JPWO2019171985A1 - Electroless plating base material containing polymer and metal fine particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a plating base layer having high heat resistance and not containing corrosive atoms, and further to realize cost reduction in its production, a new base agent used as a pretreatment step of electroless plating. To provide.
An electroless plating base material for forming a metal plating film on a base material by an electroless plating treatment.
(A) A structural unit derived from a monomer a having a metal dispersible group and one radically polymerizable double bond in the molecule, a non-radical polymerizable crosslinkable group in the molecule, and one radically polymerizable two. A polymer of a polymerizable compound containing a structural unit derived from a monomer b having a double bond (however, the copolymer has a metal dispersible group and one or more radically polymerizable double bonds in the molecule c. (Excluding the copolymer (A1) containing the structural unit derived from the structural unit derived from and the structural unit derived from the monomer d having two or more radically polymerizable double bonds in the molecule),
(B) Metal fine particles,
A base material containing (C) a cross-linking agent and (D) a solvent.
[Selection diagram] None

Description

The present invention relates to an electroless plating base material containing polymer and metal fine particles, and a plating base material.

In electroless plating, a uniform thickness film can be obtained regardless of the type and shape of the substrate simply by immersing the substrate in the plating solution, and a metal plating film can be applied to non-conductor materials such as plastic, ceramics, and glass. It is widely used in various fields such as decorative applications such as giving a sense of quality and aesthetics to resin molded bodies such as automobile parts, and wiring technology for electromagnetic shielding, printed circuit boards, large-scale integrated circuits, etc. ing.
Usually, when a metal plating film is formed on a base material (object to be plated) by electroless plating, a pretreatment for improving the adhesion between the base material and the metal plating film is performed. Specifically, first, the surface to be treated is roughened and / or made hydrophilic by various etching means, and then an adsorbent that promotes adsorption of the plating catalyst on the surface to be treated is supplied onto the surface to be treated. A treatment (sensitization) and an activation treatment (activation) in which the plating catalyst is adsorbed on the surface to be treated are performed. Typically, the sensitization treatment immerses the object to be treated in an acidic solution of stannous chloride, which causes a metal (Sn ²⁺ ) that can act as a reducing agent to adhere to the surface to be treated. Then, the sensitized surface to be treated is immersed in an acidic solution of palladium chloride as an activation treatment. As a result, the palladium ions in the solution are reduced by the metal (tin ion: Sn ²⁺ ) which is a reducing agent, and adhere to the surface to be treated as an active palladium catalyst nucleus. After such pretreatment, it is immersed in an electroless plating solution to form a metal plating film on the surface to be treated.

On the other hand, an example in which a composition containing a highly branched polymer having an ammonium group and metal fine particles is used as a base material (plating catalyst) for electroless plating has been reported, and a pretreatment step (coarse) of the conventional electroless plating treatment has been reported. Various improvements such as environmental aspects, cost aspects, and complicated operability have been achieved, such as avoiding the use of chromium compounds (chromic acid), which has been a problem in surface treatment), and reducing the number of pretreatment steps. A proposal for an electroless plating base material has been made (Patent Document 1).

International Patent Application Publication No. 2012/141215 Pamphlet

In the above-mentioned composition containing a highly branched polymer having an ammonium group and metal fine particles proposed as a base material for electroless plating, when this is applied to wiring technology in semiconductor manufacturing or the like, the highly branched contained therein Since the heat resistant temperature of the polymer is low, the highly branched polymer may be decomposed by solder reflow or high temperature treatment. Further, there is also a problem that it is difficult to impart adhesion to an LCP (liquid crystal polymer) substrate, which is a substrate having excellent electrical characteristics used in next-generation communication equipment such as 5G.
As described above, the electroless plating base materials proposed so far include plating having high heat resistance without containing corrosive atoms such as halogen atoms and sulfur atoms in addition to the plating performance as the plating base material. Various performances such as being able to be given, being easily varnished into various compositions, having high metal fine particle dispersion stability, adhesion to LCP substrates, and operability such as being easily manufactured with a small number of processes. There has been no proposal for an electroless plating base material that fully realizes the above characteristics.
Focusing on these problems, the present invention pays attention to these problems, and can form a plating base layer having high heat resistance and excellent adhesion to an LCP substrate, and further, it is possible to realize cost reduction in its production, and it is possible to realize a pretreatment for electroless plating. The purpose is to provide a new base material used as a process.

As a result of diligent studies to achieve the above object, the present inventors have investigated a polymer containing a metal dispersible group but not containing a corrosive atom, and combined the polymer with metal fine particles and based on the polymer. We have found that the layer obtained by coating on a material has not only plating properties but also high heat resistance as a base layer for electroless metal plating and is excellent in adhesion to an LCP substrate, and completed the present invention. ..

That is, the present invention is, as a first aspect, an electroless plating base material for forming a metal plating film on a base material by an electroless plating treatment.
(A) A structural unit derived from a monomer a having a metal dispersible group and one radically polymerizable double bond in the molecule, a non-radical polymerizable crosslinkable group in the molecule, and one radically polymerizable two. A copolymer containing a structural unit derived from a monomer b having a double bond (however, the copolymer is derived from a monomer c having a metal dispersible group and one or more radically polymerizable double bonds in the molecule. Copolymers (A1) containing a structural unit and a structural unit derived from a monomer d having two or more radically polymerizable double bonds in the molecule),
(B) Metal fine particles,
The present invention relates to (C) a cross-linking agent and (D) a base material containing a solvent.
A second aspect of the present invention relates to the base material according to the first aspect, which comprises a composite in which the (B) metal fine particles are adhered or coordinated to the metal dispersible group in the (A) copolymer.
As a third aspect, the base material according to the first aspect or the second aspect, wherein the monomer a is a compound having either a vinyl group or a (meth) acryloyl group.
As a fourth aspect, the base material according to the third aspect, wherein the monomer a is N-vinylpyrrolidone, N-vinylacetamide, or N-vinylformamide.
As a fifth aspect, the base material according to the fourth aspect, wherein the monomer b is a compound having either a vinyl group or a (meth) acryloyl group.
As a sixth aspect, the monomer that gives the (A) copolymer contains the monomer b in an amount of 5 to 500 mol% with respect to the number of moles of the monomer a, according to the first to fifth aspects. Regarding the base material.
As a seventh viewpoint, the metal fine particles (B) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum ( The base material according to any one of the first to sixth aspects, which is a fine particle of at least one kind of metal selected from the group consisting of Pt) and gold (Au).
As the eighth aspect, the base material according to the seventh aspect, wherein the metal fine particles (B) are palladium fine particles.
As a ninth aspect, the base material according to any one of the first to eighth aspects, wherein the metal fine particles (B) are fine particles having an average particle size of 1 to 100 nm.
As a tenth aspect, the base material according to any one of the first to ninth aspects, which further contains (E) a base resin having a non-radical polymerizable crosslinkable group.
As the eleventh viewpoint, the present invention relates to an electroless metal plating base layer obtained by using the electroless plating base material according to any one of the first to tenth viewpoints.
As a twelfth aspect, the present invention relates to a metal plating film formed on the base layer of the electroless metal plating according to the eleventh aspect.
As a thirteenth viewpoint, a base material, an electroless metal plating base layer formed on the base material according to the eleventh viewpoint, and a metal plating film formed on the electroless metal plating base layer. The present invention relates to a metal coating substrate.
As a fourteenth viewpoint, the present invention relates to a method for producing a metal coating base material, which comprises the following steps (1) and (2).
(1) Step: The electroless plating base material according to any one of the first to tenth viewpoints is applied onto a base material, and an electroless metal plating base layer is provided on the base material. Process,
(2) Step: A step of immersing a base material provided with the base layer in an electroless plating bath to form a metal plating film on the base layer.

The base material of the present invention can easily form a base layer for non-electrostatic plating simply by applying it on a base material. Further, according to the present invention, it is possible to form a base layer for plating which has excellent plating performance and high heat resistance and has excellent adhesion to an LCP substrate. Moreover, the base material of the present invention can be easily varnished with various compositions, and can have high metal fine particle dispersion stability.
Further, since the polymer used for the base material of the present invention can be easily prepared with a small number of processes, it is possible to simplify the manufacturing process of the plating base material and reduce the manufacturing cost.
Further, the electroless metal plating base layer formed from the electroless plating base agent of the present invention can easily form a metal plating film simply by immersing it in an electroless plating bath, and can easily form a base material, a base layer, and metal plating. A metal-coated base material provided with a film can be easily obtained.
That is, by forming the base layer on the base material using the electroless plating base material of the present invention, a metal plating film having excellent adhesion to the base material, particularly the LCP substrate, and having heat resistance is formed. Can be done.

Hereinafter, the present invention will be described in detail.
The base material of the present invention contains (A) a copolymer having the above-mentioned specific structural unit, (B) metal fine particles, (C) a cross-linking agent, and (D) a solvent, and if necessary, contains other components. It is a base material.
The base material of the present invention is suitably used as a catalyst for forming a metal plating film on a base material by electroless plating. Hereinafter, each component will be described.
<(A) Copolymer>

The component (A) is a structural unit derived from a monomer a having a metal-dispersible group and one radically polymerizable double bond in the molecule, a non-radical polymerizable crosslinkable group in the molecule, and one radical. A copolymer containing a structural unit derived from a monomer b having a polymerizable double bond (however, the copolymer has a metal dispersible group and one or more radically polymerizable double bonds in the molecule c. (Excluding the copolymer (A1) containing the structural unit derived from the above and the structural unit derived from the monomer d having two or more radically polymerizable double bonds in the molecule).

[Monomer a]
In the present invention, the monomer a is a compound having a metal dispersible group and one radically polymerizable double bond in the molecule.
The metal dispersible group improves the dispersibility in the composition of the metal fine particles by interacting with the metal fine particles of the component (B) such as adhesion and / or coordination, thereby forming the metal fine particles in the composition. It is a basis for stable existence. As such a metal dispersible group, a substituent having a carbonyl and a nitrogen atom covalently bonded to the carbonyl, that is, a substituent having a −C (= O) -N− moiety is preferable, and more specifically, A group selected from the group consisting of a group having an amide bond and a group having an imide bond is preferable.
The radically polymerizable double bond is preferably a compound having one of either a vinyl group or a (meth) acryloyl group. When the monomer a is a compound having a (meth) acryloyl group as a radically polymerizable double bond, the carbonyl group [-C (= O)-] contained in the (meth) acryloyl group is a metal dispersible group. It may have a structure that overlaps with the carbonyl group in the amide group as.

Examples of such monomer a include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl (meth) acrylamide, and the like.
N-Ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N- Methoxymethyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl ( Meta) Acrylamide, N-vinylphthalimide, N-vinylsuccinimide and the like can be mentioned.

Among them, as the monomer a, a monomer having an N-vinylamide group is preferable from the viewpoint of coordinating ability to a metal, and N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide are preferable in consideration of availability and the like.
These monomers a may be used alone or in combination of two or more.

[Monomer b]
Monomer b is a monomer having a non-radical polymerizable crosslinkable group and one radically polymerizable double bond in the molecule.
The non-radical polymerizable crosslinkable group is a crosslinkable group having no radical polymerizable property, that is, a crosslinkable group showing no polymerizable property even by the action of a radical polymerization initiator. Examples of such a crosslinkable group include a hydroxy group, a carboxyl group, an amino group and the like.

Examples of the monomer having such a non-radical polymerizable crosslinkable group and one radically polymerizable double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxy. Propyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy Monomers having a hydroxy group such as -6-hydroxynorbornene-2-carboxylic-6-lactone, or p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxyphenylacrylamide, N Monomers with phenolic hydroxyl groups such as -hydroxyphenylmethacrylate, p-hydroxyphenylacrylate, p-hydroxyphenylmethacrylate, or acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono -A monomer having a carboxyl group such as 2- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, or aminoethyl acrylate, aminoethyl. Examples thereof include monomers having an amino group such as methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

In the present invention, other monomers can be used together with the above-mentioned monomer a and the above-mentioned monomer b when producing the copolymer of the component (A). Such other monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, and 2 -Ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl Methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydro Flufuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinylnaphthalene , Vinyl anthracene, vinyl biphenyl and the like.

In the present invention, when the copolymer of the component (A) is produced, the resistance of the obtained copolymer of the component (A) to a plating solution or the like can be imparted by using the above-mentioned other monomers. ..

However, the copolymer (A) has a structural unit derived from a monomer c having a metal-dispersible group and one or more radically polymerizable double bonds in the molecule, and two or more radically polymerizable in the molecule. The copolymer (A1) containing a structural unit derived from the monomer d having a double bond is excluded.
<(A1) copolymer>

[Monomer c]
Specifically, in the present invention, the monomer c is not particularly limited as long as it is a compound having a metal-dispersible group and one or more radically polymerizable double bonds in the molecule. Examples of the metal dispersible group include the same examples as those mentioned in [Monomer a] described above.
Examples of the radically polymerizable double bond include compounds having at least one of either a vinyl group or a (meth) acryloyl group. When the monomer c is a compound having a (meth) acryloyl group as a radically polymerizable double bond, the carbonyl group [-C (= O)-] contained in the (meth) acryloyl group is the carbonyl in the amide group. It may have a structure that overlaps with the group.

Examples of such monomer c include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (meth). Acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (meth) Examples thereof include acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide and the like.
One of these monomers c may be used alone for the polymer (A1), or two or more of these monomers may be used in combination.

[Monomer d]
In the present invention, the monomer d can have either or both of a vinyl group and a (meth) acryloyl group.

Examples of the monomer d include the organic compounds shown in (d1) to (d7) below.
(D1) Vinyl hydrocarbons:
(D1-1) Aliphatic vinyl hydrocarbons; isoprene, butadiene, 3? Methyl? 1,2? Butadiene, 2,3? Dimethyl? 1,3? Butadiene, 1,2? Polybutadiene, pentadiene, hexadiene, octadiene Etc. (d1-2) Aliphatic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadien, norbornadien, etc. (d1-3) Aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, tri Vinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc. (d2) Vinyl esters, allyl esters, vinyl ethers, allyl ethers, vinyl ketones:
(D2-1) Vinyl esters; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itacone, vinyl (meth) acrylate, etc. (d2-2) Allyl esters; diallyl maleate, phthalic acid Dialyl, diallyl isophthalate, diallyl adipate, allyl (meth) acrylate and the like (d2-3) vinyl ethers; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like (d2-4) allyl ethers; diallyl ether, diallyl Oxyetane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetraallyloxyetane, etc. (d2-5) vinyl ketones; divinyl ketone, diallyl ketone, etc. (d3) (meth) acrylic Acid esters:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, Trimethylol Propanetri (meth) Acrylate, Ditrimethylol Propanetetra (Meta) Acrylate, Glycotrimethyl (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Alkoxytitanium Tri (Meta) Acrylate, 1,6-Hexanediol Di (Meta) acrylate, 2-methyl-1,8? Octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclo [5.2 1.0 <2,6>] Decandimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3- Di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecyleneoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl ] Sulfates, bis [2- (meth) acryloylthioethyl] sulfides, 1,3-adamantandiol di (meth) acrylates, 1,3-adamantan dimethanol di (meth) acrylates, aromatic urethane di (meth) acrylates, fats Group Urethane Di (meth) Acrylate, etc. (d4) Vinyl-based compound having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300, etc.) di (meth) acrylate, polypropylene glycol (molecular weight 500, etc.) di (meth) acrylate, etc. (d5) Nitrogen-containing vinyl compounds:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, ethoxylated isocyanuric acid di (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, methylenebis (meth) acrylamide, bismaleimide, etc. (d6) Silicon-containing vinyl compounds:
Didimethyldivinylsilane, divinyl (methyl) (phenyl)silane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3- Fluorovinyl-based compounds containing (d7) such as tetraphenyldisilazane and dietokidivinylsilane:
1,4-Divinylperfluorobutane, 1,4-divinyloctafluorobutane, 1,6-divinylperfluorohexane, 1,6-divinyldodecafluorohexane, 1,8-divinylperfluorooctane, 1,8-divinyl Hexadecafluorooctane, etc.
These monomers d may be used alone or in combination of two or more.

Specifically, the copolymer (A1) has a structural portion represented by the following formula [1], that is, a structure formed by a polymerization reaction of two or more radically polymerizable double bonds contained in the monomer d. Highly composed of at least a portion and a structural portion represented by the following formula [2] or formula [3], that is, a structural portion formed by the polymerization reaction of the radically polymerizable double bond of the monomer c. It consists of a polymer having a polymer chain branched into.
(During the ceremony,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond. Represents an alkyl group having 1 to 10 carbon atoms.
A ₁ represents a single bond or a divalent organic group.
R ₇ , R ₈ and R ₉ each independently have 1 to 10 carbon atoms which may contain at least one bond selected from the group consisting of hydrogen atoms, ether bonds, amide bonds and ester bonds. Represents an alkyl group
R ₁₀ and R ₁₁ may each independently contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond, or an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. An alkylene having 2 to 6 carbon atoms which represents a phenyl group or _{may contain at least one bond in which R 10} and R ₁₁ are combined and selected from the group consisting of ether bonds, amide bonds and ester bonds. May form a group,
R ₁₂ , R ₁₃ and R ₁₄ each independently have 1 to 10 carbon atoms which may contain at least one bond selected from the group consisting of hydrogen atoms, ether bonds, amide bonds and ester bonds. Represents an alkyl group
R ₁₅ and R ₁₆ each independently contain an alkyl group having 1 to 10 carbon atoms which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond. Represent. )

The alkyl group having 1 to 10 carbon atoms may have a branched structure or a cyclic structure, or may be an arylalkyl group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group. , N-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1-adamantyl group, benzyl group, phenethyl group and the like.
Examples of the alkylene group having 2 to 6 carbon atoms include a methylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and the like.
Further, the alkyl group having 1 to 10 carbon atoms and the alkylene group having 2 to 6 carbon atoms may contain at least one bond selected from the group consisting of their ether bond, amide bond and ester bond. For example, the alkyl group or the like may be interrupted by these bonds, or may be bonded to the bond end of the alkyl group or the like (for example, an oxyalkylene group or the like).

The divalent organic group includes an aliphatic group having 1 to 20 carbon atoms, an aromatic ring group having 3 to 30 carbon atoms, an alicyclic group having 3 to 30 carbon atoms, and 3 to 30 carbon atoms. Examples include heterocyclic groups, or one or a combination of two or more thereof. These aliphatic groups, aromatic ring groups, alicyclic groups, and heterocyclic groups may have substituents. Further, these aliphatic groups, aromatic ring groups, alicyclic groups and heterocyclic groups may contain at least one bond selected from the group consisting of ether bonds, amide bonds and ester bonds.
The aliphatic group may be linear or branched chain, or may have one or more unsaturated bonds, and examples thereof include an alkylene group having 1 to 20 carbon atoms.
Examples of the aromatic ring in the aromatic ring group include benzene, naphthalene, fluorene, phenanthrene, anthracene and the like.
Examples of the aliphatic ring in the alicyclic group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cycloalkane, and fused rings thereof.
Examples of the heterocycle in the above heterocyclic group include pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazin, pyrol, pyrazole, imidazole, pyrrolidine, pyrazoledin, imidazolidine, furan, pyran, thiophene, thiopyran, isooxazole, isooxazolidine and morpholin , Isothiazole, isothiazolidine, thiomorpholin, benzimidazole, benzofuran, benzothiophene, benzothiazole, benzoxazole, triazine, quinone and the like.

In the present invention, the copolymer (A) excludes the copolymer (A1) containing a structural unit derived from the monomer c and a structural unit derived from the monomer d.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, but for example, in a solvent in which the above-mentioned monomer a and the above-mentioned monomer b are coexisted with other monomers and a polymerization initiator or the like, if desired, at 50 to 110 ° C. It is obtained by carrying out a polymerization reaction at a temperature. At that time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having no specific functional group used if desired, a polymerization initiator and the like. Specific examples will be described in <(D) Solvent> described later.
The specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained by the above method is put into diethyl ether or water during stirring to precipitate, and the generated precipitate is filtered and washed, and then at room temperature under normal pressure or reduced pressure. It can be dried or heat-dried to obtain a powder of a specific copolymer. By the above operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the present invention, the specific copolymer may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.

Further, in the present invention, the specific copolymer of the component (A) may be a mixture of a plurality of types of specific copolymers.

In the present invention, the ratio of copolymerizing the monomer a and the monomer b is preferably 0.05 mol to 5 mol of the monomer b with respect to 1 mol of the monomer a, particularly from the viewpoint of reactivity and plating property. It is preferably 0.1 mol to 3 mol.

In the present invention, when the other monomer is used in producing the copolymer as the component (A), it is 1 mol to 200 mol%, based on the total number of moles of the monomer a and the monomer b. It is preferably 10 mol to 100 mol%.

<(B) Metal fine particles>
The (B) metal fine particles used in the base material of the present invention are not particularly limited, and the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), and silver. Examples thereof include (Ag), tin (Sn), platinum (Pt) and gold (Au), and alloys thereof, and one kind of these metals may be used, or two or more kinds of alloys may be used. Among them, palladium fine particles are mentioned as preferable metal fine particles. The metal oxide may be used as the metal fine particles.

The metal fine particles can be obtained by reducing metal ions by, for example, a method of irradiating a solution of a metal salt with light by a high-pressure mercury lamp, a method of adding a compound having a reducing action (so-called reducing agent) to the solution, or the like. For example, a metal salt solution is added to a solution in which the component polymer (A) is dissolved and irradiated with ultraviolet rays, or a metal salt solution and a reducing agent are added to the solution to obtain metal ions. By reducing the above, a base material containing the component polymer (A) and the metal fine particles can be prepared while forming a complex of the component polymer (A) and the metal fine particles.

Examples of the metal salt include gold chloride acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, first platinum chloride, platinum chloride acid, Pt (dba) ₂ [dba = dibenzylidene acetone], Pt (cod). ₂ [cod = 1,5-cyclooctadiene], Pt (CH ₃ ) ₂ (cod), palladium chloride, palladium acetate (Pd (OC (= O) CH ₃ ) ₂ ), palladium nitrate, Pd ₂ (dba) _3. CHCl ₃ , Pd (dba) ₂ , rhodium chloride, rhodium acetate, ruthenium ensemble, ruthenium acetate, Ru (cod) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni (cod) _2, etc. Can be mentioned.
The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species and the like contained in the obtained base material. Examples of the reducing agent that can be used include boron hydride metal salts such as sodium boron hydride and potassium boron hydride; aluminum lithium hydride, potassium aluminum hydride, aluminum cesium hydride, aluminum berylium hydride, and hydrogenation. Aluminum hydride salts such as aluminum magnesium and aluminum calcium hydride; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary such as methanol, ethanol, isopropanol and polyols. Class alcohols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; tri-n-propylphosphine, tri-n- Butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane [DPPE], 1,3-bis (diphenylphosphino) propane [DPPP], 1 , 1'-bis (diphenylphosphino) ferrocene [DPPF], 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl [BINAP] and the like.

The average particle size of the metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the metal fine particles to 100 nm or less, the surface area is not reduced and sufficient catalytic activity can be obtained. The average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.
The average particle size of the primary particles can be measured by the following method.
[Measurement of average particle size of primary particles]
After dispersing the metal fine particles in ethanol, they are dropped onto a carbon support film and dried to prepare a sample, and then the obtained sample is microscopically subjected to a TEM device (Hitachi, Ltd .: H-8000 acceleration voltage 200 kV). The average particle size can be determined.

The amount of the copolymer, which is the component (A), added to the base material of the present invention is preferably 20 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the metal fine particles (B). When the amount of the (A) copolymer added to 100 parts by mass of the (B) metal fine particles is 20 parts by mass or more, the metal fine particles can be sufficiently dispersed, and when it is 20 parts by mass or less, the metal fine particles can be sufficiently dispersed. The dispersibility of the metal fine particles is insufficient, and precipitates and agglomerates are likely to be formed. More preferably, it is 30 parts by mass or more. Further, when 10,000 parts by mass or more of the (A) copolymer is added to 100 parts by mass of (B) metal fine particles, the amount of Pd per unit area after coating becomes insufficient, so that the precipitation property of plating becomes poor. It may decrease.

<Ingredient (C)>
The plating nucleating agent of the present invention may contain a cross-linking agent as the component (C). Examples of the component (C) include a cross-linking agent that reacts with the non-radical polymerizable cross-linking group.

Examples of the cross-linking agent as the component (C) include an epoxy compound, a methylol compound, a blocked isocyanate compound, a phenoplast compound, a compound having two or more trialkoxysilyl groups, a compound such as an alkoxysilane compound having an amino group, an alkoxy group, and the like. / Or an organic metal compound having a chelate ligand, a polymer of N-alkoxymethylacrylamide, a polymer of a compound having an epoxy group, a polymer of a compound having an alkoxysilyl group, a polymer of a compound having an isocyanate group, and Examples thereof include polymers such as melamine formaldehyde resin.

Specific examples of the above-mentioned epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-Hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N', -tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, and N, N, N', N'-tetraglycidyl-4, 4'-diaminodiphenylmethane And so on.

Specific examples of the methylol compound described above include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of alkoxymethylated glycol uryl include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Co., Ltd. (high condensation type, trade name: Beccamin () Registered trademarks) J-300S, P-955, N) and the like.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.

Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)). ) 506, 508), Sanwa Chemical's methoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-002, same MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MX-45, MX-410, MX-302) and the like.

Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.

The above-mentioned blocked isocyanate compound has two or more isocyanate groups in one molecule in which the isocyanate group is blocked by an appropriate protective group, and when exposed to a high temperature during thermosetting, the protective group (block portion) becomes hot. It dissociates and comes off, and the generated isocyanate group causes a cross-linking reaction with the resin.

Such a polyfunctional blocked isocyanate compound can be obtained, for example, by reacting a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.

Examples of the polyfunctional isocyanate compound include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate. 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-cyclohexyldiisocyanate, 2,6 -Bis (isocyanate methyl) tetrahydrodicyclopentadiene, bis (isocyanate methyl) dicyclopentadiene, bis (isocyanate methyl) adamantan, 2,5-diisocyanate methyl norbornene, norbornan diisocyanate, dicycloheptane triisocyanate, 4,4'-diphenylmethane Diisosocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalened isocyanate , P-phenylenediisocyanate, 1,3-bis (isocyanatemethyl) benzene, dianisidine diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, diphenylether diisocyanate, 2,6-bis (isocyanatemethyl) deca Hydronaphthalene, bis (diisocyanate trill) phenylmethane, 1,1'-methylenebis (3-methyl-4-isocyanatebenzene), 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-Isocyanate-1-methylethyl) benzene, 4,4'-biphenylenediocyanate, 3,3'-dimethyl-4,4'-biphenylenediocyanate, 3,3'-dimethoxy-4,4'-biphenylenediocyanate, Bis (isocyanate methyl) thiophene, bis (isocyanate methyl) tetrahydrothiophene, and their modified compounds (eg, isocyanurate, biuret, ethylene glycol adduct, propylene glycol adduct, trimethylpropan adduct, ethanolamine adduct) , Polyester polyol adduct body, polyether polyol adduct body, polyamide adduct body, polyamine Adduct body) can be mentioned.

Examples of the blocking agent include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, and the like. Ethyl Lactate, Amil Lactate, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether, Oxime Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether), Tri Alcohols such as ethylene glycol monoethyl ether, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dibutylaminoethanol, phenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, Phenols such as chlorophenol, o-cresol, m-cresol, p-cresol, xylenol, lactams such as α-pyrrolidone, β-butyrolactam, β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam Oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, diethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3, Pyrazoles such as 5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, benzene Mercaptans such as thiols, malonic acid diesters, acetoacetate, dinitrile malonate, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivaloylmethane, active methylene compounds such as acetone dicarboxylic acid diester, dibutylamine, diisopropylamine , Di-tert-butylamine, di (2-ethylhexyl) amine, dicyclohexylamine, benzylamine, dipheni Amines such as ruamine, aniline and carbazole, imidazoles such as imidazole and 2-ethylimidazole, imines such as methyleneimine, ethyleneimine, polyethyleneimine and propyleneimine, acids such as acetoanilide, acrylamide, acetate amide and dimer acid amide. Examples thereof include acid imides such as amides, succinate imides, maleate imides and phthalate imides, and urea compounds such as urea, thiourea and ethylene urea. Further, it may be an internal block type due to a uretdione bond (dimerization of isocyanate groups).

Examples of commercially available products of the polyfunctional blocked isocyanate compound include the following products.
Takenate [registered trademark] B-815N, B-830, B-842N, B-846N, B-870, B-870N, B-874, B-874N, B-882, same B-882N, B-5010, B-7005, B-7030, B-7075 (all manufactured by Mitsui Chemicals, Inc.).

Duranate (registered trademark) ME20-B80S, MF-B60B, MF-B60X, MF-B90B, MF-K60B, MF-K60X, SBN-70D, 17B-60P, 17B-60PX, TPA-B80E, TPA-B80X, E402-B80B, E402-B80T, K6000 (all manufactured by Asahi Kasei Chemicals Co., Ltd.), Coronate (registered trademark) 2503, 2507, 2512, 2513, 2515 , 2520, 2554, BI-301, AP-M, Millionate MS-50 (all manufactured by Tosoh Corporation).

Burnock [registered trademark] D-500, D-550, DB-980K (all manufactured by DIC Corporation).

Sumijour [registered trademark] BL-3175, BL-4165, BL-4265, BL-1100, BL-1265, Death Module [registered trademark] TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, BL-3475, Desmosarm [registered trademark] 2170, 2265 (all manufactured by Sumika Bayer Urethane Co., Ltd.).

TRIXENE BI-7461, BI-7642, BI-7986, BI-7987, BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7981, BI-7982, BI-7984, BI-7986, BI-7990, BI-7991, BI-7992, BI-7770, BI-7772, BI-7779, DP9C / 214 ( Above, manufactured by Baksenden Chemicals Co., Ltd.).

VESTANAT [registered trademark] B1358A, B1358 / 100, B1370, VESTAGON [registered trademark] B1065, B1400, B1530, BF1320, BF1540 (all manufactured by Evonik Industries, Ltd.).

In addition, examples of the polyfunctional blocked isocyanate compound include homopolymers or copolymers obtained by radical polymerization of (meth) acrylates having a blocked isocyanate group. Here, the copolymer means a polymer obtained by polymerizing two or more kinds of monomers. The copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having a blocked isocyanate group, or polymerizing a (meth) acrylate having a blocked isocyanate group and another (meth) acrylate. It may be the obtained copolymer. Commercially available products of (meth) acrylates having such a blocked isocyanate group include, for example, Showa Denko KK Karens [registered trademark] MOI-BM, AOI-BM, MOI-BP, AOI-BP, and the like. Examples thereof include the MOI-DEM, the MOI-CP, the MOI-MP, the MOI-OEt, the MOI-OBu, and the MOI-OiPr.

These polyfunctional blocked isocyanate compounds may be used alone or in combination of two or more.

Specific examples of the above-mentioned phenoplast compound include the following compounds, but the phenoplast compound is not limited to the following compound examples.

Specific examples of the compound having two or more trialkoxysilyl groups include 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, and 4,4'-bis (tri). Methoxysilyl) biphenyl, 4,4'-bis (triethoxysilyl) biphenyl, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, Bis (trimethoxysilyl) ethylene, bis (triethoxysilyl) ethylene, 1,3-bis (trimethoxysilylethyl) tetramethyldisiloxane, 1,3-bis (triethoxysilylethyl) tetramethyldisiloxane, bis ( Triethoxysilylmethyl) amine, bis (trimethoxysilylmethyl) amine, bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) carbonate, bis (3-tritri) Ethoxysilylpropyl) carbonate, bis [(3-trimethoxysilyl) propyl] disulfide, bis [(3-triethoxysilyl) propyl] disulfide, bis [(3-trimethoxysilyl) propyl] thiourea, bis [(3-trimethoxysilyl) propyl] Triethoxysilyl) propyl] thiourea, bis [(3-trimethoxysilyl) propyl] urea, bis [(3-triethoxysilyl) propyl] urea, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4 -Bis (triethoxysilylmethyl) benzene, tris (trimethoxysilylpropyl) amine, tris (triethoxysilylpropyl) amine, 1,1,2-tris (trimethoxysilyl) ethane, 1,1,2-tris ( Examples thereof include compounds such as triethoxysilyl) ethane, tris (3-trimethoxysilylpropyl) isocyanurate, and tris (3-triethoxysilylpropyl) isocyanurate.

Specific examples of the alkoxysilane compound having an amino group include, for example, N, N'-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N, N'-bis [3- (tri). Ethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2- Ethandiamine, bis- {3- (trimethoxysilyl) propyl} amine, bis- {3- (triethoxysilyl) propyl} amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, trimethoxy {3 -(Methylamino) propylsilane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-allylamino) propyltriethoxysilane, 3- (diethylamino) propyltrimethoxysilane, 3- (diethylamino) propyltriethoxysilane Examples thereof include compounds such as silane, 3- (phenylamino) propyltrimethoxysilane, and 3- (phenylamino) propyltriethoxysilane.

Specific examples of the organic metal compound having an alkoxy group and / or a chelating ligand include, for example, diisopropoxyethylacetoneacetate aluminum, diisopropoxyacetylacetoneate aluminum, triacetylacetoneate aluminum, tetrakisisopropoxytitanium, and tetrakis. Compounds such as normal butoxytitanium, tetraoctyl titanate, diisopropoxybis (acetylacetoneate) titanium, titanium tetraacetylacetone, tetrakis (normalpropoxy) zirconium, tetrakis (normalbutoxy) zirconium, tetrakis (acetylacetoneate) zirconium Can be mentioned.

Further, examples of the above-mentioned N-alkoxymethylacrylamide polymer include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth). ) Examples thereof include polymers produced by using an acrylamide compound or a methacrylicamide compound substituted with a hydroxymethyl group such as acrylamide or an alkoxymethyl group.

Specific examples of such polymers include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N. Examples thereof include a copolymer of -ethoxymethylmethacrylamide and benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide, benzylmethacrylate and 2-hydroxypropylmethacrylate. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

Examples of the polymer of the compound having an epoxy group include a polymer produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate. Be done.

Specific examples of such polymers include poly (3,4-epoxycyclohexylmethylmethacrylate), poly (glycidylmethacrylate), copolymers of glycidylmethacrylate and methylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate. Examples thereof include a copolymer with methyl methacrylate and a copolymer with glycidyl methacrylate and styrene. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

Examples of the polymer of the compound having an alkoxysilyl group described above include a polymer produced by using a compound having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane.

Specific examples of such polymers include poly (3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, and 3-methacryloxypropyltrimethoxysilane and methyl. Examples thereof include a copolymer with methacrylate. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000. In the present specification, the above-mentioned "poly ((meth) acryloxipropyltrimethoxysilane)" means a poly (meth) acrylate having an alkoxysilyl group.

These cross-linking agents can be used alone or in combination of two or more.

The content of the cross-linking agent of the component (C) in the electroless plating base material of the present invention is 100, which is the total amount of the copolymer which is the component (A), the following component (E) which is an optional component, and other components. Based on the parts by mass, it is preferably 0 parts by mass to 100 parts by mass, and more preferably 0 parts by mass to 80 parts by mass. If the content of the cross-linking agent is excessive, the precipitation property of the plating and the adhesion of the metal film to the substrate may decrease.

<Base material>
The electroless plating base material of the present invention contains the above-mentioned (A) copolymer, (B) metal fine particles, (C) cross-linking agent, and (D) solvent, and further contains other components as necessary. It includes. In the electroless plating base material of the present invention, it is preferable that the copolymer which is the component (A) and the metal fine particles (B) form a composite, that is, the base material is the component (A). It is preferable to contain a composite formed by a certain copolymer and the metal fine particles (B).

Here, the composite is a composite in which both of them coexist in contact with or in close contact with the metal fine particles due to the action of the metal dispersible group of the side chain of the copolymer which is the component (A), and form a particulate form. In other words, it is expressed as a composite having a structure in which metal fine particles are attached or coordinated to the metal dispersible group of the copolymer which is the component (A).
Here, the "adhered or coordinated structure" refers to a state in which a part or all of the metal-dispersible groups of the copolymer which is the component (A) interacts with the metal fine particles, thereby forming a complex-like structure. Is considered to form. Therefore, when palladium fine particles are used as the metal fine particles, it is considered that the Pd atom on the surface layer interacts with the metal dispersible group to form a structure in which the component polymer (A) surrounds the metal fine particles.

Therefore, the "complex" in the present invention includes not only the metal fine particles and the copolymer which is the component (A) to form one complex as described above, but also the metal fine particles ( A) It is also possible to include those in which the copolymers as components exist independently without forming a bonding portion (those that appear to form one particle). ..

The formation of the complex of the copolymer (A) component and the (B) metal fine particles is carried out at the same time as the preparation of the base material containing the copolymer (A) component and the metal fine particles, and the method is as follows. , A method of exchanging a ligand with a polymer (A) after synthesizing metal fine particles stabilized to some extent by a metal dispersible group, or a metal ion in a solution of a copolymer (A). There is a method of forming a complex by directly reducing. Further, as described above, a metal salt solution is added to a solution in which the copolymer which is the component (A) is dissolved and irradiated with ultraviolet rays, or a metal salt solution and a reducing agent are added to the solution. A complex can also be formed by reducing metal ions, such as by adding them.

As a direct reduction method, the metal ion and the copolymer (A) component are dissolved in a solvent and reduced with primary or secondary alcohols such as methanol, ethanol, 2-propanol and polyol. The desired metal fine particle composite can be obtained.
As the metal ion source used here, the above-mentioned metal salt can be used.
The solvent to be used is not particularly limited as long as it can dissolve a polymer having a metal ion and a metal dispersible group in a required concentration or more, but specifically, methanol, ethanol, n-propanol, 2-propanol and the like. Alcohols; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide (DMF) ), Amidos such as N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide and a mixture of these solvents are mentioned, and alcohols, halogenated hydrocarbons, cyclic ethers and the like are preferable. , And more preferably ethanol, 2-propanol, chloroform, tetrahydrofuran and the like.
The temperature of the reduction reaction (mixing the metal ion and the copolymer which is the component (A)) can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably room temperature (about 25 ° C.) to 100 ° C. Is the range of.

As another direct reduction method, the desired metal fine particle composite can be obtained by dissolving the metal ion and the copolymer (A) component in a solvent and reacting them in a hydrogen gas atmosphere.
Examples of the metal ion source used here include the above-mentioned metal salt, hexacarbonyl chromium [Cr (CO) ₆ ], pentacarbonyl iron [Fe (Co) ₅ ], and octacarbonyl dicobalt [Co ₂ (CO) ₈ ]. , Tetracarbonyl nickel [Ni (CO) ₄ ] and other metal carbonyl complexes can be used. Further, zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
The solvent used is not particularly limited as long as it can dissolve the metal ion and the copolymer (A) component in a required concentration or more, but specifically, alcohols such as ethanol and propanol; methylene chloride. , Halogenated hydrocarbons such as chloroform; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile and a mixture of these solvents are mentioned, preferably tetrahydrofuran. ..
The temperature at which the metal ion and the copolymer as the component (A) are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent.

Further, as a direct reduction method, the desired metal fine particle composite can be obtained by dissolving the metal ion and the copolymer (A) component in a solvent and causing a thermal decomposition reaction.
As the metal ion source used here, the above-mentioned metal salt, metal carbonyl complex, other zero-valent metal complex, and metal oxide such as silver oxide can be used.
The solvent used is not particularly limited as long as it can dissolve the metal ion and the copolymer (A) component in a required concentration or more, but specifically, methanol, ethanol, n-propanol, isopropanol, etc. Alcohols such as ethylene glycol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; benzene, toluene and the like Examples thereof include aromatic hydrocarbons and a mixed solution of these solvents, and toluene is preferable.
The temperature at which the metal ion and the copolymer as the component (A) having a metal dispersible group are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably near the boiling point of the solvent, for example, toluene. In the case, it is 110 ° C. (heating reflux).

The composite of the copolymer and the metal fine particles, which is the component (A) thus obtained, can be in the form of a solid substance such as powder through a purification treatment such as reprecipitation.

The base material of the present invention contains the copolymer (A), (B) metal fine particles (preferably a composite composed of these), (C) a cross-linking agent, and (D) a solvent. Further, if necessary, it contains other components, and the base material may be in the form of a varnish used when forming the [base layer of electroless metal plating] described later.

The electroless plating base material of the present invention can contain the base resin which is the component (E), if desired. As the component (E), a group that undergoes a cross-linking reaction with the cross-linking agent that is the component (C) by heat, that is, a group having the non-radical polymerizable cross-linking group is preferable. The one described as is preferable. By adding such a component (E), the adhesion of the obtained base layer may be further improved.

When the plating base material of the present invention contains the component (E), the content is 100 in total of the copolymer of the component (A), the metal fine particles of the component (B), and the cross-linking agent of the component (C). Based on the parts by mass, it is preferably 0 parts by mass to 200 parts by mass, and more preferably 0 parts by mass to 150 parts by mass. If the content of the component (E) is excessive, the plating precipitation property may decrease.

<Other additives>
As the base material of the present invention, additives such as a surfactant, various surface conditioners, and thickeners may be appropriately added as long as the effects of the present invention are not impaired.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether and polyoxy. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, Solbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate. EF TOP (registered trademark) EF-301, EF-303, EF-352 [above, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.], Megafuck (registered trademark) F-171, F-173, R -08, R-30 [above, manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430, FC-431 [above, manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) AG-710 Fluorine-based surfactants such as [manufactured by Asahi Glass Co., Ltd.] and Surflon (registered trademark) S-382 [manufactured by AGC Seimi Chemical Co., Ltd.] can be mentioned.

Further, as the surface conditioner, a silicone-based leveling agent such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; BYK (registered trademark) -302, 307, 322, 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.

Examples of the thickener include polyacrylic acids (including crosslinked ones) such as carboxyvinyl polymer (carbomer); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and polystyrene (PS). ) And other vinyl polymers; polyethylene oxides; polyester; polycarbonate; polyamide; polyurethane; dextrin, agar, caraginan, alginic acid, Arabic gum, guar gum, tragant gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose Polysaccharides such as, and proteins such as gelatin and casein. In addition, each of the above polymers includes not only homopolymers but also copolymers. These thickeners may be used alone or in combination of two or more.
In the base material of the present invention, the viscosity and rheological characteristics of the base material can be adjusted by adding a thickener as necessary, and the base material can be appropriately applied according to the application method, application location, and the like. Can be adopted / selected.

These additives may be used alone or in combination of two or more. The amount of the additive used is preferably 0.001 to 50 parts by mass, preferably 0.005 parts by mass, based on 100 parts by mass of the composite formed of the polymer as the component (A) and the metal fine particles as the component (B). 10 parts by mass is more preferable, and 0.01 to 5 parts by mass is even more preferable.

[Base layer of electroless metal plating]
The electroless plating base material of the present invention described above can be applied onto a base material to form an electroless metal plating base layer. The base layer of this electroless metal plating is also an object of the present invention.

The base material is not particularly limited, but a non-conductive base material or a conductive base material can be preferably used.
Examples of the non-conductive base material include glass, ceramic, etc .; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene). Examples thereof include terephthalate) resin, PEEK (polyether ether ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, LCP (liquid crystal polymer) resin, and the like. These are preferably used in the form of a sheet, a film, or the like, and the thickness in this case is not particularly limited.
Examples of the conductive substrate include ITO (tin-doped indium oxide), ATO (antimon-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), and the like. Various stainless steels, aluminum alloys such as aluminum and duralmin, iron and iron alloys, copper and brass, copper alloys such as phosphor bronze, white copper and beryllium copper, nickel and nickel alloys, and metals such as silver alloys such as silver and western silver. And so on.
Further, a substrate in which a thin film is formed of these conductive substrates on the non-conductive substrate can also be used.
Further, the base material may be a three-dimensional molded product.

It contains the copolymer (A), (B) fine metal particles (preferably a composite composed of these), (C) a cross-linking agent, and (D) a solvent, and further contains (E) a base, if necessary. As a specific method for forming a base layer for electroless metal plating from an electroless plating base material containing a polymer and other components, first, the component polymer (A) and fine metal particles (B) (preferably a composite composed of these) are used. ) (And if necessary, amine compounds and other components) are dissolved or dispersed in the solvent (D) to form a varnish, and the varnish is applied to a substrate on which a metal plating film is formed by a spin coating method; blade coating. Method; Dip coating method; Roll coating method; Bar coating method; Die coating method; Spray coating method; Inkjet method; Pen lithography such as Fountain Pen Nanolithography (FPN), Dip Pen Nanolithography (DPN); Letterpress printing methods such as resin letterpress printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), nanotransfer printing (nTP); concave printing methods such as gravure printing and engraving; flat plate printing method; A stencil printing method such as screen printing or copying plate; a thin layer is formed by applying by an offset printing method or the like and then evaporating and drying the solvent.
Among these coating methods, bar coating method, flexographic printing, gravure printing, spin coating method, spray coating method, inkjet method, pen lithography, contact printing, μCP, NIL and nTP are preferable. When the spin coating method is used, since it can be applied in a single time, there is an advantage that even a highly volatile solution can be used and a highly uniform application can be performed. When the spray coating method is used, a highly uniform coating can be performed with a very small amount of varnish, which is industrially very advantageous. When the inkjet method, pen lithography, contact printing, μCP, NIL, or nTP is used, it is possible to efficiently form (draw) a fine pattern such as wiring, which is industrially very advantageous.

<(D) Solvent>
Further, as the solvent used here, the polymer which is the component (A), (B) fine metal particles (preferably a composite composed of these), (C) a cross-linking agent, and optionally the component (E) and other components are used. It is not particularly limited as long as it dissolves or disperses, but for example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene; methanol, ethanol, n-propanol, isopropanol and n-butanol. , 2-Butanol, n-hexanol, n-octanol, 2-octanol, 2-ethylhexanol and other alcohols; methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve and other cellosolves; propylene glycol monomethyl ether (PGME), propylene Glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether and other glycol ethers; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Glycol esters such as acetate (PGMEA); ethers such as tetrahydrofuran (THF), methyl tetrahydrofuran, 1,4-dioxane, diethyl ether; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone (MEK), methyl isobutyl Ketones such as ketone (MIBK), cyclopentanone, cyclohexanone; aliphatic hydrocarbons such as n-heptane, n-hexane, cyclohexane; halogenated aliphatic hydrocarbons such as 1,2-dichloroethane, chloroform; N -Methyl-2-pyrrolidone (NMP), N, N-di Amides such as methylformamide (DMF), N, N-dimethylacetamide; dimethyl sulfoxide and the like can be used. These solvents may be used alone or may be a mixture of two or more kinds of solvents. Further, glycols such as ethylene glycol, propylene glycol and butylene glycol may be added for the purpose of adjusting the viscosity of the varnish.
The concentration to be dissolved or dispersed in the solvent is arbitrary, but the concentration of the non-solvent component in the varnish [the polymer as the component (A) and the metal fine particles (B) of all the components except the solvent contained in the base material (preferably). Concentration of (complex composed of these), (C) cross-linking agent, optionally (E) base polymer and other components, etc.)] is 0.05 to 90% by mass, preferably 0.1 to 80% by mass. is there.

The method for drying the solvent is not particularly limited, and for example, it may be evaporated using a hot plate or an oven in an appropriate atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum. This makes it possible to obtain a base layer having a uniform film-forming surface. The firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably performed at 40 to 250 ° C.

[Electroless plating, metal plating film, metal film base material]
By electroless plating the base layer of the electroless metal plating formed on the base material obtained as described above, a metal plating film is formed on the base layer. The metal plating film thus obtained, and the metal coating base material provided on the base material in the order of the electroless metal plating base layer and the metal plating film are also the objects of the present invention.
The electroless plating treatment (process) is not particularly limited and can be performed by any generally known electroless plating treatment. For example, the plating is performed using a conventionally known electroless plating solution. A general method is to immerse the base layer of electroless metal plating formed on the base material in a liquid (bath).

The electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and is a pH adjuster, a pH buffer, and a reaction accelerator (second complexing agent) according to other uses. , Stabilizers, surfactants (for imparting gloss to the plating film, for improving the wettability of the surface to be treated, etc.) and the like are appropriately included.
Examples of the metal used for the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and alloys thereof, which are appropriately selected according to the purpose. Will be done.
Further, the complexing agent and the reducing agent may be appropriately selected according to the metal ions.

A commercially available electroless plating solution may be used as the electroless plating solution. For example, an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd. and an electroless copper plating chemical (Melplate (Melplate)) may be used. (Registered trademark) CU series); Electroless nickel plating solution (ICP Nicolon (registered trademark) series, Top Piena 650), electroless copper plating solution (OPC-700 electroless copper M-K,) manufactured by Okuno Pharmaceutical Co., Ltd. ATS Ad Copper IW, CT, OPC Copper (registered trademark) AF series, HFS, NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (flash gold 330, self gold OTK) -IT), electroless silver plating solution (muden silver); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd., electroless gold plating solution (dip G series, NC gold series); Sasaki Chemical Electroless silver plating solution manufactured by Yakuhin Co., Ltd. (Sdia AG-40); Electroless nickel plating solution manufactured by Nippon Kanizen Co., Ltd. (Kanizen (registered trademark) series, Schumer (registered trademark) series, Schumaer (registered trademark)) Kani Black (registered trademark) series), electroless palladium plating solution (S-KPD); electroless copper plating solution manufactured by Dow Chemical Co., Ltd. (Cuposit (registered trademark) Coppermix series, Circuposit (registered trademark) series), Electroless palladium plating solution (Palamers (registered trademark) series), electroless nickel plating solution (Duraposit (registered trademark) series), electroless gold plating solution (Aurorectores (registered trademark) series), electroless tin plating solution (Tinposit (registered trademark) series); Electroless copper plating solution manufactured by Uemura Kogyo Co., Ltd. (Sulcup (registered trademark) ELC-SP, PSY, PCY, PGT, PSR, PEA, PMK) , Electroless copper plating solution (Print Gant (registered trademark) PV, PVE) manufactured by Atotech Japan Co., Ltd. can be preferably used.

In the electroless plating step, the formation speed of the metal film is adjusted by adjusting the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring and stirring speed, presence / absence of supply of air / oxygen, supply speed, and the like. And the film thickness can be controlled.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measurement of the number average molecular weight and the weight average molecular weight is as follows.
[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the copolymers obtained according to the following synthesis examples were determined by using a GPC apparatus (Shodex column KD800 and TOSOH column TSK-GEL) manufactured by Tosoh Corporation as an elution solvent N, N-dimethylformamide. (as an additive, lithium bromide - hydrate _{(LiBr · H 2 O) 10mmol} / L ( liter) mixing) on the condition that is eluted by flowing through the column at a flow rate of 1 mL / min (column temperature 40 ° C.) It was measured. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.

The meanings of the abbreviations used in the following examples are as follows.
MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate HEA: 2-Hydroxyethyl acrylate NVA: N-vinylacetamide NVF: N-vinylformamide NVP: N-vinylpyrrolidone BMA: Benzylmethacrylate AIBN: 2, 2'-azobis-2 -Isobutyronitrile AMBN: 2, 2'-azobis-2-methylbutyronitrile PGME: propylene glycol monomethyl ether IPE: diisopropyl ether PrOH: 1-propanol MIBK: methyl isobutyl ketone DAA: diacetone alcohol epolite 400E: polyethylene Glycol # 400 Diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd.)
BI7960: Isocyanate (manufactured by Baxenden)
BL-10: Polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd.)

<Synthesis example 1>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.03 g of styrene, 1.63 g of NVA, 2.23 g of HEA, and 0.29 g of AMBN in 14.37 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P1). The obtained copolymer had Mn of 6,806 and Mw of 11,797.

<Synthesis example 2>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.00 g of styrene, 0.81 g of NVA, 3.34 g of HEA, and 0.31 g of AMBN in 15.10 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P2). The obtained copolymer had Mn of 6,512 and Mw of 10,298.

<Synthesis example 3>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.00 g of styrene, 2.45 g of NVA, 1.11 g of HEA, and 0.28 g of AMBN in 13.64 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P3). The obtained copolymer had Mn of 7,043 and Mw of 10,112.

<Synthesis example 4>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.07 g of BMA, 0.97 g of NVA, 1.32 g of HEA, and 0.21 g of AMBN in 10.50 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P4). The obtained copolymer had Mn of 15,693 and Mw of 40,962.

<Synthesis example 5>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.03 g of styrene, 1.63 g of NVA, 2.50 g of HEMA, and 0.31 g of AMBN in 15.03 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P5). The obtained copolymer had Mn of 6,823 and Mw of 12,492.

<Synthesis example 6>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.00 g of styrene, 1.37 g of NVF, 2.23 g of HEA, and 0.28 g of AMBN in 13.71 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P6). The obtained copolymer had Mn of 6,590 and Mw of 10,266.

<Synthesis example 7>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.00 g of styrene, 2.13 g of NVP, 2.23 g of HEA, and 0.32 g of AMBN in 15.59 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P7). The obtained copolymer had Mn of 5,283 and Mw of 11,499.

<Synthesis Example 8>
The copolymer solution (solid content concentration: 30% by mass) obtained by dissolving 2.00 g of MMA, 1.11 g of HEMA, and 0.16 g of AMBN in 7.63 g of PGME and reacting at 80 ° C. for 20 hours was diethyled. The polymer was precipitated by adding the mixture to 500 mL of ether with stirring. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P8). The obtained copolymer had Mn of 13,186 and Mw of 24,452.

<Synthesis example 9>
A copolymer solution (solid content concentration: 30% by mass) obtained by dissolving 2.00 g of styrene, 4.46 g of HEA, and 0.32 g of AMBN in 15.83 g of PGME and reacting at 80 ° C. for 20 hours was obtained by diethyl. The polymer was precipitated by adding the mixture to 500 mL of ether with stirring. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P9). The obtained copolymer had Mn of 5,797 and Mw of 9,880.

<Synthesis Example 10>
The copolymer solution (solid content concentration: 30% by mass) obtained by dissolving 2.00 g of styrene, 3.27 g of NVA, and 0.26 g of AMBN in 12.91 g of PGME and reacting at 80 ° C. for 20 hours was diethyled. The polymer was precipitated by adding the mixture to 500 mL of ether with stirring. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P10). The obtained copolymer had Mn of 4,265 and Mw of 5,609.

<Synthesis Example 11>
The copolymer solution (solid content concentration: 30% by mass) obtained by dissolving 2.50 g of NVA, 1.71 g of HEA, and 0.21 g of AMBN in 10.30 g of PGME and reacting at 80 ° C. for 20 hours is diethylized. The polymer was precipitated by adding the mixture to 500 mL of ether with stirring. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P11). The obtained copolymer had Mn of 7,489 and Mw of 11,252.

<Synthesis Example 12>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P1 l. Polymerized in this solution in Synthesis Example 1. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M1) as a black powder.

<Synthesis Example 13>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P2 l. Polymerized in this solution in Synthesis Example 2. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M2) as a black powder.

<Synthesis Example 14>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P3 l. Polymerized in this solution in Synthesis Example 3. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M3) as a black powder.

<Synthesis Example 15>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P4 l. Polymerized in this solution in Synthesis Example 4. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M4) as a black powder.

<Synthesis Example 16>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P5 l. Polymerized in this solution in Synthesis Example 5. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M5) as a black powder.

<Synthesis example 17>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P6 l. Polymerized in this solution in Synthesis Example 6. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M6) as a black powder.

<Synthesis Example 18>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P7 l. Polymerized in this solution in Synthesis Example 7. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M7) as a black powder.

<Synthesis Example 19>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P9 l. Polymerized in this solution in Synthesis Example 9. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M8) as a black powder.

<Synthesis Example 20>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P10 l. Polymerized in this solution in Synthesis Example 10. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M9) as a black powder.

<Synthesis example 21>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P11 l. Polymerized in this solution in Synthesis Example 11. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle composite was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle composite (M10) as a black powder.

[Evaluation of heat resistance]
The polymer / Pd particle composites obtained in Synthesis Examples 12 to 21 were subjected to a temperature range of 25 ° C. to 500 ° C., a temperature rise of 10 ° C./min, and 5% under a nitrogen atmosphere using a differential thermal balance TG8120 manufactured by Rigaku Co., Ltd. The weight loss temperature was measured. The results obtained are shown in Table 1.

[Preparation of plating solution]
<Preparation Example 1>
Top Nicolon SA-98-MLF (manufactured by Okuno Pharmaceutical Industry Co., Ltd.) 20 mL and Top Nicolon SA-98-1LF (manufactured by Okuno Pharmaceutical Industry Co., Ltd.) 11 mL were placed in a 300 mL beaker, and pure water was further added to bring the total amount of the solution to 200 mL. This solution was stirred to obtain an electroless nickel plating solution.

[Evaluation of dispersibility]
The obtained composite of Pd particles was charged as shown in Table 2, stirred for 1 hour, and then allowed to stand to visually evaluate the state of the solution. The evaluation results are summarized in Table 3 later.

<Evaluation criteria for dispersibility>
◯: A uniform solution was obtained.
X: Precipitation is seen and a uniform solution is not obtained.

[Evaluation of plating precipitation]
The LCP (Pelicule (registered trademark) LCP manufactured by Chiyoda Integra Co., Ltd.) was surface-treated for 30 seconds using a UV ozone cleaning device (UV-208 manufactured by Technovision Co., Ltd.). An electroless plating base material was applied on the surface-treated LCP with a bar coat having a film thickness of 12 μm, and then heated at 80 ° C. for 5 minutes to form a coating film. The coating film was further cured by heating at 200 ° C. for 10 minutes. The obtained cured film was immersed in the electroless nickel plating solution prepared in Preparation Example 1 for 2 minutes. Then, after washing the obtained plating base material with water, the state of the metal plating film was visually evaluated. The evaluation results are summarized in Table 3 later.

<Evaluation criteria for plating precipitation>
◯: Plating is uniformly deposited on the entire surface of the coating film.
-: Not implemented because a uniform solution cannot be obtained.

<Evaluation of adhesion>
The metal plating film portion on the plating substrate obtained above was cut with a cutter knife so as to form a 10 × 10 square at intervals of 1 mm in length and width. Nichiban Co., Ltd. cellophane tape (registered trademark) is pasted on this notch, and after rubbing strongly to make it adhere firmly, the adhesive tape that has adhered is peeled off at once, and the state of the metal plating film is visually evaluated according to the following criteria. did. The evaluation results are summarized in Table 3 later.

<Evaluation criteria for adhesion>
◯: All 100 squares remain without peeling.
X: Even 1 square is peeled off.
-: Not implemented because a uniform solution cannot be obtained.

As shown in Table 1, the polymer / Pd particle composites M1 to M7 and M10 had good heat resistance.
As shown in Table 3, Examples 1 to 11 and Comparative Examples 2 and 3 had good dispersibility and plating precipitation. On the other hand, in Comparative Example 1, sufficient dispersibility and plating precipitation could not be confirmed. In addition, the adhesiveness of Examples 1 to 11 was good. On the other hand, in Comparative Examples 1 to 3, sufficient adhesion could not be confirmed.

Claims (14)

An electroless plating base material for forming a metal plating film on a substrate by electroless plating.
(A) A structural unit derived from a monomer a having a metal dispersible group and one radically polymerizable double bond in the molecule, a non-radical polymerizable crosslinkable group in the molecule, and one radically polymerizable two. A copolymer containing a structural unit derived from a monomer b having a double bond (however, the copolymer is derived from a monomer c having a metal dispersible group and one or more radically polymerizable double bonds in the molecule. Copolymers (A1) containing a structural unit and a structural unit derived from a monomer d having two or more radically polymerizable double bonds in the molecule),
(B) Metal fine particles,
A base material containing (C) a cross-linking agent and (D) a solvent. The base material according to claim 1, which comprises a composite in which the (B) metal fine particles are adhered or coordinated to the metal dispersible group in the (A) copolymer. The base material according to claim 1 or 2, wherein the monomer a is a compound having either a vinyl group or a (meth) acryloyl group. The base material according to claim 3, wherein the monomer a is N-vinylpyrrolidone, N-vinylacetamide, or N-vinylformamide. The base material according to claim 1 or 2, wherein the monomer b is a compound having either a vinyl group or a (meth) acryloyl group. The monomer according to any one of claims 1 to 5, wherein the monomer giving the copolymer (A) contains the monomer b in an amount of 5 to 500 mol% with respect to the number of moles of the monomer a. Base material. The metal fine particles (B) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold ( The base material according to any one of claims 1 to 6, which is a fine particle of at least one kind of metal selected from the group consisting of Au). The base material according to claim 7, wherein the metal fine particles (B) are palladium fine particles. The base material according to any one of claims 1 to 8, wherein the metal fine particles (B) are fine particles having an average particle size of 1 to 100 nm. The base material according to any one of claims 1 to 9, further comprising (E) a base resin having a non-radical polymerizable crosslinkable group. An electroless metal plating base layer obtained by using the electroless plating base material according to any one of claims 1 to 10. The metal plating film formed on the base layer of the electroless metal plating according to claim 11. A metal comprising a base material, an electroless metal plating base layer formed on the base material, and a metal plating film formed on the electroless metal plating base layer. Coating substrate. A method for producing a metal film base material, which comprises the following steps (1) and (2).
(1) Step: The electroless plating base material according to any one of claims 1 to 10 is applied onto a base material, and an electroless metal plating base layer is provided on the base material. Process,
(2) Step: A step of immersing a base material provided with the base layer in an electroless plating bath to form a metal plating film on the base layer.