TWI610814B - Method for manufacturing laminate with hole, laminate with hole, method for manufacturing multilayer substrate, composition for forming underlayer - Google Patents

Abstract

The method for manufacturing a laminated body with holes according to the present invention includes a hole forming step of performing laser processing on a pre-processed laminated body having a first metal layer, a bottom layer, and a plated layer in order on the substrate to form a self-processed layer. The surface of the layered body on the plated layer side reaches the hole of the surface of the first metal layer, and the bottom layer includes a polymer having repeating units containing a cyano group and metal oxide particles; the polymer is relative to all repeating units in the polymer. The content of the cyano-containing repeating unit is 10 mol% to 60 mol%, the particle size of the metal oxide particles is 50nm to 2000nm, and relative to the total mass of the polymer and the metal oxide particles, the The content of the metal oxide particles is 20% by mass to 60% by mass.

Description

Production method of laminated body with holes, laminated body with holes, manufacturing method of multilayer substrate, and composition for forming base layer

The present invention relates to a method for manufacturing a laminated body with holes, a laminated body with holes, a method for manufacturing a multilayer substrate, and a composition for forming a bottom layer.

Conventionally, metal wiring substrates on which a wiring pattern using a metal pattern is formed on the surface of an insulating substrate have been widely used for electronic parts or semiconductor devices.

As a method of manufacturing such a metal wiring board, a "subtractive method" is mainly used. This subtractive method refers to a method in which a photosensitive layer that is photosensitive by irradiation with active light is provided on a metal layer formed on a substrate surface, the photosensitive layer is imagewise exposed, and then developed to form a resist Then, the metal layer is etched to form a metal pattern, and finally the resist image is peeled off.

In the metal wiring substrate obtained by this method, the anchoring effect generated by providing unevenness on the surface of the substrate is used to make the adhesion between the substrate and the metal layer appear. For this reason, there is a problem that the high-frequency characteristics of the substrate interface portion of the obtained metal pattern are deteriorated when used as metal wiring. In addition, in order to perform unevenness treatment on the surface of the substrate, it is necessary to treat the surface of the substrate with a strong acid such as chromic acid. Therefore, there is a problem that complicated steps are required to obtain a metal pattern having excellent adhesion between the metal layer and the substrate.

As a method for solving this problem, a method is known in which a plated layer having high adhesion to the substrate is formed on a substrate, and the plated layer is solidified. A metal layer is formed on the plated layer by plating (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. Furthermore, in Patent Document 1, an intermediate layer (adhesion auxiliary layer) is provided between the substrate and the plated layer to improve the adhesion of the metal layer.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-248464

On the other hand, in recent years, with the demand for high functionality of electronic equipment, the density of electronic components has been increased, and the density of electronic components has been continuously developed. In such a situation, wiring boards and the like corresponding to high-density mounting used in these also need to be miniaturized and high-density. In order to meet such requirements, in multilayer substrates, finer connection reliability can be achieved with finer connections. The electrical connection between multiple metal layers (wiring layers) formed by the wiring pitch becomes more important.

Generally, when manufacturing a multi-layer substrate having a plurality of metal layers, a via hole is formed to ensure conduction between the metal layers.

The inventors of the present invention have performed a hole (channel) formation process using laser processing for a multilayer body having a substrate, an intermediate layer (adhesive auxiliary layer), and a plated layer specifically disclosed in Patent Document 1. The shape accuracy of the formed hole is insufficient, and there is a concern that the connection reliability of the channel is impaired.

In addition, regarding this laminated body, after improving the shape accuracy of the holes and ensuring high connection reliability as described above, it is also necessary to ensure excellent adhesion of the metal layer formed on the plated layer.

In view of the above-mentioned circumstances, an object of the present invention is to provide a method for producing a laminated body with holes, which is excellent in the shape accuracy of holes formed by laser processing and has excellent adhesion of the metal layer to be laminated, and the manufacturing method therefor The obtained laminated body with holes.

Another object of the present invention is to provide a method for manufacturing a multilayer substrate using the laminated body with holes and having a metal layer having excellent adhesion.

Furthermore, an object of the present invention is to provide a composition for forming a primer layer for use in a method for producing a laminated body with holes.

The present inventors made diligent studies on the above-mentioned problems, and as a result, it has been found that a polymer having a repeating unit containing a cyano group is contained in a bottom layer (adhesive auxiliary layer) disposed between a plated layer and a substrate, and regulations Based on the findings, the metal oxide particles of various sizes vary greatly in shape accuracy of holes formed by laser processing and the adhesion of the metal layer laminated on the plated layer.

That is, the present inventors have found that the above problems can be solved by the following configuration.

(1) A method for manufacturing a laminated body with holes, including a hole forming step of performing laser processing on a pre-processed laminated body having a first metal layer, a bottom layer, and a plated layer in order on the substrate to form The hole on the plated layer side of the multilayer body before processing reaches the first metal layer surface. The bottom layer includes a polymer having repeating units containing a cyano group and metal oxide particles. The plated layer has contact with plating. Functional groups that are interacted with the polymer or its precursor; the polymer contains cyanide relative to all repeating units in the polymer The content of the repeating unit of the base is 10 mol% to 60 mol%, the particle size of the metal oxide particles is 50 nm to 2000 nm, and the metal in the bottom layer is oxidized relative to the total mass of the polymer and the metal oxide particles. The content of the particles is 20% by mass to 60% by mass.

(2) The method for producing a porous laminated body according to (1), wherein the content of the metal oxide particles in the bottom layer is 20% to 50% by mass relative to the total mass of the polymer and the metal oxide particles.

(3) A method for manufacturing a multi-layer substrate, comprising: a catalyst applying step of applying plating to a plated layer in the laminated body with holes obtained by the manufacturing method described in (1) or (2) A catalyst or a precursor thereof; and a plating step of performing a plating treatment on a plated layer to which the plating catalyst or a precursor thereof is provided, and a second metal layer that is in contact with and is in contact with the first metal layer through a hole It is formed on a plated layer.

(4) The method for manufacturing a multilayer substrate according to (3), further comprising a pattern forming step of etching the second metal layer into a pattern after the plating step to form a patterned metal layer.

(5) A printed wiring board including a multilayer substrate manufactured by the manufacturing method according to (3) or (4).

(6) A laminated body with holes comprising a first metal layer, a bottom layer, and a plated layer in this order on a substrate, the bottom layer comprising a polymer having repeating units containing a cyano group and metal oxide particles, and the plated layer The layer has functional groups that interact with the plating catalyst or its precursor, and the polymer contains cyanide relative to all repeating units in the polymer. The content of the repeating unit of the base is 10 mol% to 60 mol%, and the particle size of the metal oxide particles is 50 nm to 2000 nm. The metal oxide in the bottom layer is relative to the total mass of the polymer and the metal oxide particles. The content of the particles is from 20% by mass to 60% by mass, and there are holes from the surface on the side of the plating layer to the surface of the first metal layer.

(7) A composition for forming a bottom layer, comprising a polymer having repeating units containing a cyano group and metal oxide particles, and the content of the repeating units containing a cyano group in the polymer relative to all repeating units in the polymer It is 10 mol% to 60 mol%, the particle size of the metal oxide particles is 50 nm to 2000 nm, and it is in the bottom layer formed of the composition for forming the bottom layer relative to the total mass of the polymer and the metal oxide particles. The content of the metal oxide particles is 20% by mass to 60% by mass.

According to the present invention, it is possible to provide a method for producing a laminated body with holes having excellent shape accuracy of holes formed by laser processing and excellent adhesion of the metal layers to be laminated, and the attached holes obtained by the manufacturing method. Laminated body.

In addition, according to the present invention, there is also provided a method for manufacturing a multilayer substrate using the laminated body with holes and having a metal layer having excellent adhesion.

Furthermore, according to the present invention, a composition for forming a primer layer for use in a method for producing a laminated body with holes can also be provided.

Hereinafter, this embodiment will be described.

As a characteristic point of this embodiment, the characteristic point which the pre-processed laminated body which has a predetermined layer structure contains the polymer which has a repeating unit containing a cyano group, and the metal oxide particle of predetermined size is mentioned. First, by using a polymer having a predetermined functional group, the adhesion between the substrate and the plated layer is further improved, and as a result, the adhesion of the metal layer is further improved. In addition, by using metal oxide particles of a predetermined size, light scattering occurs in the bottom layer during laser processing, and the shape accuracy of the formed hole is improved.

<First Embodiment>

The first embodiment of the method for manufacturing a laminated body with holes according to this embodiment includes a hole forming step of performing laser processing on a pre-processed laminated body having a predetermined layer configuration to form a plated layer of the laminated body before processing. The side surface reaches the hole on the surface of the first metal layer.

Hereinafter, each constituent layer (substrate, first metal layer, bottom layer, plated layer, etc.) of the pre-processed laminated body used in this step is described in detail first, and then the procedure of the hole formation step is described in detail.

<Laminated body before processing>

The pre-processing laminated body used in this step will be described with reference to the drawings.

FIG. 1 (A) is a schematic cross-sectional view of a laminated body before processing. In FIG. 1A, the pre-processed laminated body 10 includes a substrate 12, a first metal layer 14, a bottom layer 16, and a plated layer 18 in this order.

Hereinafter, the configuration of each layer will be described in detail.

[Substrate]

The substrate 12 is a member for supporting each layer described later, and any substrate (for example, an insulating substrate. More specifically, a resin substrate, a ceramic substrate, and a glass substrate) may be used.

More specific examples include glass epoxy materials, bismaleimide triazine (BT) resin, polyimide film, polyimide film, liquid crystal film, and aromatic polyamidide (aramid )Wait. Among these, from the viewpoint of thermal or mechanical properties such as dimensional stability and heat resistance, glass epoxy materials and BT resins are preferred.

[First metal layer]

The first metal layer 14 is a metal layer provided on the substrate 12. The first metal layer 14 mainly functions as metal wiring in a wiring substrate. The first metal layer 14 may be provided in a pattern as shown in FIG. 1A, or may be provided on the entire surface of the substrate 12. In order to make the first metal layer 14 into a pattern, a known method (a subtractive method, a semi-additive method, or the like) can be used.

In addition, in FIG. 1A, the first metal layer 14 is disposed on only one surface of the substrate 12, but the first metal layer 14 may be disposed on both surfaces of the substrate 12.

The type of the metal constituting the first metal layer 14 is not particularly limited, and examples thereof include copper, silver, tin, nickel, and gold.

The thickness of the first metal layer 14 is not particularly limited, but is preferably about 4 μm to 50 μm in terms of application to a multilayer substrate.

[Underlayer (primer layer)]

The bottom layer 16 is for lifting the substrate 12 (or the insulating layer 30 described later) and A layer (preferably an insulating layer) provided by the adhesion between the plated layers 20. The bottom layer 16 includes at least a polymer having a cyano group-containing repeating unit and metal oxide particles.

Hereinafter, materials (polymers, metal oxide particles, etc.) constituting the underlayer 16 are described in detail first, and then a method of forming the underlayer 16 is described in detail.

(Polymer having a repeating unit containing a cyano group)

The polymer contained in the bottom layer 16 has a repeating unit containing a cyano group (-CN).

The content of the cyano-containing repeating unit in the polymer is 10 mol% to 60 mol% relative to all the repeating units in the polymer. If it is in the said range, the hole shape precision at the time of laser processing will be excellent, and the adhesiveness of a metal layer will be excellent. Among them, from the viewpoint of more excellent adhesion of the metal layer, the content of the repeating unit containing a cyano group is preferably 15 mol% to 55 mol%, and more preferably 25 mol% to 55 mol%.

The structure of the repeating unit containing a cyano group is not particularly limited as long as it contains a cyano group, but it is preferably represented by the following formula (1) from the viewpoint that the polymer can be easily synthesized and the adhesion of the metal film is more excellent. Repeating unit.

In the formula (1), R ⁷ represents a hydrogen atom or a substituted or unsubstituted alkyl group (for example, methyl, ethyl, propyl, or butyl).

In the formula (1), L ⁴ represents a single bond or a substituted or unsubstituted divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably a carbon number of 1 to 8. For example, an alkylene group such as methylene, ethylene, or propyl) , Substituted or unsubstituted divalent aromatic hydrocarbon group (preferably 6 to 12 carbons, such as phenylene), -O-, -S-, -SO _2- , -N (R)-( R: alkyl), -CO-, -NH-, -COO-, -CONH-, or a combination of these (e.g., alkyleneoxy, alkyleneoxycarbonyl, alkylenecarbonyloxy, etc. )Wait. Among these, a single bond is more preferable from the viewpoint that the adhesion of the metal layer is more excellent.

The polymer may contain repeating units other than the cyano-containing repeating units described above.

For example, it may have repeating units derived from the following monomers: aromatic vinyl monomers (e.g., styrene, α-methylstyrene, divinylbenzene, etc.), conjugated diene monomers (e.g., 1, 3 -Butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3-butane Diene, 1,3-pentadiene, 1,3-hexadiene, etc.), (meth) acrylic monomers containing amidino groups (e.g. acrylamide, methacrylamide, N- (methyl ) Acrylomethylmorpholine, N-vinyl-2-pyrrolidone, etc.), unsaturated carboxylic acid monomers (e.g. fumaric acid, maleic acid, acrylic acid, methacrylic acid, etc.), or others Monomer (e.g. ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, ethyl vinyl ether, butyl vinyl ether, etc.).

Among these, from the viewpoint that the adhesion of the metal film is more excellent, the polymer preferably has a repeating monomer derived from a conjugated diene monomer (particularly, butadiene). yuan.

Specifically, the unit derived from the monomer shown below is mentioned, for example. In the following formula, R represents a hydrogen atom or a methyl group, and X represents -O- or -NH-.

The weight average molecular weight of the polymer is not particularly limited, but from the viewpoint of more excellent film-forming properties, it is preferably 1,000 to 700,000, and more preferably 2,000 to 200,000.

Specific examples of the polymer include a nitrile rubber (Nitrile Butadiene Rubber (NBR)), a nitrile rubber containing a carboxyl group (Carboxylated Nitrile Butadiene Rubber (XNBR)), Acrylonitrile-butadiene-isoprene rubber (Arcylonitrile Butadiene Isoprene Rubber, NBIR), nitrile-butadiene-styrene copolymer (Acrylonitrile Butadiene Styrene (ABS) resin) Wait. Among these, from the viewpoint that the effect of the present invention is more excellent, NBR is preferred.

The content of the polymer in the bottom layer 16 is not particularly limited, but from the viewpoints of excellent shape accuracy of the holes formed by laser processing and excellent adhesion of the second metal layer 26 laminated on the plated layer 18 In terms of the total mass of the bottom layer, it is preferably 35 mass% to 80 mass%, and more preferably 45 mass% to 80 mass%.

(Metal oxide particles)

The particle diameter (diameter) of the metal oxide particles contained in the bottom layer 16 is 50 nm to 2000 nm. Within this range, the shape accuracy of the hole formed by laser processing is excellent, and the adhesion of the second metal layer 26 laminated on the plated layer 18 is excellent. Among them, from the viewpoint of better hole shape accuracy and adhesion of the metal layer, it is preferably 50 nm to 1000 nm, and more preferably 50 nm to 500 nm.

When the particle diameter of the metal oxide particles is less than 50 nm, the shape accuracy of the holes formed by laser processing is not good. When the particle diameter of the metal oxide particles exceeds 2000 nm, the adhesion of the formed second metal layer 26 is not good.

In addition, in the method for measuring the particle diameter of the metal oxide particles, the particle diameter of at least 100 or more metal oxide particles is measured by observation with a scanning electron microscope (SEM), and these are calculated arithmetically. The average particle diameter was calculated. When metal oxide When the shape of the particles is not circular (for example, when the shape is elliptical), the major diameter is set to the particle diameter.

The content of the metal oxide particles in the bottom layer 16 is 20% to 60% by mass based on the total mass of the polymer and the metal oxide particles. Within this range, the shape accuracy of the hole formed by laser processing is excellent, and the adhesion of the second metal layer 26 laminated on the plated layer 18 is excellent. Among these, from the viewpoint that the accuracy of the shape of the hole or the adhesion of the metal layer is more excellent, it is preferably 20% by mass to 50% by mass, and more preferably 30% by mass to 50% by mass.

When the content of the metal oxide particles is less than 20% by mass, the shape accuracy of the holes formed by laser processing is not good. When the content of the metal oxide particles exceeds 60% by mass, the adhesion of the formed second metal layer 26 is not good.

The type of the metal oxide particles is not particularly limited, and examples thereof include metal oxide particles containing at least one metal element selected from the group consisting of elements 4A, 5A, 3B, and 4B of the periodic table. Among them, metal oxide particles that can be obtained at low cost include metal oxide particles containing at least one metal element selected from the group consisting of silicon, aluminum, and titanium.

Specific examples of the metal oxide particles include titanium oxide, zinc oxide, silicon oxide, lead oxide, tungsten oxide, tin oxide, indium oxide, niobium oxide, cadmium oxide, bismuth oxide, aluminum oxide, and oxide. Gallium (III), ferrous oxide, etc.

(Formation method of the bottom layer)

The method for forming the bottom layer 16 is not particularly limited, and a known method can be used. For example, a method (coating method) in which the underlayer-forming composition including the polymer and the metal oxide particles is coated on the substrate 12 with the first metal layer 14 formed thereon (coating method) may be mentioned; A method in which a polymer composition containing metal oxide particles is directly laminated on the substrate 12 on which the first metal layer 14 is attached, and the like. From the viewpoint that the control of the film thickness of the underlayer 16 is easier, a coating method is preferred.

When a coating method is implemented, a well-known coating method (for example, spin coating, dip coating, etc.) can be used.

When a composition for forming a primer layer is used, the composition may contain a solvent as necessary. The solvent to be used may be any polymer that can dissolve and disperse the polymer and metal oxide particles, and examples thereof include ketone solvents (for example, cyclopentanone).

In order to disperse the metal oxide particles, a known surfactant (dispersant) may be used as necessary.

In addition, as in the case of the underlayer 16, the content of the metal oxide particles in the composition for forming the underlayer is preferably 20% to 60% by mass based on the total mass of the polymer and the metal oxide particles. It is more preferably 20% by mass to 50% by mass, and even more preferably 30% by mass to 50% by mass.

Furthermore, if necessary, a heat treatment may be performed after coating to remove the solvent or harden the bottom layer.

The thickness of the bottom layer 16 is not particularly limited, but it is preferably 0.1 μm to 40 μm, and more preferably 0.1 μm to 20 μm from the viewpoint of better hole shape accuracy and adhesion of the metal layer.

[Plating layer]

The plated layer 18 is a layer provided on the underlayer 16 and having a functional group (hereinafter, also referred to as an interactive group) that interacts with a plating catalyst or a precursor thereof.

The to-be-plated layer 18 efficiently absorbs a plating catalyst or a precursor thereof which will be described later in accordance with the function of a functional group contained in the plating catalyst or a precursor thereof. That is, the plated layer 18 functions as a good receiving layer for a plating catalyst (or a precursor thereof). As a result, excellent adhesion with the second metal layer 26 described later formed on the surface of the plated layer 18 can be obtained.

The interaction group is a functional group that interacts with the plating catalyst or its precursor, and a functional group that can form an electrostatic interaction with the plating catalyst or its precursor can be used, or can interact with the plating catalyst or its precursor The compounds form coordinated nitrogen-containing functional groups, sulfur-containing functional groups, oxygen-containing functional groups, and the like. Examples of the interactive group include non-dissociable functional groups (functional groups that do not generate protons due to dissociation) and the like.

Specific examples of the interacting group include an amino group, an amido group, an amido group, a urea group, a tertiary amino group, an ammonium group, an amidino group, a triazine ring, and a triazole ring. , Benzotriazolyl, imidazolyl, benzimidazolyl, quinolinyl, pyridyl, pyrimidinyl, pyrazinyl, quinazolinyl, quinoxalinyl, purinyl, triazinyl, piperidinyl, Piperazinyl, pyrrolidinyl, pyrazolyl, aniline, alkylamine-containing group, isocyanuric group-containing group, nitro, nitroso, azo, diazo, azide Nitrogen-containing functional groups such as alkyl, cyano, and cyanate ester (RO-CN); ether, hydroxyl, phenolic hydroxyl, carboxyl, carbonate, carbonyl, ester, and N-oxide-containing groups. An oxygen-containing functional group such as a group having an S-oxide structure and a group containing an N-hydroxy structure; thienyl, thiol, thiourea, trimeric thiocyanate, benzothiazolyl, mercaptotriazine, Thioether group, thiooxy group, fluorenylene group, fluorenyl group, sulfite group, sulfonium group-containing group, sulfonium oxide group-containing group, sulfonate group, sulfonate group-containing group, etc. Sulfur-containing functional groups; phosphorus-containing functional groups such as phosphate groups, phosphatidylamine groups, phosphine groups, and phosphate group-containing groups; groups containing halogen atoms such as chlorine and bromine among the functional groups that can adopt a salt structure, Salts of these functional groups can also be used.

Among them, ionic polar groups such as a carboxyl group, a sulfonic acid group, a phosphate group, and a boric acid group, or an ether group or a cyano group are particularly preferred in terms of high polarity and high adsorption ability for a plating catalyst or its precursor. , More preferably a carboxyl group or a cyano group. Furthermore, two or more of these groups may be included.

The material constituting the plated layer 18 is not particularly limited, and examples thereof include insulating resins such as thermosetting resins and thermoplastic resins. These materials need only contain the above-mentioned interactive group.

More specifically, examples of the thermosetting resin include epoxy resin, phenol resin, polyimide resin, polyester resin, bismaleimide resin, polyolefin resin, and isocyanate resin. Examples of the thermoplastic resin include phenoxy resin, polyether fluorene, polyfluorene, polyphenylene sulfone, polyphenylene sulfide, polyphenylene ether, and polyether fluorene imine.

The thickness of the plated layer 18 is not particularly limited, but from the viewpoint that the adhesion of the second metal layer 26 is more excellent, it is preferably 0.02 μm to 5.0 μm, and more preferably 0.05 μm to 2.0 μm.

The method for forming the plated layer 18 is not particularly limited, and a known layer forming method such as a coating method, a transfer method, or a printing method is used.

Specifically, a polymer having a functional group that interacts with a plating catalyst or a precursor thereof can be laminated on the underlayer 16. Alternatively, a composition containing the polymer (hereinafter, also referred to as a composition for forming a plated layer) may be used. When this composition is used, the following methods can be exemplified: immersing the substrate to be used in the composition for forming a plated layer, or coating the composition for forming a plated layer on the underlayer 16 as necessary. The plated layer 18 is formed on the bottom layer 16 by a heat treatment or an exposure treatment.

(A suitable form of the method for forming a plated layer)

Among these, as a suitable form of the formation method of the to-be-plated layer 18, the method of using the to-be-plated using the polymer containing the functional group which interacts with a plating catalyst or its precursor, and a polymerizable group is mentioned. The coating layer-forming composition forms a layer containing the polymer on the underlayer 16 and applies energy to the layer containing the polymer to form a plated layer 18. With this configuration, chemical bonding or the like is likely to occur between the plated layer 18 and the underlayer 16, and the adhesion between the two is further improved. As a result, the adhesion of the second metal layer 26 is more excellent.

First, the materials (polymer, composition for forming a plated layer, etc.) used in this embodiment will be described in detail, and the procedure of this embodiment will be described later.

(polymer)

The polymer used has an interactive group and a polymerizable group.

The interaction group is as described above.

The polymerizable group is a functional group capable of forming a chemical bond between the polymers or between the polymer and the bottom layer 16 through energy imparting, and examples thereof include a radical polymerizable group and a cation polymerizable group. Among these, a radical polymerizable group is preferred from the viewpoint of reactivity. Examples of the radical polymerizable group include an acrylate group (acrylic acid group), a methacrylate group (methacrylic acid group), an itaconate group, a crotonic acid group, and an isocrotonic acid group. Unsaturated carboxylic acid ester groups such as methyl, maleic acid ester groups, styryl, vinyl, acrylamido, methacrylamido, and the like. Among them, a methacrylate group, an acrylate group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacrylate group, an acrylate group, and a styrene group are more preferable .

The weight average molecular weight of the polymer is not particularly limited, but from the viewpoint of better handling properties such as solubility, it is preferably 1,000 or more and 700,000 or less, and more preferably 2,000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20,000 or more.

The method for synthesizing a polymer having such a polymerizable group and an interactive group is not particularly limited, and a known synthesis method is used (see paragraphs [0097] to [0125] of Japanese Patent Publication No. 2009-280905).

(Appropriate Form 1 of Polymer)

As a first preferred aspect of the polymer, a unit including a polymerizable group (hereinafter, also referred to as a polymerizable group unit) represented by the following formula (a), and a formula ( A copolymer of a unit having an interactive group (hereinafter, also referred to as an interactive group unit) represented by b). Furthermore, the unit means a repeating unit.

In the formulas (a) and (b), R ¹ to R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group (for example, methyl, ethyl, propyl, or butyl). The substituent is not particularly limited, and examples thereof include a methoxy group, a chlorine atom, a bromine atom, and a fluorine atom.

In addition, as R ¹ , a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom is preferable. 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 formulae (a) and (b), X, Y, and Z each independently represent a single bond or a substituted or unsubstituted divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably a carbon number of 1 to 8. For example, an alkylene group such as methylene, ethylene, or propyl) , Substituted or unsubstituted divalent aromatic hydrocarbon group (preferably 6 to 12 carbons, such as phenylene), -O-, -S-, -SO _2- , -N (R)-( R: alkyl), -CO-, -NH-, -COO-, -CONH-, or a combination of these (e.g., alkyleneoxy, alkyleneoxycarbonyl, alkylenecarbonyloxy, etc. )Wait.

From the viewpoints that the polymer can be easily synthesized, the function of the plated layer (catalyst adsorption, hydrolysis resistance) is excellent, and the adhesion of the metal layer is more excellent, X, Y, and Z are preferably single bonds or ester groups. (-COO-), amido (-CONH-), ether (-O-), or a substituted or unsubstituted divalent aromatic hydrocarbon group, more preferably a single bond, an ester group (-COO- ), Amido (-CONH-).

In the formulas (a) and (b), L ¹ and L ² each independently represent a single bond or a substituted or unsubstituted divalent organic group. The definition of the divalent organic group is the same as the definition of the divalent organic group described in X, Y, and Z.

From the viewpoints that the polymer can be easily synthesized, the function of the plated layer (catalyst adsorption, hydrolysis resistance) is excellent, and the adhesion of the metal layer is more excellent, L ^{1 is} preferably an aliphatic hydrocarbon group or an amino group. Among divalent organic groups (e.g., aliphatic hydrocarbon groups) having an ester bond or a urea bond, among them, those having a total carbon number of 1 to 9 are preferred. The total carbon number of L ¹ herein means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ¹ .

In addition, from the viewpoints that the polymer can be easily synthesized, the function of the plated layer (catalyst adsorption, hydrolysis resistance) is excellent, and the adhesion of the metal layer is more excellent, L ^{2 is} preferably a single bond or a bivalent An aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of these. Among them, L ^{2 is} preferably a single bond or a total carbon number of 1 to 15, particularly preferably unsubstituted. In addition, the total carbon number of L ² here means the total number of carbon atoms contained in a substituted or unsubstituted divalent organic group represented by L ² .

In the formula (b), W represents a functional group that interacts with a plating catalyst or a precursor thereof. The definition of this functional group is the same as the definition of the said interactive group.

The polymerizable unit preferably contains 5 to 50 mol% of all the units in the polymer, and more preferably 5 to 40 mol%. If it is less than 5 mol%, the reactivity (curability, polymerizability) may decrease, and if it exceeds 50 mol%, it is likely to gel during synthesis and difficult to synthesize.

In addition, from the viewpoint of the adsorptivity of the plating catalyst or its precursor, it is preferable to contain the above-mentioned interactive base unit of 5 mol% to 95 mol% with respect to all units in the polymer. More preferably, it is 10 mol% to 95 mol%.

(Polymer Appropriate Form 2)

As a second preferable aspect of the polymer, a copolymer including a unit represented by the following formula (A), formula (B), and formula (C) is mentioned.

The unit represented by the formula (A) and the unit represented by the above formula (a) The elements are the same, and the explanations of the bases are the same.

(B) a unit represented by R ^5, X, and L ² and, X and L by the same formula unit represented by the above formula (b) in R ^{5 2,} the description of each group are also the same.

Wa in formula (B) represents a functional group that interacts with a plating catalyst or a precursor thereof other than a hydrophilic group or a precursor group thereof represented by V described later. Among them, a cyano group and an ether group are preferred.

In the formula (C), R ⁶ each 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 the divalent organic group is the same as the definition of the divalent organic group represented by X, Y, and Z described above. From the viewpoints that polymers can be easily synthesized, the function of the plated layer (catalyst adsorption, hydrolysis resistance) is excellent, and the adhesion of the metal layer is more excellent, U is preferably a single bond or an ester group (-COO-) , Amido (-CONH-), ether (-O-), or a substituted or unsubstituted divalent aromatic hydrocarbon group.

In the formula (C), L ³ represents a single bond or a substituted or unsubstituted divalent organic group. The definition of the divalent organic group is the same as the definition of the divalent organic group represented by the above-mentioned L ¹ and L ² . From the viewpoints that the polymer can be easily synthesized, the function of the plated layer (catalyst adsorption, hydrolysis resistance) is excellent, and the adhesion of the metal layer is more excellent, L ^{3 is} preferably a single bond or a divalent aliphatic A hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of these.

In 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 group that exhibits hydrophilicity. For example, Examples thereof include a hydroxyl group and a carboxylic acid group. The precursor group of a hydrophilic group refers to a group that generates a hydrophilic group by a predetermined treatment (for example, treatment with an acid or an alkali), and examples thereof include THP (2-tetrahydropyranyl) Protected carboxyl, etc.

From the viewpoint that the plated layer is easily wetted with various aqueous treatment liquids or plating liquids, the hydrophilic group is preferably an ionic polar group. Specific examples of the ionic polar group include a carboxylic acid group, a sulfonic acid group, a phosphate group, and a boric acid group. Among them, a carboxylic acid group is preferred from the viewpoint of moderate acidity (without decomposing other functional groups).

The preferable content of each unit in the 2nd preferable aspect of the said polymer is as follows.

From the viewpoints of reactivity (curability, polymerizability) and inhibition of gelation during synthesis, it is preferred that the formula (A) contains 5 mol% to 50 mol% with respect to all units in the polymer. The unit indicated by) is more preferably 5 mol% to 30 mol%.

From the viewpoint of the adsorptivity of the plating catalyst or its precursor, it is preferable that the unit represented by the formula (B) contains 5 mol% to 75 mol% of all units in the polymer. , More preferably 10 mol% to 70 mol%.

From the viewpoint of utilizing the developability of an aqueous solution and the wet-tightness, it is preferable that the unit represented by the formula (C) contains 10 mol% to 70 mol% of all units in the polymer, and more preferably It is preferably 20 mol% to 60 mol%, and particularly good is 30 mol% to 50 mol%.

Specific examples of the polymer include, for example, Japanese Patent A polymer described in paragraphs [0106] to [0112] of 2009-007540, a polymer described in paragraphs [0065] to [0070] of Japanese Patent Laid-Open No. 2006-135271, and US2010 The polymers described in paragraphs [0030] to [0108] of No.-080964.

This polymer can be manufactured by a well-known method (for example, the method in the literature mentioned above).

(Composition for forming a plated layer)

The above-mentioned polymer is contained in the composition for forming a plated layer.

The content of the polymer in the composition for forming a plated layer is not particularly limited, but it is preferably 2% to 50% by mass, and more preferably 5% to 30% by mass relative to the total amount of the composition. If it is in the said range, the handleability of a composition will be excellent and it will be easy to control the layer thickness of a to-be-plated layer.

From the viewpoint of handleability, it is preferable to include a solvent in the composition for forming a plated layer.

The solvent that can be used is not particularly limited, and examples thereof include alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, 1-methoxy-2-propanol, glycerol, and propylene glycol monomethyl ether, and acids such as acetic acid. , Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, fluorene solvents such as formamidine, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile, propionitrile, In addition to ester solvents such as methyl acetate and ethyl acetate, and carbonate solvents such as dimethyl carbonate and diethyl carbonate, examples include ether solvents, glycol solvents, amine solvents, and thiol solvents. , Halogen-based solvents, etc.

Among these, alcohol-based solvents, amidine-based solvents, ketone-based solvents, nitrile-based solvents, and carbonate-based solvents are preferred.

The content of the solvent in the plating layer-forming composition is not particularly limited, but it is preferably 50% to 98% by mass, and more preferably 70% to 95% by mass with respect to the total amount of the composition. If it is in the said range, the handleability of a composition will be excellent and it will be easy to control the layer thickness of a to-be-plated layer, etc.

If necessary, a polymerization initiator (thermal polymerization initiator, photopolymerization initiator) may be added to the composition for forming a plated layer.

(Formation procedure of plated layer)

The method for forming a polymer-containing layer using the composition for forming a plated layer on the underlayer 16 is not particularly limited, and examples thereof include a known method (for example, spin coating, die coating, dip coating, etc.) A method for applying the layer-forming layer composition to the underlayer 16 and the like.

From the viewpoint of handleability and manufacturing efficiency, it is preferable that the composition for forming a plated layer is applied to the underlayer 16 and dried, and then the remaining solvent is removed to form a polymer-containing layer. .

From the viewpoint of forming a sufficient interaction with the plating catalyst or its precursor, the coating amount of the composition for forming a plated layer is preferably 0.1 g / m ² to 10 g / m ² in terms of solid content. Especially preferred is 0.5 g / m ² to 5 g / m ² .

The method of applying energy to the polymer-containing layer on the underlayer 16 is not particularly limited, but is preferably, for example, a heat treatment or an exposure treatment, and is preferably an exposure treatment from the viewpoint that the treatment is completed in a short time.

In the exposure processing, light irradiation using an ultraviolet (UV) lamp, visible light, or the like can be 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.

The exposure time varies depending on the reactivity of the polymer and the light source, but it is usually between 10 seconds and 5 hours. The exposure energy may be about 10 mJ to 8000 mJ, and a range of 100 mJ to 7000 mJ is preferable.

When the heat treatment is used to impart energy, a blow dryer, an oven, an infrared dryer, a heating drum, or the like can be used.

<Hole formation step>

Next, the procedure of the hole formation process performed with respect to the said laminated body before a process is explained in full detail.

The hole forming step is a step of performing laser processing on the pre-processed laminated body to form holes from the surface of the plated layer 18 side of the pre-processed laminated body to the surface of the first metal layer 14. More specifically, as shown in FIG. 1 (B), laser irradiation is performed from the plated layer 18 side of the multilayer body 10 before processing, and the bottom layer 16 and the plated layer 18 are penetrated to form the first metal. The holes 22 on the surface of the layer 14, thereby manufacturing the laminated body 20 with holes.

Hereinafter, first, laser processing will be described in detail.

The laser used in the laser processing is not particularly limited as long as it is a laser that removes the bottom layer 16 and the plated layer 18 and can form a hole (channel) of a desired diameter.

Among them, from the viewpoint of excellent processability, that is, the layers can be efficiently ablated, and from the viewpoint of excellent productivity, carbon dioxide laser (CO ₂ laser) and UV-yttrium aluminum garnet ( Yttrium Aluminium Garnet (YAG) laser, excimer laser, etc.

Furthermore, the laser can be continuously irradiated or intermittently irradiated, and can also be intermittently irradiated with a single pulse.

The number of shots (shot number) in a single pulse irradiation is usually 1 to 500 times, preferably 1 to 100 times. The pulse period is usually 1 kHz ~ 8 kHz, preferably 1 kHz ~ 5 kHz.

The diameter of the hole 22 formed in this step is appropriately selected according to the purpose of use. From the viewpoint of forming a high-density multilayer substrate, the top diameter (φ) is preferably 20 μm to 150 μm. The bottom diameter (φ) is 20 μm to 120 μm. From the viewpoint of miniaturization or integration of wiring, the top diameter (φ) is preferably 20 μm to 60 μm, and the bottom diameter (φ) is 20 μm to 50 μm.

The shape accuracy of the holes 22 in the laminated body 20 with holes manufactured by the above method is extremely excellent. As a result, the second metal layer 26 and the first metal are disposed on the plated layer 18 so as to fill the holes 22. The layer 14 is excellent in electrical connectivity.

That is, the laminated body with holes 20 is useful as a substrate for forming a multilayer substrate for producing a multilayer substrate having a plurality of metal layers. Hereinafter, a first embodiment of a method for manufacturing a multilayer substrate using the laminated body 20 with holes will be described in detail.

<Multilayer substrate and manufacturing method thereof>

The manufacturing method of the multilayer substrate using the laminated body with holes 20 is not particularly limited, but as a suitable embodiment, a method having the following steps: a desmear step of performing a desmear treatment, and A catalyst applying step of applying a cladding layer with a plating catalyst (or a precursor), a plating step of performing a plating treatment, and a pattern forming step of changing the metal layer into a pattern.

The procedure of each step is described in detail below.

[Steps for removing glue residue]

The dross removing step is a step provided as necessary, and is a step of performing a dross removing process that removes the dross (residue) remaining in the holes 22 in the pore-attached laminate 20.

When the bottom layer 16 and the plated layer 18 are partially removed by laser processing, there is a case where the molten material or the decomposed material when the material constituting each layer is melted or decomposed adheres to the side or bottom of the hole 22. In addition, in order to adjust the laser processing so as not to directly affect the first metal layer 14 existing at the bottom of the hole 22, a part of the bottom layer 16 may remain at the bottom of the hole 22. By setting this step to remove such residues, the connection reliability of the channel is further improved.

In addition, when there is little glue residue on the side or bottom of the hole 22, this step may not be performed.

[Catalyst provision step]

The catalyst applying step is a step of applying a plating catalyst or a precursor thereof to the plated layer 18 in the hole-attached layered body 20 after the slag removing step.

In this step, the interactive group in the plated layer 18 is adhered (adsorbed) to the plating catalyst or its precursor provided in accordance with its function. The adsorbed plating catalyst or its precursor functions as a plating core in a plating step described later. Furthermore, when this step is performed, a plating catalyst or a precursor thereof may be applied to the bottom layer 16 exposed on the wall surface inside the hole 22.

First, the materials (plating catalyst or its precursor, etc.) used in this step will be described in detail, and then the procedure of this step will be described in detail.

(Plating catalyst)

The plating catalyst or a precursor thereof functions as a plating catalyst or an electrode in a plating step described later. Therefore, the type of the plating catalyst or its precursor to be used is appropriately determined according to the type of plating.

Furthermore, from the viewpoint that the adhesion of the metal layer is more excellent, the plating catalyst or its precursor used in this step is preferably an electroless plating catalyst or its precursor. Among these, from the viewpoint of reduction potential, the plating catalyst or its precursor is preferably a compound containing Pd, Ag, or Cu.

Hereinafter, the electroless plating or its precursors will be mainly described in detail.

As the electroless plating catalyst, any electroless plating catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a catalyst having an autocatalytic reduction reaction can be mentioned. A catalytic activity metal (for example, a metal known as an electroless-platable metal having a lower ionization tendency than Ni) and the like. More specific examples include Pd, Ag, Cu, Ni, Al, Fe, and Co. Among them, Ag and Pd are particularly preferred in terms of the level of catalytic activity.

As the electroless plating catalyst, a metal colloid (metal particle) may be used. Generally, metal colloids can be produced by reducing metal ions due to the presence of a charged surfactant or a charged protective agent.

As the electroless plating catalyst precursor, any one that can be turned into an electroless plating catalyst by a chemical reaction can be used without particular limitation. The metal ions mentioned above as the electroless plating catalyst can be mainly used. Metal ions, which are precursors of electroless plating catalysts, become zero-valent metals, which are electroless plating catalysts, by reduction reactions. As electroless plating The metal ions of the catalyst precursor may be used as an electroless plating catalyst by reducing the reaction to become a zero-valent metal after the metal ions are applied to the plated layer 18 and before being immersed in the electroless plating solution. In addition, it can be immersed in an electroless plating solution in the state of an electroless plating catalyst precursor, and can be converted into a metal (electroless plating catalyst) by a reducing agent in the electroless plating solution.

The metal ions that are precursors of the electroless plating catalyst are preferably imparted to the plated layer 18 using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent to dissociate into metal ions and bases (anions), and examples thereof include M (NO ₃ ) _n , MCl _n , and M _{2 / n} ( SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As the metal ion, one obtained by dissociating the above-mentioned metal salt can be suitably used. Specific examples include Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, metal ions capable of multidentate coordination are preferred, and especially those capable of coordination From the viewpoint of the number of types of functional groups and catalytic activity, Ag ions and Pd ions are preferred.

In this step, as a catalyst for directly performing electroplating without performing electroless plating, a zero-valent metal other than the above may be used.

The plating catalyst or its precursor is preferably used in the form of a plating catalyst liquid (a dispersion or a solution obtained by dispersing or dissolving in a solvent) containing the plating catalyst or its precursor.

The plating catalyst liquid usually contains a solvent. As the type of the solvent, an organic solvent and / or water can be used. Generally, water is used as a main component. Since the plating catalyst liquid contains an organic solvent, the permeability of the plating catalyst liquid to the plated layer 18 is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the interaction group.

The organic solvent used in the plating catalyst liquid is not particularly limited as long as it is a solvent that can penetrate into the plated layer 18. Specifically, acetone, methyl ethyl acetate, and ethyl acetate can be used. Ethyl acetate, ethylene glycol diacetate, cyclohexanone, acetoacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, glyceryl triacetate, diethyl Diethylene glycol diacetate, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve, 1-methoxy 2-propanol and the like.

(Procedure of catalyst provision step)

A method of applying a plating catalyst or a precursor thereof to the plated layer 18 is not particularly limited.

For example, the above-mentioned plating catalyst liquid (a dispersion liquid in which a metal is dispersed in an appropriate dispersion medium or a solution containing metal ions obtained by dissolving and dissociating a metal salt in an appropriate solvent) can be mentioned, and A method of applying a plating catalyst liquid to the plated layer 18; or a method of immersing the porous layered body 20 on which the plated layer 18 is formed in a plating catalyst liquid, etc. Method for contacting the plated layer 18.

The contact time between the plated layer 18 and the plating catalyst liquid is preferably about 30 seconds to 10 minutes, and more preferably about 3 minutes to 5 minutes.

The temperature of the plating catalyst liquid at the time of contact is preferably about 20 ° C to 60 ° C, and more preferably about 30 ° C to 60 ° C from the viewpoint of temperature maintenance.

[Plating step]

The plating step is a plating process for the plated layer to which the plating catalyst or a precursor thereof is applied by the above-mentioned catalyst applying step, and the second metal layer that is in contact with and is in contact with the first metal layer through a hole. Step formed on the plated layer Step. More specifically, by implementing this step, as shown in FIG. 1 (C), a second metal layer 26 is provided on the plated layer 18 so as to fill the hole 22, and the first metal layer 14 can be obtained. A multilayer substrate 24 with a second metal layer 26. The second metal layer 26 is in contact with the first metal layer 14 through the hole 22 and is electrically connected.

The types of plating treatment performed in this step include electroless plating and electrolytic plating. In the above steps, the functions of the plating catalyst or its precursor provided on the plated layer 18 can be used. Make a selection.

Among these, from the viewpoint that the adhesion of the formed second metal layer 26 is more excellent, electroless plating is preferably performed. In addition, in order to obtain the second metal layer 26 having a desired layer thickness, a more preferable form is electrolytic plating after electroless plating.

Hereinafter, the plating which can be suitably performed in this step is demonstrated.

(Electroless plating)

The electroless plating refers to an operation in which a metal is precipitated by a chemical reaction using a solution in which metal ions to be deposited as a plating layer are dissolved.

The electroless plating in this step is performed as follows. For example, the porous laminated body 20 provided with the electroless plating catalyst is washed with water to remove excess electroless plating catalyst (metal), and then immersed in the electroless plating. In the bath. As the electroless plating bath used, a known electroless plating bath can be used. Furthermore, from the viewpoint of easiness of obtaining, it is preferable that the electroless plating bath is a case where an alkaline electroless plating bath (pH is preferably about 9 to 14) is used.

In addition, in a state in which the electroless plating catalyst precursor is adsorbed or impregnated in the to-be-plated layer 18, the adhesion to the electroless plating catalyst precursor is provided. When the porous layered body 20 is immersed in an electroless plating bath, it is preferred that the porous layered body 20 be washed with water to remove excess precursors (metal salts, etc.), and then immersed in the electrolytic plating bath. In this case, in the electroless plating bath, the reduction of the plating catalyst precursor and the electroless plating immediately following it are performed. As the electroless plating bath used here, a known electroless plating bath can be used in the same manner as described above.

Furthermore, it is also possible to prepare a catalyst activating liquid (reducing liquid) different from the form using the electroless plating solution as described above, and perform the reduction of the electroless plating catalyst precursor as another step before the electroless plating. . The catalyst activating solution is a solution in which a reducing agent capable of reducing the electroless plating catalyst precursor (mainly metal ions) to a zero-valent metal is dissolved. The concentration of the reducing agent relative to the entire solution is preferably 0.1% by mass. ~ 50 mass%, more preferably 1 mass% to 30 mass%. As the reducing agent, a known reducing agent (for example, a boron-based reducing agent such as sodium borohydride or dimethylamine borane, formaldehyde, hypophosphite, etc.) can be used.

At the time of dipping, it is preferable to keep the concentration of the electroless plating catalyst or its precursor near the surface of the plated layer 18 in contact with the electroless plating catalyst or its precursor fixed, and then apply agitation. Or oscillate while dipping.

As a composition of a general electroless plating bath, for example, in addition to a solvent (for example, water), it mainly contains 1. metal ions for plating, 2. reducing agents, and 3. additives (stabilizers) for improving the stability of metal ions. .

The organic solvent used in the plating bath must be a water-soluble solvent. From this viewpoint, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol can be preferably used.

As the kind of metal 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 preferred from the viewpoint of conductivity. In addition, the above-mentioned metal is blended to select an optimal reducing agent and additive.

The thickness of the second metal layer 26 obtained by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath, but from the viewpoint of conductivity In particular, it is preferably 0.1 μm or more, and more preferably 0.2 μm to 2 μm.

However, when the second metal layer 26 formed by electroless plating is used as a conductive layer and the electrolytic plating described later is performed, it is preferable to uniformly provide a layer of at least 0.1 μm or more.

The immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.

(Electrolytic plating (plating))

In this step, when the plating catalyst or its precursor provided in the above step has a function as an electrode, electrolytic plating may be performed on the plated layer 18 provided with the catalyst or its precursor.

In addition, after the above-mentioned electroless plating, the formed metal layer may be used as an electrode, and further electrolytic plating may be performed. This makes it possible to easily newly form the second metal layer 26 having an arbitrary thickness on the basis of the electroless plated film having excellent adhesion to the laminated body 20 with holes. As described above, since the metal layer can be formed to a thickness corresponding to the purpose by performing electrolytic plating after electroless plating, the second metal layer 26 is suitable for various applications.

As a method of electrolytic plating, a conventionally known method can be used. Furthermore, Examples of the metal used in electrolytic plating include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferred, and copper is more preferred. .

The thickness of the second metal layer 26 obtained by electrolytic plating can be controlled by adjusting the concentration of the metal contained in the plating bath, the current density, and the like.

When applied to general electric wiring and the like, the layer thickness of the second metal layer 26 is preferably 0.5 μm or more, and more preferably 1 μm to 30 μm from the viewpoint of conductivity.

[Pattern forming step, step]

The pattern forming step is a step provided as necessary, and is a step of etching the second metal layer obtained by the plating step into a pattern shape to form a pattern metal layer.

More specifically, as shown in FIG. 1 (D), in this step, an unnecessary portion of the second metal layer 26 is removed, thereby forming a patterned metal layer 28 on the plated layer 18. In this step, an unnecessary portion of the metal layer 26 formed on the entire surface of the substrate 12 is removed by etching, whereby a metal layer 28 having a desired pattern can be formed.

The pattern can be formed by any method. Specifically, a known subtractive method is generally used (a patterned mask is provided on the metal layer, and the mask is removed after etching the area where the mask is not formed. And a method for forming a patterned metal layer), a semi-additive method (a patterned mask is provided on the metal layer, and a metal layer is formed in a region where the mask is not formed, and then the mask is processed. A method of removing and performing an etching process to form a patterned metal layer).

The subtractive method refers to a method in which a resist layer is provided on the formed second metal layer 26, and the same pattern as the metal layer pattern portion is formed by pattern exposure and development, and then the resist pattern is formed. As a mask, the second metal layer 26 is removed by an etching solution to form a patterned metal layer 28.

As the resist, any material can be used, and a negative, positive, liquid, or film resist can be used. In addition, as the 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 as long as it is arbitrarily selected. From the viewpoint of the simplicity of the apparatus and the like in terms of operation of the work, wet etching is preferred. As the etching solution, for example, an aqueous solution such as copper chloride or ferric chloride can be used.

The semi-additive method is a method in which a resist layer is provided on the formed second metal layer 26, and the same pattern as that of the non-metal layer pattern portion is formed by pattern exposure and development, and then the resist is The agent pattern is used as a mask for electrolytic plating, and after the resist pattern is removed, a rapid etching is performed, and the second metal layer 26 is removed into a pattern, thereby forming a patterned metal layer 28.

The same materials as the subtractive method can be used for the resist and the etchant. As the electrolytic plating method, the method described above can be used.

In addition, the second metal layer 26 may be removed, and the plated layer 18 may be removed together by a known method (for example, dry etching) or the like.

The multilayer substrate obtained by the above manufacturing method can be applied to Flexible Printed Circuit (FPC), Chip On Film (COF), Tape Automated Bonding (TAB), female Motherboard, package interposer substrate, and other applications. Particularly useful for wiring substrates (e.g., Printed wiring board). In addition, in this specification, a multilayer substrate means the metal layer substrate which has two or more layers. By patterning the metal layers (the first metal layer 14 and the second metal layer 26) into a patterned wiring, a multilayer wiring board can also be obtained.

If necessary, an insulating layer may be further provided on the second metal layer 26 (or the patterned metal layer 28). As the insulating layer, a known material can be used, and examples thereof include a known interlayer insulating film, a solder resist, and the like.

Further, the second metal layer 26 (or the patterned metal layer 28) may be further provided with the above-mentioned underlayer 16 and the plated layer 18, and used as a material for forming the hole (laminated body before processing).

<Second Embodiment>

As shown in FIG. 2 (A), the second embodiment of the method for manufacturing a laminated body with holes and a multilayer wiring according to this embodiment differs from the first embodiment in that the substrate 12, the first metal layer 14, Pre-processed laminated body 100 of insulating layer 30, bottom layer 16, and plated layer 18.

In the following, the insulating layer 30 in the laminated body 100 before processing is mainly described in detail, and this embodiment is described in detail with reference to FIG. 2. In addition, in FIG. 2, the same reference numerals are given to the same constituent elements as the respective constituent elements of the multilayer substrate shown in FIG. 1, and description thereof is omitted.

[Insulation]

The insulating layer 30 is a layer provided to ensure insulation reliability between the first metal layer 14 and the second metal layer 26.

The material constituting the insulating layer 30 is not particularly limited, and examples thereof include thermosetting Insulating resins such as chemical resins and thermoplastic resins. That is, the form in which the insulating layer 30 is an insulating resin layer is mentioned.

More specifically, examples of the thermosetting resin include epoxy resin, phenol resin, polyimide resin, polyester resin, bismaleimide resin, polyolefin resin, and isocyanate resin. Examples of the thermoplastic resin include phenoxy resin, polyether fluorene, polyfluorene, polyphenylene fluorene, polyphenylene sulfide, polyphenylene ether, polyether fluorene, and imine.

Among these, epoxy resin is preferred from the viewpoints that the insulating properties of the insulating layer 30, compatibility with the inorganic filler, and resistance to a chemical solution are more excellent.

The thickness of the insulating layer 30 is appropriately selected according to the purpose of use of the laminate, but from the viewpoint of ensuring the insulation properties of the first metal layer 14 and the second metal layer 26, it is preferably 10 μm to 150 μm, and more preferably 20 μm ~ 100 μm.

The insulating layer 30 may contain an inorganic filler. The inorganic filler is generally used to reduce the coefficient of thermal expansion (CTE) and increase the insulation of the insulating layer 30. When an inorganic filler is contained in the insulating layer 30, the film strength of the insulating layer 30 is improved, and as a result, the adhesion of the second metal layer 28 described later to the substrate is improved.

The type of the inorganic filler is not particularly limited, and examples thereof include metal compounds (for example, oxides, nitrides, sulfides, carbides, and composites thereof) of the metal. From the viewpoint of the insulation properties and film strength of the insulating layer 30, In other words, metal oxide particles (especially SiO ₂ ) are preferred.

Specific examples of the inorganic filler include silicon dioxide, aluminum oxide, clay, talc, aluminum hydroxide, and calcium carbonate.

The shape of the inorganic filler is not particularly limited, and any shape such as a spherical shape, a plate shape, a fibrous shape, a rod shape, an irregular shape, and a hollow shape can be preferably used.

The method for forming the insulating layer 30 is not particularly limited. For example, a method (coating method) of applying an insulating resin composition containing an insulating resin to the substrate 12 and applying a heat treatment or an exposure treatment to form the insulating layer 30 as required; or an insulating resin A method of laminating the insulating layer 30 on the substrate 12 and the like.

As shown in FIG. 2 (B), the laser processing is performed on the pre-processed laminated body 100 to penetrate the insulating layer 30, the bottom layer 16 and the plated layer 18 to form a hole 22 reaching the surface of the first metal layer 14. Thus, the laminated body 200 with holes is manufactured.

Thereafter, by executing the procedure described in the first embodiment, the multilayer substrate 240 shown in FIG. 2 (C) can be formed, and as shown in FIG. 2 (D), the above-mentioned etching step can be used. A patterned metal film 28 is manufactured.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples.

Hereinafter, a method for synthesizing the polymer used in this example will be described in detail.

(Synthesis Example 1: Polymer 1)

1 L of ethyl acetate and 159 g of 2-aminoethanol were added to a 2 L three-necked flask, and the mixture was cooled with an ice bath. It adjusted so that internal temperature might become 20 degreeC or less, and 150 g of 2-bromoisobutyric acid bromide was dripped at it. Thereafter, the internal temperature was raised to room temperature (25 ° C), and the reaction was performed for 2 hours. End of reaction Then, 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 then dried with magnesium sulfate, and then ethyl acetate was distilled off to obtain 80 g of a raw material A.

Next, 47.4 g of raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were added to a 500 mL three-necked flask, and the mixture was cooled in an ice bath. It adjusted so that internal temperature might become 20 degreeC or less, and 25 g of propylene chloride was dripped at it. Thereafter, the liquid temperature of the reaction solution was raised to room temperature and reacted for 3 hours. After the reaction was completed, 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 then dried with magnesium sulfate, and the ethyl acetate was distilled off. Thereafter, the monomer M1 (20 g) shown below was purified by column chromatography.

8 g of N, N-dimethylacetamide was added to a 500 mL three-necked flask, and heated to 65 ° C. under a stream of nitrogen. To this was added dropwise a monomer M1: 14.3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.0 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.5 g, and V-65 (manufactured by Wako Pure Chemical Industries) 0.4 g of N over a period of 4 hours. , N-dimethylacetamide 8 g solution.

After completion of the dropwise addition, the reaction solution was further stirred for 3 hours. Thereafter, 41 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature to stop. To the above reaction solution was added 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical (2,2,6,6-tetramethylpiperidine 1-Oxyl, TEMPO) (manufactured by Tokyo Chemical Industry) 0.09 g, 1,8-diazabicyclo [5.4.0] undec-7-ene (1,8-Diazabicyclo [5.4.0] undec-7-ene, DBU) 54.8 g, and at room temperature The reaction was performed for 12 hours. Then, 54 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction liquid. After completion of the reaction, reprecipitation was performed in water, and then the solid matter was taken out to obtain polymer 1 (12 g). In addition, a polymerizable group-containing unit: a nitrile group-containing unit: a carboxylic acid group unit = 30: 30: 40 (mol%).

<Examples and Comparative Examples> [Fabrication of substrate]

GX-13 (Ajinomoto Fine-Techno) (film thickness: 40 μm) was vacuum-laminated on a copper-clad FR-4 (Hitachi Kasei, glass epoxy substrate). Bake at 1 degreeC for 1 hour, and the obtained thing was made into board | substrate A. Furthermore, the copper layer (equivalent to the first metal layer) The thickness is 18 μm.

[Underlying production]

Any one of the below-described underlayer-forming compositions P01 to P22 was dropped on the surface of the substrate A, and spin-coated at 1000 rpm for 20 seconds. Then, it baked at 180 degreeC for 15 minutes, and obtained the substrate S001 with a bottom layer-the substrate S022 with a bottom layer.

(Composition for forming a base layer)

A predetermined amount of the components described in Table 1 below was added to a 1000 ml bottle made of polypropylene (Polypropylene, PP), and the homogenizer (Homo Disper) manufactured by TK was used to disperse it at 8000 rpm for 30 minutes. To obtain a composition for forming a bottom layer.

As the dispersant, SOLSPERSE 24000GR (manufactured by Lubrizol) was used.

[Production of plated layer]

A composition for forming a plated layer having a composition described later was dropped on the bottom surface of any one of the substrate S001 with a substrate to the substrate S022 with a substrate and spin-coated at 3000 rpm for 20 seconds. Thereafter, it was baked at 150 ° C. for 15 minutes, and further subjected to UV irradiation (energy: 500 mJ, 10 mW, wavelength: 365 nm) to form a plated layer, thereby obtaining a pre-processed laminated body S101-pre-processed laminated body S122.

(Composition for forming a plated layer)

Add the above polymer 1 (2g), MFG (methylpropanediol) (78.3g), water (19.6g), IRGACURE OXE-02 (BASF) to a 200ml beaker filled with a magnetic stirrer. (Manufactured by the company) (0.1 g) to prepare a composition for forming a plated layer.

[Hole formation step]

A CO ₂ laser processing machine (manufactured by Hitachi Via Mechanics, LC) set up with a hole size of 90 μm on the surface of the plated layer and a conditional output of 70 μm on the GX-13 / copper interface. -K), performing CO ₂ laser channel processing (the number of holes: 961) on any one of the pre-processed laminated body S101 to the pre-processed laminated body S122 to obtain a hole-attached layered body S201-hole-attached layered body S222.

[Catalyst providing step and plating step]

At 50 ° C., immerse any one of the porous layered body S201 to porous body layered body S222 in the detergent solution ACL-009 (Uemura Industries) for 5 minutes, and then wash it twice with pure water. After that, it was immersed in Pd catalyst-imparting solution MAT-2 (Uemura Industries) for 5 minutes at room temperature, and then purified water was used. Wash 2 times.

Then, the laminated body with pores subjected to the above treatment was immersed in a reducing agent MAB (Kamimura Kogyo) for 5 minutes at 36 ° C, and then washed twice with pure water. After that, it was immersed in the activation treatment liquid MEL-3 (Kamimura Kogyo) for 5 minutes at room temperature, and then immersed in the electroless plating solution Thru-Cup PEA (Kamimura Kogyo) for 60 minutes at room temperature without cleaning. Minutes, thereby forming an electroless plated layer (thickness: 1 μm) on the plated layer.

Furthermore, a mixed solution of 1283 g of water, 135 g of copper sulfate pentahydrate, 342 g of 98% concentrated sulfuric acid, 0.25 g of 36% concentrated hydrochloric acid, and 39.6 g of ET-901M (Rohm and Haas) was used as the electrolytic plating. After applying the liquid, the laminated body with holes formed with an electroless plating layer and a copper plate were mounted on a holder, and then connected to a power source, and then subjected to electrolytic copper plating treatment at 3 A / dm ² for 45 minutes to obtain a plating having a thickness of about 18 μm. Multilayer substrate (level 1 to level 22) of copper layer (metal layer).

[Adhesiveness evaluation]

The multilayer substrates obtained in Levels 1 to 22 (Examples and Comparative Examples) were baked at 150 ° C for 15 minutes. A portion of the metal layer of the obtained sample where no holes (channels) were present was cut at a distance of 10 mm, and a 130 mm incision was cut in parallel, and a cut was made at the end with a cutter and raised by 10 mm. The peeled end was grasped and the peel strength was measured using Tensilon (SHIMAZU) (tensile speed: 50 mm / min). The results are summarized and shown in Table 2.

Furthermore, the case where the adhesion is 0.7 kN / m or more is "A", and the case where the adhesion is 0.5 kN / m or more and less than 0.7 kN / m is "B", The case where the adhesion is less than 0.5 kN / m is set to "C".

[Evaluation of hole shape]

The shape evaluation of the laminated body with pores obtained in Levels 1 to 22 (Examples and Comparative Examples) was performed using cross-sectional SEM images.

More specifically, 100 holes were arbitrarily selected from the laminated body with holes after the above-mentioned [hole formation step] was performed, and the shape defects were confirmed by observing the 100 holes. When the channel hole diameter is set to 100%, a case where the plating layer has a protrusion (overhang) of 2% or more relative to the channel diameter of 90 μm is regarded as a failure.

When 100 holes were observed, the case where the number of holes identified as having the above failure was 1 or less was evaluated as "A", and the number of holes identified as having the above failure was 2 or more and 10 or less. The evaluation was "B", and the case where the number of holes identified as having the above-mentioned failure was 11 or more was evaluated as "C". The results are summarized and shown in Table 2.

In Table 2, the column "Type of composition for formation of underlayer" shows the type of composition for formation of underlayer used at each level.

In Table 2, the "cyano group ratio" indicates the content (mole%) of the cyano group-containing repeating unit in the polymer having the cyano group-containing repeating unit in the bottom layer with respect to all the repeating units.

In Table 2, "silicon dioxide particle size" and "silicon dioxide concentration" indicate the "particle diameter (nm)" of the silicon dioxide particles in the bottom layer, and the relative proportion of the silicon dioxide particles in the bottom layer to the polymer and the "Concentration (mass%)" of the total mass of the silica particles.

As shown in Table 2, in a form (Example 1 to Example 14) containing a polymer showing a predetermined cyano ratio and containing a predetermined amount of metal oxide particles of a predetermined size, it showed excellent pore shape accuracy and excellent The adhesion of the metal layer.

In particular, when the content of the metal oxide particles is 20% by mass to 50% by mass (for example, level 3 to level 6), more excellent adhesion of the metal layer is exhibited.

On the other hand, in Comparative Examples 1 to 8 which did not contain a predetermined polymer or a predetermined metal oxide particle, at least one of the accuracy of the pore shape and the adhesion of the metal layer was not good.

<Example 15>

The multilayer substrate obtained in Example 1 was heat-treated at 180 ° C for 1 hour, and then a dry resist film was applied at 70 ° C and 0.2 MPa using a vacuum laminator (Made by Seiki Seisakusho Co., Ltd .: MVLP-600). (Manufactured by Hitachi Chemical Co., Ltd .; RY3315, film thickness 15 μm) laminated on the surface of the second metal layer of the multilayer substrate. Next, the multilayer substrate on which the dry-resist film is laminated is brought into close contact with a glass mask capable of forming comb wiring (according to JPCA-BU01-2007) specified in JPCA-ET01, and an exposure machine having a center wavelength of 405 nm is used. The resist was irradiated with 70 mJ of light energy. The exposed multilayer substrate was sprayed with a 1% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.2 MPa for development. Thereafter, the multilayer substrate is washed with water and dried to form a resist pattern for the subtractive method on the second metal layer.

The second substrate in the region where the resist pattern was not formed was etched by immersing the multilayer substrate on which the resist pattern was formed in an aqueous FeCl ₃ / HCl solution (etching solution) at a temperature of 40 ° C. Layer removed. Thereafter, a 3% NaOH aqueous solution was sprayed on the multilayer substrate with a spray pressure of 0.2 MPa to swell and peel the resist pattern, and then neutralized with a 10% sulfuric acid aqueous solution and washed with water to obtain a comb type. Wiring (patterned metal layer). L / S of the obtained wiring was 75 μm / 75 μm.

Further, for a multilayer substrate having a patterned metal layer, a solder resist (PFR800; manufactured by TAIYO INK MFG) (stock) was vacuum-laminated under conditions of 110 ° C and 0.2 MPa, and a center wavelength of 365 nm The exposure machine radiates 420 mJ of light energy.

Next, the multilayer substrate was subjected to a heating treatment at 80 ° C. for 10 minutes, and then a NaHCO ₃ : 10% aqueous solution was applied to the surface of the multilayer substrate at a spray pressure of 2 kg / m ² to perform development and drying. Thereafter, the multi-layer substrate was irradiated with light energy of 1000 mJ again using an exposure machine having a center wavelength of 365 nm. Finally, heat treatment was performed at 150 ° C / 1hr to obtain a wiring substrate covered with a solder resist.

10、100‧‧‧Laminated body before processing

12‧‧‧ substrate

14‧‧‧ 1st metal layer

16‧‧‧ ground floor

18‧‧‧ is plated

20, 200‧‧‧ Laminated with holes

22‧‧‧hole

24, 240‧‧‧ multilayer substrate

26‧‧‧Second metal layer

28‧‧‧ patterned metal layer

30‧‧‧ Insulation

FIGS. 1 (A) to 1 (D) are schematic cross-sectional views showing respective manufacturing steps in the first embodiment of the method for manufacturing a laminated body with holes and a multilayer substrate according to the present invention, respectively.

FIGS. 2 (A) to 2 (D) are schematic cross-sectional views showing respective manufacturing steps in the second embodiment of the method for manufacturing a laminated body with holes and a multilayer substrate according to the present invention, respectively.

10‧‧‧Laminated body before processing

12‧‧‧ substrate

14‧‧‧ 1st metal layer

16‧‧‧ ground floor

18‧‧‧ is plated

20‧‧‧ Laminated with Pore

22‧‧‧hole

24‧‧‧Multi-layer substrate

26‧‧‧Second metal layer

28‧‧‧ patterned metal layer

Claims (7)

A method for manufacturing a laminated body with holes includes a hole forming step of performing laser processing on a pre-processed laminated body having a first metal layer, a bottom layer, and a plated layer in order on the substrate to form the pre-processed laminated layer. The surface of the plated layer side of the body reaches the hole of the surface of the first metal layer, the bottom layer contains a polymer having repeating units containing a cyano group and metal oxide particles, and the plated layer has a contact with a plating catalyst. Or its precursor interacts with a functional group, and the cyano-containing repeating unit has a structure represented by formula (1), and the cyano-containing repeating in the polymer is relative to all the repeating units in the polymer. The content of the unit is 10 mol% to 60 mol%, and the metal oxide particles include a metal of at least one metal element selected from the group consisting of 4A element, 5A element, 3B element, and 4B element of the periodic table. Oxide particle, the particle diameter of the metal oxide particle is 50 nm to 2000 nm, and the metal oxide particle in the bottom layer is relative to the total mass of the polymer and the metal oxide particle The content is 20% by mass to 60% by mass. The plating catalyst includes a compound of a metal having a catalytic activity for a self-catalytic reduction reaction, and the functional group is selected from the following groups or salts thereof: amine group, amidine group, Hydrazone, ureido, tertiary amine, ammonium, formamidine, triazine ring, triazole ring, benzotriazolyl, imidazolyl, benzimidazolyl, quinolinyl, pyridyl, pyrimidine Group, pyrazinyl group, quinazolinyl group, quinoxaline group, purinyl group, triazinyl group, piperidinyl group, piperazinyl group, pyrrolidinyl group, pyrazolyl group, aniline group, group containing alkylamine structure, Isocyanuric group-containing group, nitro, nitroso, azo, diazo, azide, cyano, cyanate, ether, hydroxyl, phenolic hydroxyl, carboxyl, carbonate Group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, group containing N-hydroxy structure, thienyl group, thiol group, thiourea group, trimeric thiocyanate group , Benzothiazolyl, mercaptotriazinyl, thioether, thiooxy, fluorenyl, fluorenyl, sulfite, fluorenimine-containing group, oxidizing group Group, a sulfonic acid salt structure-containing group, a phosphate group, phosphorous acyl group, a phosphino group sulfonic acid ester structure, a group containing a phosphoric ester structure-containing group and a group containing chlorine atoms, bromine atoms,

In the formula (1), R ⁷ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ⁴ represents a single bond or a substituted or unsubstituted divalent organic group. The method for manufacturing a laminated body with pores according to item 1 of the scope of the patent application, wherein the content of the metal oxide particles in the bottom layer is 20% to 50% of the total mass of the polymer and the metal oxide particles. quality%. A method for manufacturing a multi-layer substrate, comprising: a catalyst providing step for applying the above-mentioned plated layer in the laminated body with holes obtained by the manufacturing method described in the first or second aspect of the patent application scope; Providing a plating catalyst or a precursor thereof; and a plating step of subjecting the plated layer to which the above-mentioned plating catalyst or its precursor is provided to a plating layer to contact the first metal layer through the hole and The conductive second metal layer is formed on the plated layer. The method for manufacturing a multilayer substrate according to item 3 of the scope of the patent application, further comprising a pattern forming step of etching the second metal layer into a pattern after the plating step, and forming a patterned metal layer. A printed wiring board includes a multilayer substrate manufactured by a manufacturing method as described in item 3 or 4 of the scope of patent application. A laminated body with holes includes a first metal layer, a bottom layer, and a plated layer in this order on a substrate. The bottom layer includes a polymer having a repeating unit containing a cyano group and metal oxide particles. A functional group that interacts with a catalyst or a precursor thereof. The cyano-containing repeating unit has a structure represented by formula (1). The cyano group is contained in the polymer with respect to all the repeating units in the polymer. The content of the repeating unit is 10 mol% to 60 mol%. The metal oxide particles include at least one metal element selected from the group consisting of 4A element, 5A element, 3B element, and 4B element of the periodic table. The metal oxide particles have a particle diameter of 50 to 2000 nm, and the content of the metal oxide particles in the underlayer is 20 to 60% by mass relative to the total mass of the polymer and the metal oxide particles. % By mass, and has a hole from the surface on the side to be plated to the surface of the first metal layer, the plating catalyst contains a compound of a metal having a catalytic activity for a self-catalytic reduction reaction, The functional group is selected from the following groups or salts thereof: amine group, amidine group, amido group, urea group, tertiary amino group, ammonium group, formamidine group, triazine ring, triazole ring, benzene Benzotriazolyl, imidazolyl, benzimidazolyl, quinolinyl, pyridyl, pyrimidinyl, pyrazinyl, quinazolinyl, quinoxaline, purinyl, triazinyl, piperidinyl, piperazine Group, pyrrolidinyl group, pyrazolyl group, aniline group, group containing alkylamine structure, group containing isocyanuric acid structure, nitro group, nitroso group, azo group, diazo group, azide group, Cyano, cyanate, ether, hydroxyl, phenolic hydroxyl, carboxyl, carbonate, carbonyl, ester, N-oxide structure-containing group, S-oxide structure-containing group, N-hydroxy group Structural groups, thienyl, thiol, thiourea, trimeric thiocyanate, benzothiazolyl, mercaptotriazine, thioether, thiooxy, fluorenyl, fluorenyl, sulfite , A group containing a sulfonium imine structure, a group containing a sulfonium oxide structure, a sulfonic acid group, a group containing a sulfonate structure, a phosphate group, a phosphoramido group, a phosphine group, a phosphate group structure Group, a group containing a group containing chlorine atoms and bromine atoms,

In the formula (1), R ⁷ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ⁴ represents a single bond or a substituted or unsubstituted divalent organic group. A composition for forming a bottom layer, comprising a polymer having a cyano group-containing repeating unit and metal oxide particles, and the cyano group-containing repeating unit has a structure represented by formula (1), and is relative to all repeats in the polymer. Unit, the content of the cyano-containing repeating unit in the polymer is 10 mol% to 60 mol%, and the metal oxide particles include a member selected from the group consisting of 4A element, 5A element, 3B element, and 4B element of the periodic table The metal oxide particles of at least one kind of metal element in the group have a particle diameter of 50 nm to 2000 nm, and are used for the formation of the underlayer relative to the total mass of the polymer and the metal oxide particles. The content of the metal oxide particles in the bottom layer formed by the composition is 20% by mass to 60% by mass,

In the formula (1), R ⁷ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and L ⁴ represents a single bond or a substituted or unsubstituted divalent organic group.