. The method of apply | coating on the top or the method of immersing the inorganic board | substrate with which the to-be-plated layer was formed in a plating catalyst liquid are mentioned.
The contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 10 minutes, more preferably about 1 minute to 5 minutes.
The temperature of the plating catalyst solution at the time of contact is preferably about 20 to 60 ° C, and more preferably about 30 to 50 ° C.

[Step (4): Plating step]
Step (4) is a step of forming a metal layer on the layer to be plated by performing a plating process on the layer to be plated to which the plating catalyst or its precursor has been applied in step (3). More specifically, as shown in FIG. 1C, in this step, a metal layer 16 is formed on the layer 14 to be plated, and a laminate 18 is obtained.

Examples of the plating treatment performed in this step include electroless plating and electrolytic plating. In the above step, the plating treatment can be selected depending on the function of the plating catalyst applied to the layer to be plated or its precursor.
Especially, it is preferable to perform electroless plating from the point of the adhesive improvement of a metal layer. Further, in order to obtain a metal layer having a desired layer thickness, it is a more preferable aspect that electrolytic plating is further performed after electroless plating.
Hereinafter, the plating process 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 immersing the layer to be plated, to which the electroless plating catalyst has been applied, in water and removing the 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 electroless plating catalyst precursor is immersed or impregnated in the electroless plating bath, after the electroplating bath is washed with water to remove excess precursor (metal salt, etc.) And soaking 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, known reducing agents (for example, boron-based reducing agents such as sodium borohydride or dimethylamine borane, formaldehyde, hypophosphorous acid, etc.) can be used.
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, for example, in addition to a solvent (for example, water), 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 thickness of the metal layer obtained by electroless plating can be controlled by the metal ion concentration in the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. When performing electroplating, which will be described later, as a layer, it is preferable that a film of at least 0.1 μm or more is uniformly applied. Further, from the viewpoint of conductivity, when electroplating described later is not performed, it is preferably 0.1 μm or more, more preferably 1 μm, and most preferably 3 to 20 μm.
Further, the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 10 minutes 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.
Moreover, after the above-mentioned electroless plating, the formed metal layer may be used as an electrode, and electrolytic plating may be further performed. As a result, a new metal layer having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the inorganic substrate. As described above, by performing electroplating after electroless plating, the metal layer can be formed in a thickness according to the purpose, which is suitable for applying the metal layer to various applications.

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

Further, the thickness of the metal layer obtained by electrolytic plating can be controlled by adjusting the concentration of metal contained in the plating bath, the current density, or the like.
In addition, when applying to general electrical wiring etc., the layer thickness of the metal layer is preferably 0.5 μm or more, more preferably 1 to 30 μm from the viewpoint of conductivity.

[Laminate (surface metal layer material)]
By passing through each process mentioned above, the laminated body (laminated body which has a metal layer in an outermost layer) which comprises an inorganic substrate, a primer layer, a to-be-plated layer, and a metal layer in this order can be obtained. In addition, this laminated body may have layers other than the said layer. For example, an insulating layer may be provided between the inorganic substrate and the primer layer. In order to obtain such a laminate, an inorganic substrate with an insulating layer having an insulating layer may be used as the inorganic substrate in the step (1).
The obtained laminate 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 layer in the laminate in a pattern, a laminate (metal pattern material) having the pattern-like metal layer on the surface can be produced.
This etching step (step (5)) will be described in detail below.

[Step (5): Etching step]
Step (5) is a step of etching the metal layer (plating film) formed in the step (4) into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the formed metal layer by etching. More specifically, as shown in FIG. 1D, in this step, a patterned metal layer 20 is formed.
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 layer, the same pattern as the metal pattern part is formed by pattern exposure and development, and the metal layer 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 layer, form the same pattern as the non-metal pattern part by pattern exposure and development, and perform electroplating using the dry film resist pattern as a mask, In this method, quick etching is performed after the dry film resist pattern is removed, and the metal layer 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.

In addition, a pattern-form to-be-plated layer can be obtained by implementing the following processes (6) instead of a process (2). For the development and removal in the step (6), a developer capable of dissolving and removing the polymer-containing layer is appropriately used.
Step (6): forming a layer containing the polymer on the primer layer, applying pattern-like energy to the layer containing the polymer, curing the layer containing the polymer in the energy application region, and then forming the non-energy application region. Step of developing and removing to form a patterned layer to be plated By performing steps (3) and (4) on the patterned layer to be plated obtained in step (6), a patterned metal layer is provided. Metal pattern materials can also be manufactured (full additive method).

[Usage]
The obtained laminate having a patterned metal layer is used in various applications such as semiconductor chips, various electric wiring boards (for example, printed wiring boards), FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, etc. Can be applied to. Especially, the use used as a wiring board is preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
First, the synthesis method of the polymer used in the examples will be described in detail.

(Synthesis 1: Polymer A)
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 M 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 M 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% 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 12 g of polymer A (weight average molecular weight 53,000) was obtained.

(Synthesis 2: Polymer B)
A 1000 ml three-necked flask was charged with 35 g of N, N-dimethylacetamide and heated to 75 ° C. under a nitrogen stream. There, a solution of 6.60 g of 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry), 28.4 g of 2-cyanoethyl acrylate, 0.65 g of V-601 (manufactured by Wako Pure Chemical Industries), 35 g of N, N-dimethylacetamide For 2.5 hours. After completion of dropping, the mixture was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.
Ditertiary butyl hydroquinone 0.29 g, dibutyltin dilaurate 0.29 g, Karenz AOI (manufactured by Showa Denko KK) 18.56 g, N, N-dimethylacetamide 19 g are added to the above reaction solution, at 55 ° C. for 4 hours. Reaction was performed. Thereafter, 3.6 g of methanol was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with ethyl acetate: hexane = 1: 1, and the solid matter was taken out to obtain 32 g of polymer B (weight average molecular weight 62,000) having an interactive group and a polymerizable group.

[Example 1]
A glass substrate (manufactured by Corning, Eagle 2000) was subjected to ultrasonic cleaning with pure water for 10 minutes, and then a primer layer forming composition A having the following composition was applied onto the glass substrate by a spin coating method (condition: primer) After drying the layer, it was applied so that the film thickness was 5 μm), and dried at 150 ° C. for 60 minutes to obtain a substrate A.

(Primer layer forming composition A)
Hydrogenated acrylonitrile-butadiene rubber (H-NBR) (manufactured by Zeon Corporation, Zetpol0020, residual unsaturated bond ratio (content of aliphatic unsaturated group): 10.5%): 1 g, cyclopentanone (Nippon Zeon Corporation) 9 g) was mixed and stirred to prepare a mixed solution. Then, 1 mol / L acetic acid: 0.1 g was added to adjust the pH of the mixed solution to 4, and a silane coupling agent (manufactured by Shin-Etsu Silicone, KBM5103, functional group: acryloyloxy group): 0.5 g mixed solution And the silane coupling agent was hydrolyzed by stirring for 60 minutes to prepare a primer layer forming layer composition A.

A composition A for forming a layer to be plated containing polymer A is applied onto substrate A by spin coating (condition: applied so that the film thickness after drying of the layer to be plated is 0.5 μm), and 10 at 80 ° C. After partial drying, exposure was performed with an exposure energy of 3000 mJ using a UV exposure machine (manufactured by Mitsunaga Electric Manufacturing Co., Ltd., model number: UVF-502S, lamp: UXM-501MD).
The substrate after the exposure was immersed in a 1% by mass NaHCO ₃ aqueous solution for 10 minutes, and then washed with distilled water to obtain a substrate B.

(Composition A for Plating Layer Formation)
Polymer A: 0.36 g, sodium hydrogen carbonate: 0.19 g, and water: 1.75 g were mixed and stirred to dissolve polymer A, and then methanol: 2.66 g was further added, followed by stirring. A composition A for forming a plating layer was prepared.

Next, the substrate B having the layer to be plated was immersed in a 1% by mass aqueous solution of silver nitrate for 10 minutes, and then washed by immersing it in water to give a plating catalyst to the layer to be plated.
A substrate having a plating layer provided with a plating catalyst was immersed in an electroless plating bath having the following composition at 26 ° C. for 60 minutes to perform electroless plating. The obtained metal layer (plating layer) had a thickness of about 0.5 μm.

(Composition of electroless plating bath)
・ Distilled water 770.88g
・ Sulcup PGT-A (manufactured by Uemura Kogyo) 97.24 g
・ Sulcup PGT-B (manufactured by Uemura Kogyo) 66.58 g
・ Sulcup PGT-C (manufactured by Uemura Kogyo) 43.26 g
・ Formalin 22.39g

Subsequently, the electroless plating film (electroless copper plating film) obtained above was used as a power feeding layer, electroplating was performed for 20 minutes under the condition of 3 A / dm ² using an electrolytic copper plating bath having the following composition, and metal A laminate having a layer was produced. The thickness of the obtained electrolytic copper plating film was 15 μm.

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

  With respect to the obtained sample, an interval of 5 mm was provided in the metal layer, a 130 mm incision was made in parallel, and the end was incised with a cutter and started up 10 mm. Using a tensile testing machine (RTM-100, manufactured by A & D Co., Ltd.), the peeled end of the metal layer was grasped and the 90 ° peel strength was measured (tensile speed: 10 mm / min). The results are shown in Table 1.

Further, the Young's modulus of the primer layer was measured by the following method. The results are shown in Table 1.
The primer composition is dissolved in a solvent (such as cyclopentanone), dropped onto a Teflon petri dish so that the film thickness after drying falls within the range of 150 to 200 μm, dried at room temperature for one week, and further under vacuum. A model membrane was prepared by drying for 1 week. Using the obtained model membrane, the SS curve was measured using a tensile testing machine (RTM-100, manufactured by A & D Co., Ltd.) to determine the Young's modulus.

[Example 2]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition B having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming layer composition B)
A primer layer forming layer except that styrene-butadiene rubber (SBR) (product No: 182907, manufactured by Aldrich) is used instead of hydrogenated acrylonitrile-butadiene rubber (H-NBR) (manufactured by Nippon Zeon Co., Ltd., Zetpol0020). In the same manner as in the composition A, a primer layer forming layer composition B was prepared.

[Example 3]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition C having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming layer composition C)
Instead of using hydrogenated acrylonitrile-butadiene rubber (H-NBR) (manufactured by Nippon Zeon Co., Ltd., Zetpol0020), an acrylonitrile-butadiene-styrene copolymer (ABS) resin [Product No .: 430145, manufactured by Aldrich] is used. The primer layer forming layer composition C was prepared in the same manner as the primer layer forming layer composition A.

[Example 4]
Instead of the primer layer forming composition A used in Example 1, a primer layer forming composition D having the following composition was used, and the drying temperature was changed from 150 ° C. to 180 ° C. Instead of the above, the composition B for plating layer formation was used, the drying time after spin coating was changed from 10 minutes to 5 minutes, the exposure energy was changed from 3000 mJ to 500 mJ, and the catalyst application was immersed in a 1% by weight aqueous solution of silver nitrate for 10 minutes. Instead of this, a laminate was produced according to the same procedure as in Example 1 except that it was immersed in a 0.25 mass% palladium acetate aqueous solution for 5 minutes. Each evaluation result is shown in Table 1.

(Primer layer forming composition D)
Instead of hydrogenated acrylonitrile-butadiene rubber (H-NBR) (manufactured by ZEON Corporation, Zetpol0020), jER806 (bisphenol F type epoxy resin: made by Japan Epoxy Resin) 12.3 parts by mass, LA7052 (phenolite, curing agent: Dai Nippon Ink Chemical Co., Ltd.) 4.3 parts by mass, YP50-35EK (phenoxy resin, manufactured by Tohto Kasei) 20.9 parts by mass, 62.5 parts by mass of cyclohexanone, and 2-ethyl-4-methylimidazole (curing accelerator) A primer layer forming layer composition D was prepared in the same manner as the primer layer forming layer composition A except that a mixed solution in which 0.1 parts by mass was mixed was used.

(Composition B for Plating Layer Formation)
Polymer B (10.5 parts by mass), acetone (73.3 parts by mass), methanol (33.9 parts by mass), and N, N-dimethylacetamide (4.8 parts by mass) were mixed and stirred, and the layer to be plated A forming composition B was prepared.

[Example 5]
A laminate was manufactured according to the same procedure as in Example 1 except that the thickness of the primer layer was changed from 5 μm to 8 μm. Each evaluation result is shown in Table 1.

[Example 6]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition E having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming composition E)
The primer layer forming composition A and the primer layer forming composition D were mixed at a mass ratio of A: D = 3: 7 to prepare a primer layer forming composition E.

[Example 7]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition F having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming composition F)
The primer layer forming composition A and the primer layer forming composition D were mixed at a mass ratio of A: D = 5: 5 to prepare a primer layer forming composition F.

[Example 8]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition G having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming composition G)
The primer layer forming composition A and the primer layer forming composition D were mixed at a weight ratio of A: D = 7: 3 to prepare a primer layer forming composition G.

[Example 9]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition H having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming layer composition H)
A primer layer-forming layer composition except that acrylonitrile-butadiene rubber (NBR) (manufactured by ZEON Corporation, Nipol 101L) was used instead of hydrogenated acrylonitrile-butadiene rubber (H-NBR) (manufactured by ZEON Corporation, Zetpol0020). In the same manner as A, a primer layer forming layer composition H was prepared.

[Example 10]
A laminated body was produced according to the same procedure as in Example 1 except that a silicon wafer was used instead of the glass substrate used in Example 1. Each evaluation result is shown in Table 1.

[Example 11]
A laminated body was produced according to the same procedure as in Example 1 except that a ceramic substrate (manufactured by Kyocera Corporation) was used instead of the glass substrate used in Example 1. Each evaluation result is shown in Table 1.

[Example 12]
A laminated body was prepared according to the same procedure as in Example 1 except that a glass substrate (Matsunami Glass Industry Co., Ltd., D263) was used instead of the glass substrate (Corning Corp., Eagle 2000) used in Example 1. Manufactured. Each evaluation result is shown in Table 1.

[Example 13]
A laminated body was prepared according to the same procedure as in Example 1 except that a glass substrate (Matsunami Glass Industry Co., Ltd., quartz) was used instead of the glass substrate (Corning Corp., Eagle 2000) used in Example 1. Manufactured. Each evaluation result is shown in Table 1.

[Example 14]
A laminated body was prepared according to the same procedure as in Example 1 except that a glass substrate (Matsunami Glass Industry Co., Ltd., 0200) was used instead of the glass substrate (Corning Corp., Eagle 2000) used in Example 1. Manufactured. Each evaluation result is shown in Table 1.

[Example 15]
According to the same procedure as in Example 1, except that the acetic acid used in the preparation of the primer layer forming composition A was not used, the pH of the mixed solution was 7.2, and the stirring time was changed to 30 minutes. A laminate was produced. Each evaluation result is shown in Table 1.

[Example 16]
A laminated body was produced according to the same procedure as in Example 1 except that hydrochloric acid (35% hydrochloric acid manufactured by Wako Pure Chemical Industries) was used instead of acetic acid, and the stirring time was changed to 30 minutes. Each evaluation result is shown in Table 1.

[Example 17]
A laminate was produced according to the same procedure as in Example 1 except that hydrochloric acid (35% hydrochloric acid manufactured by Wako Pure Chemical Industries) was used instead of acetic acid and the stirring time was changed to 10 minutes. Each evaluation result is shown in Table 1.

[Example 18]
A laminate was produced according to the same procedure as in Example 1, except that hydrochloric acid (35% hydrochloric acid manufactured by Wako Pure Chemical Industries) was used instead of acetic acid, and the stirring time was changed to 1 minute. Each evaluation result is shown in Table 1.

[Example 19]
A laminate was prepared according to the same procedure as in Example 1 except that hydrochloric acid (manufactured by Wako Pure Chemicals, 35% hydrochloric acid) was used instead of acetic acid and the pH of the mixed solution was changed to 1 and the stirring time was changed to 30 minutes. Manufactured. Each evaluation result is shown in Table 1.

[Example 20]
A laminate was prepared according to the same procedure as in Example 1 except that hydrochloric acid (manufactured by Wako Pure Chemicals, 35% hydrochloric acid) was used instead of acetic acid, and the pH of the mixed solution was changed to 1 and the stirring time was changed to 10 minutes. Manufactured. Each evaluation result is shown in Table 1.

[Example 21]
The laminate was prepared according to the same procedure as in Example 1 except that hydrochloric acid (manufactured by Wako Pure Chemicals, 35% hydrochloric acid) was used instead of acetic acid, and the pH of the mixed solution was changed to 1 and the stirring time was changed to 1 minute. Manufactured. Each evaluation result is shown in Table 1.

[Example 22]
The same as Example 1 except that 3-mercaptopropyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., functional group: mercapto group) was used instead of KBM5103 used in the preparation of the primer layer forming composition A. A laminate was produced according to the procedure. Each evaluation result is shown in Table 1.

[Example 23]
According to the same procedure as in Example 1, except that Dynasilane AMMO (Evonik Degussa, functional group: amino group) was used instead of KBM5103 used in the preparation of the primer layer forming composition A, the laminate was used. Manufactured. Each evaluation result is shown in Table 1.

[Example 24]
A laminated body according to the same procedure as in Example 1 except that LS2940 (manufactured by Shin-Etsu Chemical Co., Ltd., functional group: epoxy group) was used instead of KBM5103 used in the preparation of the primer layer forming composition A. Manufactured. Each evaluation result is shown in Table 1.

[Example 25]
According to the same procedure as in Example 1, except that LS5300 (manufactured by Shin-Etsu Chemical Co., Ltd., functional group: phenyl group) was used instead of KBM5103 used in the preparation of the primer layer forming composition A, the laminate Manufactured. Each evaluation result is shown in Table 1.

[Example 26]
A laminate was manufactured according to the same procedure as in Example 1 except that the thickness of the primer layer was changed from 5 μm to 4.2 μm. Each evaluation result is shown in Table 1.

[Example 27]
A laminate was manufactured according to the same procedure as in Example 1 except that the thickness of the primer layer was changed from 5 μm to 3.4 μm. Each evaluation result is shown in Table 1.

[Comparative Example 1]
A laminate was produced according to the same procedure as in Example 1 except that a primer layer was formed on a glass substrate without forming a primer layer using the primer layer forming composition. Each evaluation result is shown in Table 1.

[Comparative Example 2]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition I having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming composition I)
Hydrogenated acrylonitrile-butadiene rubber (H-NBR) (manufactured by Nippon Zeon Co., Ltd., Zetpol0020, residual unsaturated bond ratio = 10.5%): 1 g, cyclopentanone (manufactured by Nippon Zeon Co., Ltd.): 9 g are mixed and stirred, and primer Layer forming composition I was prepared. The composition does not contain a hydrolysis condensate.

[Comparative Example 3]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition J having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming composition J)
Acrylonitrile-butadiene rubber (NBR) (manufactured by Nippon Zeon Co., Ltd., Nipol 101L): 1 g and cyclopentanone (manufactured by Nippon Zeon Co., Ltd.): 9 g were mixed and stirred to prepare primer layer forming composition J. The composition does not contain a hydrolysis condensate.

[Comparative Example 4]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition K having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming composition K)
Styrene-butadiene rubber (SBR) (product No: 182907, manufactured by Aldrich): 1 g and cyclopentanone (manufactured by Nippon Zeon): 9 g were mixed and stirred to prepare a primer layer forming composition K. The composition does not contain a hydrolysis condensate.

[Comparative Example 5]
Instead of the primer layer forming composition A used in Example 1, a laminate was produced according to the same procedure as in Example 1 except that the primer layer forming composition L having the following composition was used. Each evaluation result is shown in Table 1.

(Primer layer forming composition L)
Hydrogenated acrylonitrile-butadiene rubber (H-NBR) (manufactured by Zeon Corporation, Zetpol0020, residual unsaturated bond ratio = 10.5%): 1 g, tetrahydroxyfuran (manufactured by Wako Pure Chemical Industries, Ltd.): 9 g are mixed and stirred. A mixed solution was prepared. Thereafter, the pH of the mixed solution is adjusted to 12 using sodium hydroxide, and 0.5 g of silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., KBM5103): 0.5 g is added and stirred for 30 minutes to add silane coupling agent The primer layer forming layer composition L was prepared by performing decomposition.

[Comparative Example 6]
According to the same procedure as in Example 1, except that Dynasilane 4148 (Evonik Degussa, functional group: alkoxy group) was used instead of KBM5103 used in the preparation of the primer layer forming composition A, the laminate was used. Manufactured. Each evaluation result is shown in Table 1.

[Comparative Example 7]
The same as Example 1 except that triethoxysilylpropylmaleic acid (manufactured by Gelest. Inc., functional group: carboxyl group) was used instead of KBM5103 used in the preparation of the primer layer forming composition A. A laminate was produced according to the procedure. Each evaluation result is shown in Table 1.

[Comparative Example 8]
Using the polymer C described below, a laminate was produced according to the following procedure (production of laminate), and each of the above evaluations was performed.
In addition, the comparative example 8 corresponds to the aspect implemented by changing the glass epoxy substrate into the glass substrate from the aspect using the glass epoxy substrate as described in paragraphs [0229] to [0236] of Patent Document 1.

(Synthesis of polymer C)
A 500 ml three-necked flask was charged with 10 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. Monomer M having the following structure: 6.61 g, 9.01 g of 2-cyanoethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), HOA-HH (monomer having alicyclic carboxylic acid) 15.14 g, V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.32 g of a 10 g solution of N, N-dimethylacetamide was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was further stirred for 3 hours. Thereafter, 51 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature.

  To the above reaction solution, 0.06 g of 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and 22.26 g of triethylamine were added and reacted at room temperature for 4 hours. Thereafter, 29 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 19 g of polymer C (weight average molecular weight 42,000) was obtained.

(Preparation of composition for forming plated layer)
Polymer C obtained by the above synthesis method: 0.2 g, sodium carbonate: 0.04 g, water: 1.5 g, and acetonitrile: 0.3 g were mixed and stirred to prepare a composition for forming a layer to be plated.

(Manufacture of laminates)
A cyclohexane solution of 9% by mass of ABS resin (manufactured by Aldrich) on a glass substrate (Corning, Eagle 2000) as a close-contact auxiliary layer is spin-coated (conditions: 250 rpm for 5 seconds, then 750 rpm for 20 seconds) And dried to obtain a substrate C1.

The prepared composition for forming a layer to be plated was applied on the adhesion auxiliary layer of the substrate C1 by a spin coating method so as to have a thickness of 1 μm, and dried at 80 ° C. for 30 minutes.
Thereafter, an irradiation power (USHIO) of 10 mW / cm ² was applied to the composition for forming a layer to be plated using a UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD). Exposure was performed for 300 seconds using an ultraviolet ray integrating light meter UIT150 manufactured by Denki Co., Ltd. (irradiation power measurement with UVD-S254).
The substrate after exposure was immersed in a 1% by mass Na ₂ CO ₃ aqueous solution for 5 minutes and then washed with distilled water to obtain a substrate C2.

  The substrate C2 having the layer to be plated was immersed in a 10% by mass aqueous silver nitrate solution for 10 minutes, and then immersed in acetone for cleaning.

  As described above, electroless plating was performed at 26 ° C. for 10 minutes using the electroless plating bath having the following composition on the substrate C2 having the layer to be plated with the plating catalyst. The thickness of the obtained electroless copper plating film was 0.1 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 1.8mg

[Electroplating]
Subsequently, electroplating was performed for 20 minutes under the conditions 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. The thickness of the obtained electrolytic copper plating film was 18 μm.

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

In Table 1, the pH column means the pH of the mixed solution during hydrolysis of the silane coupling agent.
Moreover, the stirring time column in Table 1 means the stirring time (hydrolysis treatment time) in the mixed solution at the time of hydrolysis of the silane coupling agent.
In Table 1, the functional group column means a functional group contained in the silane coupling agent, and the symbol of the functional group described in each column means the following functional group.
A group: acryloyloxy group, M group: mercapto group, Am group: amino group, E group, epoxy group, Ph group, phenyl group, Al group: alkoxy group, C group: carboxyl group In addition, linear photoelectron spectroscopy (XPS) ), It was confirmed that a hydroxyl group was present on the surface of the inorganic substrate (glass substrate or the like) used in Examples 1 to 27. Monochrome AlKα was used as the X-ray source.

As shown in Table 1, the metal layer in the laminate obtained by the production method of the present invention showed excellent adhesion.
In addition, it was confirmed from the comparison with Example 15 and Example 16 that it is excellent by the adhesiveness of a metal layer, when pH is 4 or less.
Moreover, it was confirmed from the comparison with Example 1 and Example 4 that the resin which comprises a primer layer is excellent in the adhesiveness of a metal layer in Example 1 which is an elastomer.
Moreover, it was confirmed from the comparison with Example 1 and 2 that it is excellent by the adhesiveness of a metal layer in Example 1 which is an aspect in which resin has a cyano group.
Moreover, it was confirmed from the comparison with Example 26 and 27 that it is excellent in the adhesiveness of a metal layer, so that the thickness of a primer layer is thick (4 micrometers or more).
Furthermore, it was confirmed from the comparison with Examples 2-3 and 6-8 that when the elasticity modulus (Young's modulus) of a primer layer is below a predetermined value (500 MPa or less), it is excellent by the adhesiveness of a metal layer.

On the other hand, as shown in Comparative Examples 1 to 4, when the hydrolyzate and / or the condensate thereof was not used, the adhesion of the metal layer was inferior.
Moreover, as shown to Comparative Examples 5-7, when a silane coupling agent did not have a predetermined functional group, the adhesiveness of the metal layer was inferior.
Further, Comparative Example 8 is an embodiment in which the glass epoxy substrate used in the embodiment specifically disclosed in Patent Document 1 is changed to a glass substrate. As shown above, even when the aspect described in Patent Document 1 was used for a glass substrate as it was, the adhesion of the metal layer was inferior.

10: Inorganic substrate 12: Primer layer 14: Plated layer 16: Metal layer 18: Laminate 20: Patterned metal layer

Claims (9)

Hydrolysis of a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, an acryloyloxy group, a phenyl group, and a cyano group under conditions of pH 1-8. A step (1) of forming a primer layer on an inorganic substrate using a composition for forming a primer layer containing a hydrolyzate and / or a condensate thereof obtained from the resin, and a resin;
On the primer layer, a layer containing a polymer having a functional group and a polymerizable group that interacts with a plating catalyst or a precursor thereof is formed, and then energy is applied to the layer containing the polymer, A step (2) of forming a layer to be plated on the primer layer;
A step (3) of applying a plating catalyst or a precursor thereof to the layer to be plated;
Step (4) of performing a plating process on the layer to be plated to which a plating catalyst or a precursor thereof is applied and forming a metal layer on the layer to be plated, and a method for producing a laminate having a metal layer .   The manufacturing method of the laminated body which has a metal layer of Claim 1 whose range of the said pH is 1-4.   The manufacturing method of the laminated body of Claim 1 or 2 whose said resin contained in the said composition for primer layer formation is an elastomer.   The manufacturing method of the laminated body which has a metal layer in any one of Claims 1-3 whose Young's modulus of the said primer layer is 500 Mpa or less. The manufacturing method of the laminated body which has a metal layer in any one of Claims 1-4 in which the said resin contained in the said composition for primer layer formation has a unit represented by General formula (1).

(In General 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 manufacturing method of the laminated body which has a metal layer in any one of Claims 1-5 whose film thickness of the said primer layer is 4 micrometers or more.   The laminated body which has a metal layer manufactured by the manufacturing method in any one of Claims 1-6.   The manufacturing method of the laminated body which has a pattern-shaped metal layer provided with the pattern formation process which etches the metal layer in the laminated body of Claim 7 to pattern shape, and forms a patterned metal layer. The printed wiring board containing the laminated body which has a pattern-shaped metal layer obtained from the manufacturing method of Claim 8.