KR102621646B1 - Electroless plating agent containing polymer and metal particles - Google Patents

Abstract

[Problem] To provide a new base material used as a pretreatment process for electroless plating that has high heat resistance, can form a plating base layer that does not contain corrosive atoms, and can further reduce costs in its production. It is done.
[Solution] As an electroless plating agent for forming a metal plating film by electroless plating on a substrate, (A) a structural unit derived from monomer a having a metal dispersible group and one radically polymerizable double bond in the molecule. and a polymerizable compound containing a structural unit derived from monomer b having a non-radically polymerizable crosslinkable group and one radically polymerizable double bond in the molecule (however, the copolymer has a metal dispersible group and a metal dispersible group in the molecule) Excluding copolymers (A1) containing structural units derived from monomer c having one or more radically polymerizable double bonds and structural units derived from monomer d having two or more radically polymerizable double bonds in the molecule) , (B) metal fine particles, (C) crosslinking agent, and (D) solvent.

Description

Electroless plating agent containing polymer and metal particles

The present invention relates to an electroless plating agent containing polymer and metal fine particles.

In electroless plating, a film of uniform thickness is obtained regardless of the type or shape of the substrate by simply immersing the substrate in a plating solution, and a metal plating film can be formed even on non-conducting materials such as plastic, ceramic, and glass. For example, it is widely used in a variety of fields, including decorative purposes such as giving a sense of luxury and aesthetics to resin molded bodies such as automobile parts, electronic shielding, and wiring technology such as printed circuit boards and large-scale integrated circuits.

Normally, when forming a metal plating film on a base material (body to be plated) by electroless plating, pretreatment is performed to increase the adhesion between the base material and the metal plating film. Specifically, a sensitization treatment in which the surface to be treated is first roughened and/or made hydrophilic by various etching means, and then an adsorption material that promotes the adsorption of the plating catalyst on the surface to be treated is supplied to the surface to be treated. ) and an activation treatment to adsorb the plating catalyst on the surface to be treated. Typically, the sensitization treatment involves immersing the object to be treated in an acidic solution of stannous chloride, which causes metal (Sn ²⁺ ), which can act as a reducing agent, to adhere to the surface to be treated. Then, for the sensitized surface to be treated, the object to be treated is immersed in an acidic solution of palladium chloride as an activation treatment. For this reason, the palladium ions in the solution are reduced by the metal (tin ion: Sn ²⁺ ) as a reducing agent, and adhere to the surface to be treated as active palladium catalyst nuclei. After pretreatment in this way, the metal plating film is formed on the surface to be treated by immersing it in an electroless gold solution.

On the other hand, an example of using a composition containing a highly branched polymer having an ammonium group and metal fine particles as a base agent (plating catalyst) for electroless plating was reported, causing problems in the pretreatment process (roughening treatment) of the conventional electroless plating treatment. A proposal has been made for an electroless plating agent that avoids the use of chromium compounds (chromic acid), reduces the number of pretreatment steps, and achieves various improvements in environmental aspects, cost, and cumbersome operability ( Patent Document 1).

International Patent Application Publication No. 2012/141215 Pamphlet

In the composition containing a highly branched polymer having an ammonium group and metal fine particles proposed as a base material for electroless plating described above, when this composition is applied to wiring technology in semiconductor manufacturing, etc., the heat resistance temperature of the highly branched polymer contained therein is Because it is low, there is a risk that this highly branched polymer may decompose due to solder reflow or high temperature treatment. In addition, there was a problem that it was difficult to provide adhesion to LCP (liquid crystal polymer) substrates, which are substrates with excellent electrical characteristics used in next-generation communication devices such as 5G.

In this way, in the electroless plating agent proposed so far, in addition to the plating performance as a plating agent, it is possible to provide plating with high heat resistance without containing corrosive atoms such as halogen atoms or sulfur atoms, and can be used in various compositions. Proposal of an electroless plating agent that fully realizes these characteristics, including the ability to be easily varnished, various performance characteristics such as high metal particle dispersion stability, adhesion to the LCP substrate, and further operability that can be easily manufactured with a few processes. has never been so far.

Focusing on this problem, the present invention is a pretreatment process for electroless plating that can form a plating base layer with high heat resistance and excellent adhesion to the LCP substrate, and further realizes low cost in manufacturing the same. The purpose is to provide a new substrate to be used.

As a result of intensive studies to achieve the above object, the present inventors examined a polymer containing metal dispersible groups but not containing corrosive atoms, combined this polymer with metal fine particles, and applied this onto a substrate to obtain a polymer. It was discovered that the layer had not only plating properties as a base layer for electroless metal plating, but also had high heat resistance and excellent adhesion to the LCP substrate, thereby completing the present invention.

That is, the present invention, as a first aspect, is an electroless plating agent for forming a metal plating film on a substrate by electroless plating treatment,

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

(B) metal particles,

(C) cross-linking agent, and

(D)Solvent

It is about the summer solstice, including.

As a second aspect, it relates to the base material described in the first aspect, comprising a complex in which the metal fine particles (B) are attached or coordinated to a metal dispersing group in the copolymer (A).

As a third aspect, it relates to the base material described in the first or second aspect, wherein the monomer a is a compound having either a vinyl group or a (meth)acryloyl group.

As a fourth aspect, it relates to the base material described in the third aspect, wherein the monomer a is N-vinylpyrrolidone, N-vinylacetamide, or N-vinylformamide.

As a fifth aspect, it relates to the primer 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 giving the copolymer (A) includes the monomer b in an amount of 5 to 500 mol% relative to the number of moles of the monomer a. It's about.

As a seventh aspect, the metal fine particles (B) include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), and platinum ( It relates to the base material according to any one of the first to sixth aspects, which is fine particles of at least one metal selected from the group consisting of Pt) and gold (Au).

As an eighth aspect, it relates to the base material described in the seventh aspect, wherein the metal fine particles (B) are palladium fine particles.

As a ninth aspect, it relates to 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 diameter of 1 to 100 nm.

As a tenth aspect, the base resin according to any one of the first to ninth aspects, further comprising (E) a base resin having a non-radically polymerizable crosslinkable group.

As an eleventh aspect, it relates to a base layer for electroless metal plating obtained by using the electroless plating base agent according to any one of the first to tenth aspects.

As a twelfth aspect, it relates to a metal plating film formed on the base layer of electroless metal plating described in the eleventh aspect.

As a thirteenth aspect, it relates to a metal film substrate comprising a base material, a base layer of electroless metal plating as described in the eleventh aspect formed on the base material, and a metal plating film formed on the base layer of electroless metal plating. .

As a fourteenth aspect, it relates to a method for manufacturing a metal film base material, including the following steps (1) and (2).

(1) Process: A process of applying the electroless plating base agent according to any one of the first to tenth aspects onto a base material, and providing a base layer of electroless metal plating on the base material,

(2) Process: A process of immersing the base material provided with this base layer in an electroless plating bath and forming a metal plating film on this base layer.

The base agent of the present invention can easily form a base layer for electroless plating simply by applying it on a substrate. In addition, according to the present invention, it is possible to form a plating base layer that has excellent plating performance and high heat resistance, and has excellent adhesion to the LCP substrate. Furthermore, the base agent of the present invention can be easily varnished with various compositions and can have high metal fine particle dispersion stability.

Furthermore, since the polymer used in the base material of the present invention can be easily prepared with a few processes, the manufacturing process of the plating base material can be simplified and the manufacturing cost can be reduced.

In addition, the base layer of electroless metal plating formed from the electroless plating agent of the present invention can easily form a metal plating film simply by immersing it in an electroless plating bath, and can form a metal plating film comprising a base material, a base layer, and a metal plating film. It can be easily obtained from a film base material.

That is, by forming a base layer on a substrate using the electroless plating agent of the present invention, a metal plating film having excellent adhesion to the substrate, especially the LCP substrate, and heat resistance can be formed.

Hereinafter, the present invention will be described in detail.

The base material of the present invention contains (A) a copolymer having the specific structural units described above, (B) metal fine particles, (C) a crosslinking agent, and (D) a solvent, and, if necessary, other components. Jada.

The base agent of the present invention is suitably used as a catalyst for forming a metal plating film on a substrate by electroless plating treatment. Below, each component is explained.

<(A) Copolymer>

Component (A) is a structural unit derived from monomer a, which has a metal dispersible group and one radically polymerizable double bond in the molecule, and a monomer that has a non-radical polymerizable crosslinkable group and one radically polymerizable double bond in the molecule. A copolymer containing a structural unit derived from b (however, the copolymer contains a structural unit derived from monomer c, which has a metal dispersible group and one or more radically polymerizable double bonds in the molecule, and two or more radicals in the molecule) (excluding copolymer (A1) containing structural units derived from monomer d having a polymerizable double bond).

[Monomer a]

In the present invention, monomer a is a compound having a metal dispersible group and one radically polymerizable double bond in the molecule.

The metal dispersible group has interactions such as attachment and/or coordination with the metal fine particles that are component (B), thereby improving the dispersibility of the metal fine particles in the composition, thereby allowing the metal fine particles to exist stably in the composition. It's for. As such a metal dispersible group, a substituent having a carbonyl and a site having a nitrogen atom covalently bonded thereto, that is, a -C(=O)-N- site, is preferable, and more specifically, a substituent having an amide bond is preferred. A group selected from the group consisting of a group and a group having an imide bond is preferred.

The radically polymerizable double bond is preferably a compound having either a vinyl group or a (meth)acryloyl group. On the other hand, when monomer a is a compound having a (meth)acryloyl group as a radically polymerizable double bond, the carbonyl group [-C(=O)-] contained in this (meth)acryloyl group is an amide as a metal dispersing group. It may have a structure that overlaps with the carbonyl group in the group.

Such monomer a includes, for example, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl (meth)acrylamide,

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 (meth)acrylamide, N-vinyl phthalimide, N-vinyl succinimide, etc. are mentioned.

Among them, as monomer a, a monomer having an N-vinylamide group is preferable from the viewpoint of coordination ability with respect to metal, and considering availability, etc., N-vinylpyrrolidone, N-vinylformamide, and N-vinylacet are selected. Amides are preferred.

These monomers a may be used individually, or two or more types may be used in combination.

[Monomer b]

Monomer b is a monomer that has a non-radically polymerizable crosslinkable group and one radically polymerizable double bond in the molecule.

A non-radically polymerizable crosslinkable group is a crosslinkable group that does not have radical polymerization, that is, a crosslinkable group that does not exhibit polymerization even by the action of a radical polymerization initiator. Examples of such crosslinkable groups include hydroxy groups, carboxyl groups, and amino groups.

Monomers having such a non-radically polymerizable crosslinkable group and one radically polymerizable double bond include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate. , 2-hydroxypropyl methacrylate, 4-hydroxybutylacrylate, 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 acrylic. Rate, poly(ethylene glycol)ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynovo Monomers having a hydroxyl group such as nene-2-carboxylic-6-lactone, or p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxyphenylacryl Monomers having a phenolic hydroxyl group such as amide, N-hydroxyphenyl methacrylamide, p-hydroxyphenylacrylate, p-hydroxyphenyl methacrylate, or acrylic acid, methacrylic acid, crotonic acid, mono-(2 -(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxylic acid) Monomers having a carboxyl group such as phenyl)acrylamide or monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate can be mentioned.

In the present invention, when producing the copolymer of component (A), other monomers may be used together with the monomer a and monomer b. Other such monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, and phenyl methacrylate. , Cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 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, tetrahydrofurfuryl acrylate, 3-methoxybutylacrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8- Examples include tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinylnaphthalene, vinylanthracene, and vinylbiphenyl.

In the present invention, when producing the copolymer as component (A), resistance to plating solutions, etc. can be imparted to the copolymer as component (A) obtained by using the other monomers.

However, the copolymer (A) consists of a structural unit derived from monomer c, which has a metal dispersible group and one or more radically polymerizable double bonds in the molecule, and a monomer d that has two or more radically polymerizable double bonds in the molecule. Excludes the copolymer (A1) containing the derived structural units.

<(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 dispersing group include the same ones as those given in the above-mentioned [Monomer a].

Examples of the radically polymerizable double bond include compounds having at least one vinyl group or (meth)acryloyl group. On the other hand, 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 group in the amide group. It may have an overlapping structure.

Such monomer c includes, for example, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl (meth)acrylamide, 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-methoxy Methyl (meth)acrylamide, N-methoxybutyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide , N-isobutoxyethyl (meth)acrylamide, etc.

These monomer c may be used individually in the polymer (A1), or two or more types may be used in combination.

[Monomer d]

In the present invention, monomer d may have one or both of a vinyl group and a (meth)acryloyl group.

Examples of the monomer d include 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) alicyclic vinyl hydrocarbons; Cyclopentadiene, cyclohexadiene, cyclooctadiene, norbonadiene, etc.

(d1-3) Aromatic vinyl hydrocarbons; Divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, 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 itaconate, vinyl (meth)acrylate, etc.

(d2-2) allyl esters; Diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate, allyl (meth)acrylate, etc.

(d2-3) vinyl ethers; Divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc.

(d2-4) allyl ethers; Diallyl ether, diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametharyloxyethane, 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, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxy titanium tri( Meth)acrylate, 1,6-hexanediol di(meth)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>]decane dimethanol 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)acryloyl Oxyethoxy)phenyl]fluorene, undecyleneoxyethylene glycol di(meth)acrylate, bis[4-(meth)acryloylthiophenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide , 1,3-adamantane diol di(meth)acrylate, 1,3-adamantane dimethanol di(meth)acrylate, aromatic urethane di(meth)acrylate, aliphatic 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-based compound:

Diallylamine, diallyl isocyanurate, diallyl cyanurate, ethoxylated isocyanuric acid di(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, methylenebis(meth)acrylamide, bis. maleimide, etc.

(d6) Silicon vinyl-containing compound:

Dimethyldivinylsilane, divinyl(methyl)(phenyl)silane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1 , 1,3,3-tetraphenyldisilazane, diethoxyvinylsilane, etc.

(d7) Fluorinated vinyl-based compound:

1,4-divinylperfluorobutane, 1,4-divinyloctafluorobutane, 1,6-divinylperfluorohexane, 1,6-divinyldodecafluorohexane, 1,8-di Vinylperfluorooctane, 1,8-divinylhexadecafluorooctane, etc.

These monomers d may be used individually, or two or more types may be used in combination.

Specifically, the copolymer (A1) includes a structural portion represented by the following formula [1], that is, a structural portion formed by the polymerization reaction of two or more radically polymerizable double bonds contained in the monomer d, and the following formula: It has a highly branched polymer chain composed of at least a structural moiety represented by formula [2] or formula [3], that is, a structural moiety formed by the polymerization reaction of the radically polymerizable double bond of the monomer c. It consists of a polymer.

[Formula 1]

(During the ceremony,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ 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. 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 represent 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; ,

R ₁₀ and R ₁₁ each independently represent an alkyl group or phenyl group having 1 to 10 carbon atoms that 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, or , R ₁₀ and R ₁₁ may be combined to form an alkylene group having 2 to 6 carbon atoms that may contain at least one bond selected from the group consisting of an ether bond, an amide bond, and an ester bond,

R ₁₂ , R ₁₃ and R ₁₄ each independently represent an alkyl group of 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; ,

R ₁₅ and R ₁₆ each independently represent 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.)

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, cyclophene. Tyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1-adamantyl group, benzyl group, phenethyl group, etc.

Examples of the alkylene group having 2 to 6 carbon atoms include methylene group, propylene group, butylene group, pentylene group, and hexylene group.

In addition, 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 ether bond, amide bond, and ester bond, for example, these The alkyl group, etc. may be interrupted by bonding, or may be bonded to the binding end of the alkyl group, etc. (for example, an oxyalkylene group, etc.).

In addition, 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, a heterocyclic group having 3 to 30 carbon atoms, or one or two thereof. There can be combinations of more than one species. These aliphatic groups, aromatic groups, alicyclic groups, and heterocyclic groups may have substituents. Additionally, these aliphatic groups, aromatic groups, alicyclic groups, and heterocyclic groups may contain at least one bond selected from the group consisting of an ether bond, an amide bond, and an ester bond.

The aliphatic group may be linear or branched, and may have one or more unsaturated bonds. Examples of the aliphatic group 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, and anthracene.

Examples of the aliphatic ring in the alicyclic group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cycloalkane, and condensed rings thereof.

Heterocycles in the above heterocyclic group include pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, pyrrole, pyrazole, imidazole, pyrrolidine, pyrazolidine, imidazolidine, and furan. , pyran, thiophene, thiopyran, isoxazole, isoxazolidine, morpholine, isothiazole, isothiazolidine, thiomorpholine, benzoimidazole, benzofuran, benzothiophene, benzothiazole, benzo Oxazole, triazine, quinone, etc. can be mentioned.

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, the monomer a, the monomer b, and optionally other monomers, a polymerization initiator, etc. are coexisted in a solvent at a temperature of 50 to 110° C. It is obtained by polymerization reaction under the following conditions. At that time, the solvent used is not particularly limited as long as it dissolves the monomer having a specific functional group, the monomer without a specific functional group used as necessary, the polymerization initiator, etc. Specific examples are 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.

In addition, the solution of the specific copolymer obtained by the above method is precipitated by adding it to stirred diethyl ether or water, and the resulting precipitate is filtered and washed, then dried at room temperature or heat-dried under normal or reduced pressure, and then dried in a specific copolymer. It can be made from a composite powder. Through the above operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer is obtained. If sufficient purification is not possible in 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 can be used in powder form or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.

Moreover, in this invention, the specific copolymer of (A) component may be a mixture of multiple types of specific copolymers.

In the present invention, the copolymerization ratio of the monomer a and the monomer b is preferably 0.05 to 5 moles of the monomer b per 1 mole of the monomer a, particularly preferably 0.1 from the viewpoint of reactivity and plating properties. It's a mole to 3 moles.

In the present invention, when using the other monomers above when producing the copolymer of component (A), the amount is 1 to 200 mol%, more preferably 10, relative to the total number of moles of monomer a and monomer b. It ranges from 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 metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), and silver. (Ag), tin (Sn), platinum (Pt), gold (Au), and alloys thereof, and may be one type of these metals or an alloy of two or more types. Among them, palladium fine particles are preferred as metal fine particles. On the other hand, as metal fine particles, oxides of the above metals can also be used.

The metal fine particles are obtained by reducing metal ions, for example, by irradiating a solution of a metal salt with light using a high-pressure mercury lamp or by adding a compound having a reducing effect (a so-called reducing agent) to this solution. For example, by adding a solution of a metal salt to the solution in which the component polymer (A) is dissolved and irradiating it with ultraviolet rays, or by reducing the metal ion by adding a solution of the metal salt and a reducing agent to this solution, ( A base agent containing the component polymer (A) and metal fine particles can be prepared while forming a complex of the component polymer and metal fine particles.

The metal salts include chloroauric acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, platinum chloride, chloroplatinic acid, Pt(dba) ₂ [dba=dibenzylideneacetone], 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 chloride, ruthenium acetate, Ru(cod)(cot)[cot=cyclooctatriene], iridium chloride, iridium acetate, Ni(cod) _2, etc. You can.

The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent based on the metal species to be contained in the obtained base material. Examples of reducing agents that can be used include metal borohydride salts such as sodium borohydride and potassium borohydride; Aluminum hydride salts such as lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, magnesium aluminum hydride, and calcium aluminum hydride; hydrazine compounds; citric acid and its salts; Succinic acid and its salts; Ascorbic acid and its salts; Primary or secondary alcohols such as methanol, ethanol, isopropanol, and polyol; Tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], and 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)- Phosphines such as 1,1'-binaphthyl [BINAP], etc. can be mentioned.

The average particle diameter of the metal fine particles is preferably 1 to 100 nm. By setting the average particle diameter of these metal fine particles to 100 nm or less, the reduction in surface area is small and sufficient catalytic activity is obtained. As for the average particle diameter, 75 nm or less is more preferable, and 1 to 30 nm is particularly preferable.

The average primary particle diameter can be measured by the following method.

[Measurement of average primary particle diameter]

After dispersing the metal particles in ethanol, dropping them on the carbon support membrane and drying them to produce samples, the average primary particle diameter of the obtained samples can be determined by microscopy using a TEM device (Hitachi Works: H-8000, acceleration voltage 200 kV). there is.

The addition amount of the copolymer as component (A) in the brush 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). (B) If the amount of the copolymer (A) added to 100 parts by mass of the metal fine particles is 20 parts by mass or more, the metal fine particles can be sufficiently dispersed, and if it is 20 parts by mass or less, the dispersibility of the metal fine particles is low. If it is insufficient, it becomes easy to generate sediment or aggregates. More preferably, it is 30 parts by mass or more. Additionally, if 10,000 parts by mass or more of the copolymer (A) is added to 100 parts by mass of the metal fine particles (B), the amount of Pd per unit area after application becomes insufficient, and there is a risk that the precipitation properties of plating may decrease.

<(C) Ingredient>

The plating core agent of the present invention can contain a crosslinking agent as component (C). (C) As a component, the crosslinking agent which reacts with the said non-radically polymerizable crosslinkable group is mentioned.

The crosslinking agent as component (C) includes compounds such as epoxy compounds, methylol compounds, block isocyanate compounds, phenoplast compounds, compounds having two or more trialkoxysilyl groups, alkoxysilane compounds having amino groups, alkoxy groups, and/or Examples include polymers such as organometallic compounds having a chelating ligand, polymers of N-alkoxymethylacrylamide, polymers of compounds having an epoxy group, polymers of compounds having an alkoxysilyl group, polymers of compounds having an isocyanate group, and melamine formaldehyde resin. there is.

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, and 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-xylenediamine, 1,3-bis(N,N-digly Cydylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

Specific examples of the above-mentioned methylol compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1 , 3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl )-4,5-dimethoxy-2-imidazolinone, etc. Commercially available products include compounds such as glycoluril compounds manufactured by Mitsui Cytech Co., Ltd. (brand name: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174), methylated urea resin (brand name: UFR (registered trademark) 65), and butyl. Urea resin (product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin (high condensation type, product name: Beckamine (registered trademark) manufactured by DIC Co., Ltd. Examples include J-300S, P-955, and N).

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products include Mitsui Cytech Co., Ltd. (brand name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (brand name: Nikalac (registered trademark) BX-4000, BX-37, BL-60, BX-55H) etc. can be mentioned.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. As commercial products, methoxymethyl-type melamine compounds (brand name: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytech Co., Ltd., butoxymethyl-type melamine compounds (brand name: Mycoat (registered trademark) ) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical (Product name: Nikalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, etc. MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nikalak (registered trademark) MX-45, MX-410, MX-302).

In addition, it may be a compound obtained by condensing 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 prepared from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6323310 can be mentioned. Commercially available products of the melamine compound include Brand Name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytech Co., Ltd.), and commercially available products of the benzoguanamine compound include Brand Name: Cymel (registered trademark) 1123. (manufactured by Mitsui Cytech Co., Ltd.), etc. can be mentioned.

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 protecting group. When exposed to high temperature during thermal curing, the protecting group (block portion) is thermally dissociated and separated, and the generated isocyanate group is separated from the resin. It causes a cross-linking reaction between the

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

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(isocyanate methyl)cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6-bis(isocyanate methyl)tetrahydrodicyclopentadiene, bis(isocyanate methyl)dicyclopentadiene, bis(isocyanate methyl)adamantane, 2,5-diisocyanate Methylnorbornene, norbornene diisocyanate, dicycloheptane triisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylyl Lendiisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 1,3-bis(isocyanate methyl)benzene, dianisidine diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, Diphenyl ether diisocyanate, 2,6-bis(isocyanate methyl)decahydronaphthalene, bis(diisocyanatetolyl)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'-biphenylene diisocyanate, 3,3'-dimethyl-4,4 '-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, bis (isocyanate methyl) thiophene, bis (isocyanate methyl) tetrahydrothiophene, and their modified compounds (e.g. For example, isocyanurate body, buret body, ethylene glycol adapter body, propylene glycol adduct body, trimethylol propane adip body, ethanolamine adduct body, polyester polyol adip body, polyether polyol adip body, polyamide adduct body. , polyamine adduct).

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, ethyl lactate, amyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), triethylene glycol monoethyl ether, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol, etc. Alcohols, phenols such as phenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, chlorophenol, o-cresol, m-cresol, p-cresol, xylenol, α-pyrrolidone , lactams such as β-butyrolactam, β-propiolactam, γ-butyrolactam, δ-valerolactam, and ε-caprolactam, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, diethyl Oximes such as ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4 -Pyrazoles such as nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole, butyl mercaptan, hexyl mercaptan, and dodecyl mercaptan , mercaptans such as benzenethiol, active methylene compounds such as malonic acid diester, acetoacetic acid ester, dinitrile malonate, acetylacetone, methylene disulfone, dibenzoylmethane, dipivaloylmethane, and acetonedicarboxylic acid diester, Amines such as dibutylamine, diisopropylamine, di-tert-butylamine, di(2-ethylhexyl)amine, dicyclohexylamine, benzylamine, diphenylamine, aniline, carbazole, imidazole, 2- Imidazoles such as ethyl imidazole, imines such as methylene imine, ethylene imine, polyethylene imine, and propylene imine, acid amides such as acetanilide, acrylamide, acetic acid amide, and dimer acid amide, succinimide, and maleic acid. Examples include acid imides such as mead and phthalic imide, and urea compounds such as urea, thiourea, and ethylene urea. Additionally, it may be an internal block type formed by a urethione bond (dimerization of an isocyanate group).

Commercially available products of the polyfunctional block isocyanate compound include, for example, the following products.

Takenate [registered trademark] B-815N, B-830, B-842N, B-846N, B-870, B-870N, B-874, B-874N, B-882, B-882N, B-5010, B-7005, B-7030, B-7075 (manufactured by Mitsui Chemicals Co., Ltd.).

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 (manufactured by Asahi Kasei Chemicals Co., Ltd.), Coronate [registered trademark] 2503, 2507, 2512, etc. 2513, 2515, 2520, 2554, BI-301, AP-M, Millionate MS-50 (manufactured by Tosoh Corporation).

Bannock [registered trademark] D-500, D-550, DB-980K (above, manufactured by DIC Co., Ltd.).

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

TRIXENE BI-7641, 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 Baxenden Chemicals Co., Ltd.).

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

In addition, examples of the polyfunctional block isocyanate compound include homopolymers or copolymers obtained by radically polymerizing (meth)acrylate having a block isocyanate group. Here, copolymer means a polymer obtained by polymerizing two or more types of monomers. The copolymer may be a copolymer obtained by polymerizing two or more types of (meth)acrylates having a block isocyanate group, or may be a copolymer obtained by polymerizing a (meth)acrylate having a block isocyanate group and other (meth)acrylates. there is. Commercially available products of (meth)acrylate having such a block isocyanate group include, for example, Showa Denko Co., Ltd. Karens [registered trademark] MOI-BM, AOI-BM, MOI-BP, and AOI-BP. , MOI-DEM, MOI-CP, MOI-MP, MOI-OEt, MOI-OBu, and MOI-OiPr.

These polyfunctional block isocyanate compounds may be used individually or in combination of two or more types.

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

[Formula 2]

Specific examples of compounds having two or more trialkoxysilyl groups include, for example, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 4,4'- Bis(trimethoxysilyl)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-triethoxysilylpropyl)carbonate, bis[(3-trimethoxysilyl)propyl]disulfide, bis[(3-triethoxysilyl) )propyl]disulfide, bis[(3-trimethoxysilyl)propyl]thiourea, bis[(3-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(triethoxysilyl)ethane, tris(3-trimethoxysilylpropyl) ) Compounds such as isocyanurate and tris(3-triethoxysilylpropyl)isocyanurate can be mentioned.

Specific examples of alkoxysilane compounds having an amino group include, for example, N,N'-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N,N'-bis[3- (triethoxysilyl)propyl]-1,2-ethanediamine, N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N-[3-(triethoxysilyl)propyl] -1,2-ethanediamine, bis-{3-(trimethoxysilyl)propyl}amine, bis-{3-(triethoxysilyl)propyl}amine, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, trimethoxy{3-(methylamino)propylsilane, 3-(N-allylamino)propyltrimethoxysilane, 3-(N-allylamino)propyltriethoxysilane, 3-( Compounds such as diethylamino)propyltrimethoxysilane, 3-(diethylamino)propyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, and 3-(phenylamino)propyltriethoxysilane. can be mentioned.

Specific examples of organometallic compounds having an alkoxy group and/or chelate ligand include, for example, diisopropoxyethylacetoacetate aluminum, diisopropoxyacetylacetonate aluminum, triacetylacetonate aluminum, tetrakisisopropyl Titanium poxy, tetrakis(normal-butoxy)titanium, tetraoctyl titanate, diisopropoxybis(acetylacetonate)titanium, titanium tetraacetylacetonate, tetrakis(normal-butoxy)zirconium, tetrakis(normal-butoxy)zirconium and compounds such as tetrakis(acetylacetonate)zirconium.

Furthermore, polymers of the above-mentioned N-alkoxymethylacrylamide include, for example, N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and N-ethoxymethyl(meth)acrylamide. Examples include polymers manufactured using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups such as amide and N-butoxymethyl (meth)acrylamide.

Specific examples of such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, and N-hydroxymethylmethacrylamide and methyl methacrylate. Copolymers include copolymers of N-ethoxymethyl methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl acrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. . The weight average molecular weight of this polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

Examples of polymers of compounds having an epoxy group include compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Examples include polymers manufactured using:

Specific examples of such polymers include, for example, poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), a mixture of glycidyl methacrylate and methyl methacrylate. Examples include polymers, copolymers of 3,4-epoxycyclohexylmethyl methacrylate and methyl methacrylate, and copolymers of glycidyl methacrylate and styrene. The weight average molecular weight of this polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

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

Specific examples of such polymers include, for example, poly(3-methacryloxypropyltrimethoxysilane), copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, 3-methacryloxypropyltrimeth A copolymer of oxysilane and methyl methacrylate, etc. can be mentioned. The weight average molecular weight of this polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000. Meanwhile, in this specification, “poly((meth)acryloxypropyltrimethoxysilane)” means poly(meth)acrylate having an alkoxysilyl group.

These crosslinking agents can be used individually or in combination of two or more types.

The content of the cross-linking agent as component (C) in the electroless plating agent of the present invention is 0 based on 100 parts by mass of the total amount of the copolymer as component (A), the optional component (E) below, and other components. It is preferably from 0 parts by mass to 100 parts by mass, more preferably from 0 parts by mass to 80 parts by mass. If the content of the crosslinking agent is excessive, the deposition properties of the plating and the adhesion of the metal film to the substrate may decrease.

<Hajije>

The electroless plating agent of the present invention contains the above-mentioned (A) copolymer, (B) metal fine particles, (C) crosslinking agent, and (D) solvent, and further contains other components as necessary. In the electroless plating agent of the present invention, it is preferable that the copolymer of component (A) and the metal fine particles (B) form a complex, that is, the primer is formed of a complex of the copolymer of component (A) and the ( B) It is preferable to include a complex formed by metal fine particles.

Here, the complex means that the two coexist in a state in contact with or close to metal fine particles by the action of the metal dispersing group of the side chain of the copolymer, which is the component (A), and form a particulate form. In other words, the above (A) It is expressed as a composite having a structure in which metal particles are attached or coordinated to the metal dispersion group of the copolymer, which is a component.

Here, “attached or coordinated structure” refers to a state in which part or all of the metal dispersing groups of the copolymer, which is component (A), interacts with metal particles, and is thought to form a complex-like structure as a result. Therefore, when palladium fine particles are employed as metal fine particles, it is thought that the Pd atoms in the surface layer interact with the metal dispersible group, thereby forming a structure in which the (A) component polymer surrounds the metal fine particles.

Therefore, the “composite” in the present invention includes not only the metal fine particles and the copolymer as component (A) bonded to form one composite as described above, but also the metal fine particles and the copolymer as component (A). It may also include those that exist independently without forming a bonded part (those that appear to form a single particle on the outside).

The formation of the composite of the copolymer as component (A) and the metal fine particles (B) is carried out simultaneously when preparing the base material containing the copolymer as component (A) and the metal fine particles, and the method includes metal dispersion. A method of synthesizing metal fine particles stabilized to some extent by the group and then exchanging the ligand with the polymer of component (A), or a method of forming a complex by directly reducing metal ions in a solution of the copolymer of component (A). There is. In addition, as described above, a solution of a metal salt is added to the solution in which the copolymer as component (A) is dissolved and irradiated with ultraviolet rays, or a solution of a metal salt and a reducing agent are added to this solution to form metal ions. A complex can also be formed by reducing .

In the direct reduction method, the metal ion and the copolymer as component (A) are dissolved in a solvent and reduced with primary or secondary alcohols such as methanol, ethanol, 2-propanol, and polyol to produce the target metal. A fine particle complex 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 is a solvent that can dissolve the polymer having metal ions and metal dispersible groups in excess of the required concentration, but specifically, alcohols such as methanol, ethanol, n-propanol, and 2-propanol. Ryu; Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; Amides such as N,N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP); Examples include sulfoxides such as dimethyl sulfoxide, and mixed solutions of these solvents, preferably alcohols, halogenated hydrocarbons, and cyclic ethers, and more preferably ethanol, 2-propanol, and chloroform. , tetrahydrofuran, etc.

The temperature of the reduction reaction (mixing the metal ion and the copolymer as component (A)) usually ranges from 0°C to the boiling point of the solvent, and is preferably in the range from room temperature (approximately 25°C) to 100°C. .

As another direct reduction method, the target metal fine particle composite can be obtained by dissolving the metal ion and the copolymer as component (A) in a solvent and reacting in a hydrogen gas atmosphere.

Metal ion sources used here include the above-mentioned metal salts, 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. Additionally, zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.

The solvent to be used is not particularly limited as long as it is a solvent that can dissolve the metal ion and the copolymer as component (A) above the required concentration, and specifically includes alcohols such as ethanol and propanol; Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran; Examples include nitriles such as acetonitrile and butyronitrile, and mixed solutions of these solvents, and tetrahydrofuran is preferable.

The temperature at which the metal ion and the copolymer as component (A) are mixed can usually range from 0° C. to the boiling point of the solvent.

Additionally, as a direct reduction method, the target metal fine particle composite can be obtained by dissolving the metal ion and the copolymer as component (A) in a solvent and subjecting it to a thermal decomposition reaction.

As the metal ion source used here, the above-mentioned metal salts, metal carbonyl complexes, other zero-valent metal complexes, and metal oxides such as silver oxide can be used.

The solvent to be used is not particularly limited as long as it is a solvent that can dissolve the metal ion and the copolymer as component (A) above the required concentration, but specifically includes methanol, ethanol, n-propanol, isopropanol, ethylene glycol, etc. alcohol; Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; Examples include aromatic hydrocarbons such as benzene and toluene, and mixed solutions of these solvents, preferably toluene.

The temperature for mixing the copolymer, which is component (A) having a metal ion and a metal dispersible group, can generally range from 0° C. to the boiling point of the solvent, and is preferably near the boiling point of the solvent, for example, in the case of toluene. It is 110℃ (heated reflux).

The composite of the copolymer and metal fine particles as component (A) thus obtained can be formed into a solid product such as powder through purification treatment such as reprecipitation.

The brush of the present invention contains the copolymer as the component (A) above, (B) metal fine particles (preferably a composite consisting of these), (C) a crosslinking agent, and (D) a solvent, and further, as necessary. Accordingly, as it contains other components, this base agent may be in the form of a varnish used when forming the "base layer of electroless metal plating" described later.

The electroless plating agent of the present invention may, if necessary, contain the base resin as component (E). As component (E), it is preferable to have a group that crosslinks with the crosslinking agent of component (C) by heat, that is, a non-radically polymerizable crosslinkable group, and for example, in WO2014/171376, as component (B) It is desirable that it is described. By adding such (E) component, the adhesion of the resulting base layer may be further improved.

When the plating base of the present invention contains component (E), the content is 100 parts by mass in total of the copolymer as component (A), the metal fine particles as component (B), and the crosslinking agent as component (C). Based on this, it is preferably 0 parts by mass to 200 parts by mass, and more preferably 0 parts by mass to 150 parts by mass. (E) When the content of component is excessive, plating depositability may decrease.

<Other additives>

The brush of the present invention may additionally contain additives such as surfactants, various surface modifiers, and thickeners as appropriate, as long as the effect of the present invention is 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 alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene and polyoxypropylene block copolymers; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, and sorbitan trioleate; Polyoxyethylene nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate; F-Top (registered trademark) EF-301, EF-303, EF-352 [Mitsubishi Material Electronic Hwaseong Co., Ltd.], Megapak (registered trademark) F-171, F-173, R -08, R-30 [above, manufactured by DIC Corporation], 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 [Asahi Glass Co., Ltd.] and Suplon (registered trademark) S-382 [AGC Semichemical Co., Ltd.] can be mentioned.

In addition, the surface adjusting agent includes silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK (registered trademark) - Silicone-based surface conditioners such as 302, 307, 322, 323, 330, 333, 370, 375, and 378 (manufactured by Big Chemi Japan Co., Ltd.) I can hear it.

Examples of the thickener include polyacrylic acids (including crosslinked ones) such as carboxyvinyl polymer (carbomer); Vinyl polymers such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and polystyrene (PS); polyethylene oxide; Polyester; polycarbonate; polyamide; Polyurethane; Polysaccharides such as dextrin, agar, carrageenan, alginic acid, gum arabic, guar gum, tragang gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; Proteins such as gelatin and casein can be mentioned. In addition, each of the above polymers includes not only homopolymers but also copolymers. These thickeners may be used individually, or two or more types may be used in combination.

The viscosity and rheological properties of the base agent of the present invention can be adjusted by mixing a thickener as necessary, and can be appropriately adopted and selected depending on the application, such as the application method and application location of the base agent.

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

[Base layer of electroless metal plating]

The electroless plating base agent of the present invention described above can form a base layer for electroless metal plating by applying it on a substrate. The base layer of this electroless metal plating is also the subject of the present invention.

The substrate is not particularly limited, but a non-conductive substrate or a conductive substrate can be preferably used.

Non-conductive substrates include, for example, glass, ceramics, etc.; Polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene terephthalate) resin, PEEK (polyether ether) ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, LCP (liquid crystal polymer) resin, etc.; Paper, etc. may be mentioned. These are suitably used in the form of sheets or films, and the thickness in this case is not particularly limited.

Additionally, the conductive base material includes, for example, ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), In addition, various stainless steels, aluminum alloys such as aluminum and duralumin, iron and iron alloys, copper and copper alloys such as phosphorus copper, cupronickel and beryllium copper, nickel and nickel alloys, and silver alloys such as silver and nickel silver. Metals, etc. can be mentioned.

Furthermore, a substrate in which a thin film is formed with these conductive substrates on the non-conductive substrate can also be used.

Additionally, the substrate may be a three-dimensional molded body.

It contains the above-mentioned (A) component copolymer, (B) metal fine particles (preferably a composite consisting of these), (C) crosslinking agent, and (D) solvent, and further, if necessary, (E) base polymer and As a specific method of forming a base layer for electroless metal plating from an electroless plating agent containing other components, first, the polymer of component (A) and (B) metal particles (preferably a composite consisting of them) (required) Accordingly, the amine compound and other components) are dissolved or dispersed in the solvent (D) to form a varnish, and the varnish is spin coated on a base material to form a metal plating film; blade coat method; Dip coat method; roll coat method; barcot law; die coat method; Spray coat method; inkjet method; pen lithography such as fountain pen nanolithography (FPN) and dip pen nanolithography (DPN); relief printing methods such as letterpress printing, flexographic printing, resin relief printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), and nanotransfer printing (nTP); Intaglio printing methods such as gravure printing and engraving; Flatbed printing; stencil printing methods such as screen printing and mimeograph; It is applied by an offset printing method or the like, and then the solvent is evaporated and dried to form a thin layer.

Among these application methods, barcoating, flexographic printing, gravure printing, spin coating, spray coating, inkjet, pen lithography, contact printing, μCP, NIL and nTP are preferred. When using the spin coating method, there is an advantage that application can be done in a short time, so even a highly volatile solution can be used, and application with high uniformity can be performed. When using the spray coating method, highly uniform application can be performed with a very small amount of varnish, which is very advantageous industrially. When using inkjet methods, pen lithography, contact printing, μCP, NIL, and nTP, fine patterns such as wiring, for example, can be efficiently formed (drawn), which is very advantageous industrially.

<(D) Solvent>

In addition, the solvent used herein includes the polymer as component (A), metal fine particles (B) (preferably a composite thereof), (C) a crosslinking agent, and, if necessary, dissolve or dissolve component (E) and other components. There is no particular limitation as long as it is dispersed, but examples include water; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, and dichlorobenzene; Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n-hexanol, n-octanol, 2-octanol, and 2-ethylhexanol; Cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and phenyl cellosolve; 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, triethylene glycol monomethyl ether Propylene 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, Glycol ethers such as diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tripropylene glycol dimethyl ether; Glycol esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate (PGMEA); ethers such as tetrahydrofuran (THF), methyltetrahydrofuran, 1,4-dioxane, and diethyl ether; esters such as ethyl acetate and butyl acetate; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone; Aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; Halogenated aliphatic hydrocarbons such as 1,2-dichloroethane and chloroform; Amides such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide; Dimethyl sulfoxide, etc. can be used. These solvents may be used individually, or two or more types of solvents may be mixed. Furthermore, for the purpose of adjusting the viscosity of the varnish, glycols such as ethylene glycol, propylene glycol, and butylene glycol may be added.

In addition, the concentration of the solvent dissolved or dispersed in the solvent is arbitrary, but the concentration of the non-solvent component in the varnish [all components excluding the solvent contained in the paint ((A) component polymer and (B) metal fine particles (preferably these) [Concentration of (C) crosslinking agent, (E) base polymer and other components, etc.] as necessary] is 0.05 to 90% by mass, preferably 0.1 to 80% by mass.

The method of drying the solvent is not particularly limited, and may be evaporated using, for example, a hot plate or oven under an appropriate atmosphere, that is, in the air, in an inert gas such as nitrogen, or in a vacuum. Accordingly, it is possible to obtain a base layer having a uniform film formation surface. The calcination temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably carried out at 40 to 250°C.

[Electroless plating treatment, metal plating film, metal film substrate]

By electroless plating the base layer of electroless metal plating formed on the base material obtained as described above, a metal plating film is formed on this base layer. The metal plating film obtained in this way and the metal film base material provided on the base material in the order of the base layer of electroless metal plating and the metal plating film are also the subject 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, a conventionally known electroless plating solution is used, and is described in this plating solution (bath). A common method is to immerse the base layer of electroless metal plating formed on the surface.

The electroless electrolytic solution mainly contains metal ions (metal salts), complexing agents, and reducing agents, and for other purposes, pH adjusters, pH buffers, reaction accelerators (second complexing agents), stabilizers, and surfactants (to form a plating film). Use for providing gloss, use for improving wettability of the surface to be treated, etc.) are appropriately included.

Here, metals used in the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, and are appropriately selected depending on the purpose.

Additionally, the complexing agent and reducing agent may be appropriately selected depending on the metal ion.

Additionally, commercially available electroless plating solutions can be used as the electroless plating solution, for example, electroless nickel plating chemicals (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd., electroless copper plating chemicals (Melplate (registered trademark) ) CU series); Electroless nickel plating solution (ICP Nicolon (registered trademark) series, Toppiena 650) manufactured by Okuno Pharmaceutical Co., Ltd., electroless copper plating solution (OPC-700 Electroless Copper M-K, ATS Ado Copper IW, same product) ) CT, OPC Copper (registered trademark) AF series, copper HFS, copper NCA), electroless tin plating solution (Subster SN-5), electroless gold plating solution (Flash Gold 330, Self Gold OTK-IT), electroless silver Plating solution (Muden Silver); Electroless palladium plating solution (Palette II) and electroless gold plating solution (Deep G series, NC Gold series) manufactured by Kojima Chemical Co., Ltd.; Electroless silver plating solution (Sdia AG-40) manufactured by Sasaki Chemical Co., Ltd.; Electroless nickel plating solution (Kanigen (registered trademark) series, Shuma (registered trademark) series, Shuma (registered trademark) Kani Black (registered trademark) series), electroless palladium plating solution (S) manufactured by Japan Kanigen Co., Ltd. -KPD); Dow Chemical's electroless copper plating solution (Q Posite (registered trademark) Copper Mix series, Circu Posite (registered trademark) series), electroless palladium plating solution (Paramus (registered trademark) series), electroless nickel plating solution ( Duraposite (registered trademark) series), electroless gold plating solution (Orolectrores (registered trademark) series), electroless tin plating solution (Tin Posite (registered trademark) series); Electroless copper plating solution (Thru Cup (registered trademark) ELC-SP, PSY, PCY, PGT, PSR, PEA, PMK) manufactured by Uemura Kogyo Co., Ltd., Atotech Japan Co., Ltd. Electroless copper plating amounts (Print Gaunt (registered trademark) PV, Copper PVE), etc. can be used conveniently.

The electroless plating process adjusts the temperature, pH, immersion time, metal ion concentration of the plating bath, the presence or absence or stirring speed of the plating bath, the presence or absence or supply speed of air and oxygen, etc., thereby increasing the formation rate of the metal film or film. Thickness can be controlled.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Meanwhile, the measurement of number average molecular weight and 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 copolymer obtained according to the following synthesis example were measured using a GPC device (Shodex column KD800 and TOSOH column TSK-GEL) manufactured by Tosoh Co., Ltd. using the elution solvent N,N-dimethylformamide. (As an additive, 10 mmol/L (liter) of lithium bromide-hydrate (LiBr·H ₂ O) was mixed) and measured under the condition that the mixture was eluted by flowing it through the column (column temperature 40°C) at a flow rate of 1 mL/min. Meanwhile, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in polystyrene conversion values.

The meanings of the abbreviations used in the examples below are as follows.

MMA: Methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

HEA: 2-hydroxyethyl acrylate

NVA: N-vinylacetamide

NVF: N-vinylformamide

NVP: N-vinylpyrrolidone

BMA: Benzyl methacrylate

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

Eporite 400E: Polyethylene glycol #400 diglycidyl ether (manufactured by Kyoeisha Chemical)

BI7960: Isocyanate (manufactured by Baxenden)

BL-10: Polyvinyl acetal resin (manufactured by Sekisui Chemical Industries, Ltd.)

<Synthesis Example 1>

2.00 g of styrene, 1.63 g of NVA, 2.23 g of HEA, and 0.29 g of AMBN were dissolved in 14.37 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring. Thus, the polymer was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P1). The Mn of the obtained copolymer was 6,806 and Mw was 11,797.

<Synthesis Example 2>

2.00 g of styrene, 0.81 g of NVA, 3.34 g of HEA, and 0.31 g of AMBN were dissolved in 15.10 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring. Thus, the polymer was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P2). The Mn of the obtained copolymer was 6,512 and Mw was 10,298.

<Synthesis Example 3>

2.00 g of styrene, 2.45 g of NVA, 1.11 g of HEA, and 0.28 g of AMBN were dissolved in 13.64 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30 mass%) was added to 500 mL of diethyl ether while stirring. Thus, the polymer was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P3). The Mn of the obtained copolymer was 7,043 and Mw was 10,112.

<Synthesis Example 4>

2.00 g of BMA, 0.97 g of NVA, 1.32 g of HEA, and 0.21 g of AMBN were dissolved in 10.50 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring. Thus, the polymer was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P4). The Mn of the obtained copolymer was 15,693 and Mw was 40,962.

<Synthesis Example 5>

2.00 g of styrene, 1.63 g of NVA, 2.50 g of HEMA, and 0.31 g of AMBN were dissolved in 15.03 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring. Thus, the polymer was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P5). The Mn of the obtained copolymer was 6,823 and Mw was 12,492.

<Synthesis Example 6>

2.00 g of styrene, 1.37 g of NVF, 2.23 g of HEA, and 0.28 g of AMBN were dissolved in 13.71 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30 mass%) was added to 500 mL of diethyl ether while stirring. Thus, the polymer was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P6). The Mn of the obtained copolymer was 6,590 and Mw was 10,266.

<Synthesis Example 7>

2.00 g of styrene, 2.13 g of NVP, 2.23 g of HEA, and 0.32 g of AMBN were dissolved in 15.59 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30 mass%) was added to 500 mL of diethyl ether while stirring. Thus, the polymer was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P7). The Mn of the obtained copolymer was 5,283 and Mw was 11,499.

<Synthesis Example 8>

2.00 g of MMA, 1.11 g of HEMA, and 0.16 g of AMBN were dissolved in 7.63 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring, and the polymer was It was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain copolymer powder (P8). The Mn of the obtained copolymer was 13,186 and Mw was 24,452.

<Synthesis Example 9>

2.00 g of styrene, 4.46 g of HEA, and 0.32 g of AMBN were dissolved in 15.83 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring, and the polymer was It was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain copolymer powder (P9). The Mn of the obtained copolymer was 5,797 and Mw was 9,880.

<Synthesis Example 10>

2.00 g of styrene, 3.27 g of NVA, and 0.26 g of AMBN were dissolved in 12.91 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring, and the polymer was It was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain a copolymer powder (P10). The Mn of the obtained copolymer was 4,265 and Mw was 5,609.

<Synthesis Example 11>

2.50 g of NVA, 1.71 g of HEA, and 0.21 g of AMBN were dissolved in 10.30 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring, and the polymer was It was precipitated. The precipitated polymer was filtered under reduced pressure and dried under vacuum at 50°C to obtain copolymer powder (P11). The Mn of the obtained copolymer was 7,489 and Mw was 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P1 polymerized in Synthesis Example 1 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M1) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P2 polymerized in Synthesis Example 2 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M2) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P3 polymerized in Synthesis Example 3 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle complex. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M3) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P4 polymerized in Synthesis Example 4 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M4) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P5 polymerized in Synthesis Example 5 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M5) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P6 polymerized in Synthesis Example 6 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle complex. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M6) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P7 polymerized in Synthesis Example 7 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle complex. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M7) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P9 polymerized in Synthesis Example 9 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle complex. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M8) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P10 polymerized in Synthesis Example 10 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle complex. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M9) as 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 added to a 100 mL reaction flask equipped with a cooler, and stirred until uniform. To this solution, a solution in which 1.0 g of P11 polymerized in Synthesis Example 11 was dissolved in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. This mixture was stirred at 60°C under a nitrogen atmosphere for 8 hours.

After cooling to a liquid temperature of 30°C, this solution was added while stirring to 341 g of IPE/hexane solution (mass ratio 10:1) to precipitate the polymer/Pd particle complex. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried under vacuum at 50°C to obtain 0.9 g of Pd particle composite (M10) as black powder.

[Evaluation of heat resistance]

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

[Preparation of plating solution]

<Preparation example 1>

Into a 300 mL beaker, 20 mL of Sawtooth Colon SA-98-MLF (Okuno Pharmaceutical Co., Ltd.) and 11 mL of Sawtooth Colon SA-98-1LF (Okuno Pharmaceutical Co., Ltd.) were added, and pure water was further added to bring the total amount of solution to 200 mL. This solution was stirred and used as an electroless nickel plating solution.

[Evaluation of dispersibility]

The obtained Pd particle complex was added as shown in Table 2, stirred for 1 hour, left to stand, and the state of the solution was evaluated visually. The evaluation results are summarized and shown in Table 3 later.

<Evaluation criteria for dispersibility>

○: A uniform solution was obtained.

×: A precipitate was observed and a uniform solution was not obtained.

[Evaluation of plating precipitation]

The LCP (Pellicul (registered trademark) LCP, manufactured by Chiyoda Integration Co., Ltd.) substrate was subjected to surface treatment for 30 seconds using a UV ozone cleaning device (UV-208, manufactured by Techno Vision Co., Ltd.). An electroless plating agent was applied as a bar coat to a film thickness of 12 μm on the surface-treated LCP, and then heated at 80°C for 5 minutes to form a film. This coating film was again 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. Thereafter, the obtained plating substrate was washed with water, and the state of the metal plating film was evaluated with the naked eye. The evaluation results are later shown in Table 3.

<Evaluation criteria for plating precipitation>

○: Plating is deposited uniformly on the entire surface of the coating film.

-: Not carried out because a uniform solution was not obtained.

<Evaluation of adhesion>

In the metal plating film portion on the plating substrate obtained above, cuts were made with a cutter knife to form 10 × 10 cells at 1 mm intervals in length and width. Sellotape (registered trademark) manufactured by Nichiban Co., Ltd. was attached to this sheath, strongly rubbed to adhere it tightly, and then the adhered adhesive tape was removed at once, and the state of the metal plating film was evaluated visually according to the following standards. The evaluation results are later shown in Table 3.

<Evaluation criteria for adhesion>

○: All 100 divisions remain without peeling off.

×: Even 1 scale is peeled off.

-: Not carried out because a uniform solution was not obtained.

As shown in Table 1, 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. Additionally, Examples 1 to 11 had good adhesion. On the other hand, Comparative Examples 1 to 3 could not confirm sufficient adhesion.

Claims (14)

As an electroless plating agent for forming a metal plating film on a substrate by electroless plating,
(A) A structural unit derived from monomer a, which has a metal dispersible group and one radically polymerizable double bond in the molecule, and a structural unit derived from monomer b, which has a hydroxyl group and one radically polymerizable double bond in the molecule. A copolymer containing (however, the copolymer includes a structural unit derived from monomer c, which has a metal dispersible group and one or more radically polymerizable double bonds in the molecule, and a monomer that has two or more radically polymerizable double bonds in the molecule. Excluding copolymers (A1) containing structural units derived from d),
(B) metal particles,
(C) cross-linking agent, and
(D)Solvent
Hajije, including . According to paragraph 1,
A base material comprising a complex in which the metal fine particles (B) are attached or coordinated to a metal dispersing group in the copolymer (A). According to claim 1 or 2,
A primer in which the monomer a is a compound having either a vinyl group or a (meth)acryloyl group. According to paragraph 3,
A base material wherein the monomer a is N-vinylpyrrolidone, N-vinylacetamide, or N-vinylformamide. According to claim 1 or 2,
A primer in which the monomer b is a compound having either a vinyl group or a (meth)acryloyl group. According to claim 1 or 2,
The monomer giving the copolymer (A) includes the monomer b in an amount of 5 to 500 mol% relative to the number of moles of the monomer a. According to claim 1 or 2,
The metal fine particles (B) include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold ( A base material that is fine particles of at least one metal selected from the group consisting of Au). In clause 7,
(B) A base material in which the metal fine particles are palladium fine particles. According to claim 1 or 2,
(B) A base material in which the metal fine particles are fine particles having an average particle diameter of 1 to 100 nm. According to claim 1 or 2,
Additionally, (E) a base resin containing a base resin having a non-radically polymerizable crosslinkable group. A method for producing a base layer, comprising a step of forming a base layer for electroless metal plating from the electroless plating base agent according to claim 1 or 2. A method for producing a metal plating film, comprising the following steps (1) and (2).
(1) Process: A process of forming a base layer for electroless metal plating from the electroless plating base agent described in paragraph 1 or 2,
(2) Process: A process of forming a metal plating film on this base layer. A method for manufacturing a metal film substrate, comprising the following steps (1) and (2).
(1) Process: A process of applying the electroless plating base agent according to paragraph 1 or 2 on a base material and providing a base layer of electroless metal plating on the base material,
(2) Process: A process of immersing the base material provided with this base layer in an electroless plating bath and forming a metal plating film on this base layer. delete