KR102878303B1 - Electroless plating agent containing high molecular weight polymer and metal particles - Google Patents

Abstract

[Task] To provide a new base material used as a pretreatment process for electroless plating, which has high heat resistance, can form a plating base layer that does not contain corrosive atoms, and further, can realize cost reduction in its manufacturing.
[Solution] An electroless plating base for forming a metal plating film on a substrate by electroless plating, comprising: (a) a highly branched polymer formed by polymerizing a polymerizable compound including at least a monomer A having two or more radically polymerizable double bonds in the molecule and a monomer B having an amide group and at least one radically polymerizable double bond in the molecule, and a polymerization initiator C in an amount of 5 to 200 mol% based on the mole number of the monomer A, wherein the polymer has a highly branched polymer chain and a radical cleavage fragment of the polymerization initiator C is mounted at the end of the polymer chain, and (b) a base comprising metal fine particles.

Description

Electroless plating agent containing high molecular weight polymer and metal particles

The present invention relates to an electroless plating agent comprising a high-branched polymer and metal fine particles.

Electroless plating is widely used in various fields, such as decorative purposes such as imparting a sense of luxury and aesthetics to resin molded bodies such as automobile parts, and wiring technology for electronic shielding, printed circuit boards, and large-scale integrated circuits, because a film with a uniform thickness is obtained regardless of the type or shape of the substrate simply by immersing the substrate in a plating solution, and a metal plating film can be formed on non-conductive materials such as plastics, ceramics, and glass.

Typically, when forming a metal plating film on a substrate (plated body) by electroless plating, a pretreatment is performed to increase the adhesion between the substrate and the metal plating film. Specifically, first, the surface to be treated is roughened and/or made hydrophilic by various etching means, followed by a sensitization treatment (sensitization) to supply an adsorbent that promotes the adsorption of a plating catalyst onto the surface to be treated, and an activation treatment (activation) to adsorb the plating catalyst onto the surface to be treated. Typically, the sensitization treatment is performed by immersing the object to be treated in an acidic solution of stannous chloride, thereby attaching a metal (Sn2 ⁺ ) that can act as a reducing agent 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. Accordingly, the palladium ions in the solution are reduced by the reducing metal (tin ion: Sn ²⁺ ) and attached to the surface to be treated as active palladium catalyst nuclei. After this pretreatment, the surface to be treated is immersed in an electroless plating solution to form a metal plating film.

Meanwhile, highly branched polymers classified as dendritic polymers actively introduce branches, and as a notable feature, they have a large, spherical, bulky skeleton, so they have excellent dispersion stability. Furthermore, they have a large number of terminal groups. When reactive functional groups are added to these terminal groups, the polymer has a very high density of reactive functional groups, so applications such as highly sensitive scavengers for functional substances such as catalysts, highly sensitive multifunctional crosslinking agents, and dispersants or coating agents for metals or metal oxides are expected.

For example, 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 has been reported, and a proposal has been made for an electroless plating base agent that avoids the use of chromium compounds (chromic acid), which was a problem in the pretreatment process (roughening process) of conventional electroless plating, and also reduces the number of pretreatment processes, thereby improving various aspects such as the environment, cost, and cumbersome operability (Patent Document 1).

International Patent Application Publication No. 2012/141215 Pamphlet

In the composition comprising a highly branched polymer having an ammonium group and metal fine particles proposed as a base material for the electroless plating described above, when applied to wiring technology in semiconductor manufacturing, etc., there is a concern that the highly branched polymer may decompose during solder reflow or high-temperature processing due to the low heat resistance temperature of the highly branched polymer contained therein. Furthermore, the highly branched polymer contains a halogen as a counter anion to the quaternary ammonium group contained therein, and furthermore, sulfur atoms may remain in the polymer during the manufacturing process of the highly branched polymer, which also raises concerns about corrosion of the substrate. Furthermore, the synthesis of the highly branched polymer is performed in multiple steps, which makes the manufacturing cost high. In addition, quaternary ammonium salts often act as catalysts in curing components using epoxies, isocyanates, etc., and thus, when using a highly branched polymer containing a quaternary ammonium salt structure, problems with the storage stability of the varnish used as an electroless plating base material are likely to occur.

Thus, among the electroless plating bases proposed so far, in addition to the plating performance as a plating base, there has not been a proposal for an electroless plating base that has sufficiently realized various performances such as being able to impart plating with high heat resistance without containing corrosive atoms such as halogen atoms or sulfur atoms, being easily varnishable with various compositions, and having high dispersion stability, and furthermore, operability such as being able to be easily manufactured with a small number of processes.

The present invention, taking these problems into consideration, aims to provide a novel base material used as a pretreatment process for electroless plating, which can form a base layer having high heat resistance and not containing corrosive atoms, and further, can realize cost reduction in its manufacture.

The present inventors, as a result of extensive studies to achieve the above-described object, have examined a highly branched polymer containing an amide group and preferably a cyclic skeleton and containing only no corrosive atoms, and have discovered that a layer obtained by combining this highly branched polymer with metal fine particles and applying this on a substrate has not only plating properties as a base layer for electroless metal plating but also high heat resistance and, furthermore, no risk of corrosion, 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 highly branched polymer comprising a polymerizable compound including at least a monomer A having two or more radically polymerizable double bonds in the molecule, a monomer B having an amide group and at least one radically polymerizable double bond in the molecule, and a polymerization initiator C in an amount of 5 to 200 mol% based on the mole number of the monomer A.

A highly branched polymer, comprising a highly branched polymer chain comprising at least a structural portion represented by the following formula [1] and formula [2] or formula [3], and further comprising a radical cleavage fragment of the polymerization initiator C mounted at the end of the polymer chain, and

(b) metal particles

It is about a system that includes:

[Chemical Formula 1]

(During the meal,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent an alkyl 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,

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 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,

R ₁₀ and R ₁₁ each independently represent an alkyl group or phenyl 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, or R ₁₀ and R ₁₁ may form an alkylene group having 2 to 6 carbon atoms which 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 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 ₁₅ and R ₁₆ each independently represent an alkyl 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.

As a second aspect, it relates to the agent described in the first aspect, which comprises a complex in which (b) metal fine particles are attached or coordinated to an amide group in the (a) high-branched polymer.

As a third aspect, the present invention relates to the agent described in the first or second aspect, wherein the monomer A is a compound having one or both of a vinyl group and a (meth)acryloyl group.

As a fourth aspect, the present invention relates to the agent described in the third aspect, wherein the monomer A is a divinyl compound or a di(meth)acrylate compound.

As a fifth aspect, the present invention relates to the agent described in the fourth aspect, wherein the monomer A is a compound having an aromatic ring having 3 to 30 carbon atoms or an alicyclic ring having 3 to 30 carbon atoms.

As a sixth aspect, the present invention relates to the agent described in the fifth aspect, wherein the monomer A is divinylbenzene or tricyclo[5.2.1.0 ^2,6 ]decane dimethanol di(meth)acrylate.

As a seventh aspect, the present invention relates to a polymerization initiator according to any one of the first to sixth aspects, wherein the polymerization initiator C is an azo polymerization initiator.

As an eighth aspect, the polymerizable compound relates to a polymerization agent as described in any one of the first to seventh aspects, wherein the polymerizable compound comprises 5 to 300 moles of the monomer B relative to the mole number of the monomer A.

As a ninth viewpoint, the above A ₁ relates to the agent described in the first viewpoint, which represents a divalent organic group having an aromatic ring having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.

As a tenth viewpoint, the (a) high-branched polymer is a high-branched polymer composed of a polymer that forms a polymer chain including at least the structural portions represented by the above formula [1] and formula [2],

In equation [1],

R ₁ , R ₂ , R ₅ and R ₆ represent hydrogen atoms,

R ₃ and R ₄ represent hydrogen atoms or methyl groups,

A ₁ represents a phenylene group or a tricyclo[5.2.1.0 ^2,6 ]decane-4,8-diyl-di(methyleneoxycarbonyl) group,

In equation [2],

R ₇ , R ₈ and R ₉ represent hydrogen atoms,

R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a methyl group, or R ₁₀ and R ₁₁ become one to represent an n-propylene group,

A polymer chain comprising a radical cleavage fragment of a polymerization initiator C selected from 2,2'-azobis(2-methylbutyronitrile) and dimethyl2,2'azobis(2-methylpropionate) at the end thereof.

It is about the Hajije described in the first viewpoint.

As an eleventh aspect, the present invention relates to a coating composition according to any one of the first to tenth aspects, wherein the (b) metal particles are particles of at least one metal selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold (Au).

As a 12th viewpoint, the present invention relates to the agent described in the 11th viewpoint, wherein the above (b) metal particles are palladium particles.

As a 13th viewpoint, the present invention relates to a method according to any one of the first to twelfth viewpoints, wherein the (b) metal fine particles are fine particles having an average particle diameter of 1 to 100 nm.

As a 14th aspect, it relates to a haze agent described in any one of the 1st to 13th aspects, which additionally contains (c) an amine compound.

As a 15th viewpoint, it relates to an electroless metal plating base layer, which is a layer made of an electroless plating agent described in any one of the 1st to 14th viewpoints.

As a 16th viewpoint, it relates to a metal plating film formed on the base layer of the electroless metal plating described in the 15th viewpoint.

As a 17th viewpoint, it relates to a metal film substrate comprising a substrate, an electroless metal plating base layer formed on the substrate as described in the 15th viewpoint, and a metal plating film formed on the electroless metal plating base layer.

As an 18th viewpoint, it relates to a method for manufacturing a metal film substrate, including the following processes A and B.

Process A: A process of applying an electroless plating agent described in any one of the first to fourteenth aspects onto a substrate and providing an electroless metal plating base layer on the substrate.

Process B: A process of immersing a substrate having this base layer in an electroless plating bath and forming a metal plating film on this base layer.

The coating composition of the present invention can easily form an electroless plating base layer simply by applying it to a substrate. Furthermore, the present invention enables the formation of a plating base layer that exhibits excellent plating performance and high heat resistance, and is free from substrate corrosion concerns. Furthermore, the coating composition of the present invention can be easily varnished with various compositions and exhibits high dispersion stability.

Furthermore, since the high-branched polymer used in the plating agent of the present invention can be easily prepared with a small number of processes, it is possible to simplify the manufacturing process of the plating agent and reduce the manufacturing cost.

In addition, the electroless metal plating base layer 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 a metal film base material comprising a base material, a base layer, and a metal plating film can be easily obtained.

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 and heat resistance can be formed.

Figure 1 is a drawing showing ^{the 13} C NMR spectrum of the highly branched polymer 5 (DVB, NVA, V-59) obtained in polymerization example 5.
Figure 2 is a drawing showing ^{the 13} C NMR spectrum of the highly branched polymer 6 (DVB, NVP, V-59) obtained in polymerization example 6.
Figure 3 is a drawing showing ^{the 13} C NMR spectrum of the highly branched polymer 7 (DCP, NVP, V-59) obtained in polymerization example 7.

Hereinafter, the present invention will be described in detail.

The present invention provides a coating composition comprising (a) a highly branched polymer having the specific structural portion described above, (b) metal fine particles, and, if necessary, (c) an amine compound.

The present invention is suitably used as a catalyst for forming a metal plating film on a substrate by electroless plating.

<(a)Highly branched polymer>

The hyperbranched polymer used in the present invention (hereinafter also referred to as an amide group-containing hyperbranched polymer) is a hyperbranched polymer composed of a polymerizable compound including at least a monomer A having two or more radically polymerizable double bonds in the molecule, a monomer B having an amide group and at least one radically polymerizable double bond in the molecule, and a polymerization initiator C in an amount of 5 to 200 mol% based on the mole number of the monomer A. The hyperbranched polymer is a so-called initiator fragment-loaded (IFIRP) type hyperbranched polymer, and has a fragment (radical cleavage fragment) of the polymerization initiator C used in the polymerization reaction at its terminal.

Meanwhile, the “highly branched polymer” in the present invention includes not only high molecular weight polymers of the monomers A and B, but also oligomers that are low molecular weight polymers. In other words, the high molecular weight polymer of the present invention can also be understood as a “branched polymer.”

The highly branched polymer of the present invention is a polymer having a highly branched polymer chain comprising at least a structural part represented by the following formula [1], that is, a structural part formed by a polymerization reaction of at least two radically polymerizable double bonds included in the monomer A, and a structural part represented by the following formula [2] or formula [3], that is, a structural part formed by a polymerization reaction of the radically polymerizable double bond of the monomer B, and further comprising a polymer product in which a radical cleavage fragment of a polymerization initiator C is mounted at the end of the polymer chain.

[Chemical Formula 2]

(During the meal,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent an alkyl 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,

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 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,

R ₁₀ and R ₁₁ each independently represent an alkyl group or phenyl 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, or R ₁₀ and R ₁₁ may form an alkylene group having 2 to 6 carbon atoms which 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 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 ₁₅ and R ₁₆ each independently represent an alkyl 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.

The above alkyl group having 1 to 10 carbon atoms may have a branched structure, a cyclic structure, or may be an arylalkyl group. Specifically, examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, a 1-adamantyl group, a benzyl group, and a phenethyl group.

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

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 an ether bond, an amide bond and an ester bond, and for example, the alkyl group may be interrupted by these bonds, or may be bonded to a bonding group of the alkyl group (for example, an oxyalkylene group, etc.).

In addition, examples of the divalent organic group include 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 a combination of one or more of these. These aliphatic groups, aromatic ring groups, alicyclic groups, and heterocyclic groups may have a substituent. In addition, these aliphatic groups, aromatic ring 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 above aliphatic group may be linear or branched, and may also have one or more unsaturated bonds, and may include, for example, an alkylene group having 1 to 20 carbon atoms.

Aromatic rings in the above-mentioned aromatic ring include benzene, naphthalene, fluorene, phenanthrene, anthracene, etc.

Aliphatic rings in the above alicyclic group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cycloalkane, and condensed rings thereof.

Examples of the heterocyclic ring in the above heterocyclic group include pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, pyrrole, pyrazole, imidazole, pyrrolidine, pyrazolidine, imidazolidine, furan, pyran, thiophene, thiopyran, isoxazole, isoxazolidine, morpholine, isothiazole, isothiazolidine, thiomorpholine, benzimidazole, benzofuran, benzothiophene, benzothiazole, benzoxazole, triazine, quinone, etc.

Among these, it is preferable that the above A ₁ is a divalent organic group having an aromatic ring having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.

The above-mentioned high-branched polymer can be produced in one step by polymerizing a polymerizable compound containing at least monomer A and monomer B, which will be described later, in the presence of a predetermined amount of polymerization initiator C with respect to the monomer A.

[Monomer A]

In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule preferably has one or both of a vinyl group and a (meth)acryloyl group, and is particularly preferably a divinyl compound or a di(meth)acrylate compound. Among these, from the viewpoint of improving heat resistance, the monomer A is preferably a compound having an aromatic ring group having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.

Meanwhile, in the present invention, the term "(meth)acrylate compound" refers to both an acrylate compound and a methacrylate compound. For example, "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid.

Examples of monomers A usable in the present invention include organic compounds shown in (A1) to (A7) below.

(A1) Vinyl hydrocarbons:

(A1-1) Aliphatic vinyl hydrocarbons; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene, etc.

(A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc.

(A1-3) Aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc.

(A2) Vinyl esters, allyl esters, vinyl ethers, allyl ethers, vinyl ketones:

(A2-1) Vinyl esters; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth)acrylate, etc.

(A2-2) Allyl esters; diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate, allyl (meth)acrylate, etc.

(A2-3) Vinyl ethers; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc.

(A2-4) Allyl ethers; diallyl ether, diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametharyloxyethane, etc.

(A2-5) Vinyl ketones; divinyl ketone, diallyl ketone, etc.

(A3)(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 ]Decanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, undecyleneoxyethylene glycol di(meth)acrylate, bis[4-(meth)acryloylthiophenyl]sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, aromatic urethane di(meth)acrylate, aliphatic urethane di(meth)acrylate, etc.

(A4) Vinyl 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.

(A5) Nitrogen-containing vinyl compounds:

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

(A6) Silicon vinyl compounds:

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

(A7) Fluorinated vinyl compounds:

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

Preferred among these are aromatic vinyl hydrocarbon compounds of the above (A1-3) group, vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the (A2) group, (meth)acrylic acid esters of the (A3) group, vinyl compounds having a polyalkylene glycol chain of the (A4) group, and nitrogen-containing vinyl compounds of the (A5) group.

Particularly preferred are divinylbenzene belonging to the (A1-3) group, diallyl phthalate belonging to the (A2) group, ethylene glycol di(meth)acrylate, 1,3-adamantane dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate belonging to the (A3) group, and methylene bis(meth)acrylamide belonging to the (A5) group. Among these, divinylbenzene, ethylene glycol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate are preferred, and divinylbenzene or tricyclodecane dimethanol di(meth)acrylate is more preferred.

These monomers A may be used alone, or two or more may be used in combination.

[Monomer B]

In the present invention, monomer B is not particularly limited as long as it is a compound having an amide group and at least one radically polymerizable double bond in the molecule, but is preferably a compound having at least one vinyl group or a (meth)acryloyl group as the radically polymerizable double bond. Meanwhile, when monomer B is a compound having a (meth)acryloyl group as the radically polymerizable double bond, the carbonyl group [-C(=O)-] contained in the (meth)acryloyl group may have a structure overlapping with the carbonyl group in the amide group.

Examples of such monomers B include 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, etc.

These monomers B may be used alone, or two or more may be used in combination.

In the present invention, the copolymerization ratio of the monomer A and the monomer B is preferably 0.05 to 20 moles of the monomer B per 1 mole of the monomer A, particularly preferably 0.1 to 10 moles, from the viewpoint of reactivity or plating properties.

[Other monomers]

The above polymerizable compound may contain, together with the above monomer A and the above monomer B, a monomer D having at least one radically polymerizable double bond in the molecule and having only an amide group as another monomer.

As such monomer D, a compound having at least one vinyl group or (meth)acrylic group, and a maleimide compound are preferred.

Among them, vinyl ether group-containing (meth)acrylate compounds such as 2-(2-vinyloxyethoxy)ethyl acrylate; epoxy group-containing (meth)acrylate compounds such as glycidyl methacrylate; alkoxysilyl group-containing (meth)acrylate compounds such as 3-methacryloxypropyltriethoxysilane; maleimide compounds such as cyclohexylmaleimide and N-benzylmaleimide are preferable.

In the present invention, when the polymerizable compound includes the monomer D, the mixing ratio is preferably 0.05 to 3.0 mol of the monomer D per 1 mol of the monomer A, particularly preferably 0.1 to 1.5 mol, from the viewpoint of reactivity or surface modification effect.

[Polymerization initiator C]

In the present invention, the polymerization initiator C is preferably an azo polymerization initiator. Examples of the azo polymerization initiator include the compounds shown in (1) to (6) below.

(1) Azonitrile compounds:

2,2'-Azobisisobutyronitrile, 2,2'-Azobis(2-methylbutyronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), 1,1'-Azobis(1-cyclohexanecarbonitrile), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoyl azo)isobutyronitrile, etc.;

(2) Azoamide compounds:

2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-Azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide}, 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-Azobis(N-butyl-2-methylpropionamide), 2,2'-Azobis(N-cyclohexyl-2-methylpropionamide), etc.;

(3) Cyclic azoamidine compounds:

2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-Azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(1-imino-1-pyrrolidino-2-methylpropane)dihydrochloride, etc.;

(4) Azoamidine compounds:

2,2'-Azobis(2-methylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate, etc.;

(5) Others:

Dimethyl 2,2'-azobisisobutyrate [dimethyl 2,2-azobis(2-methylpropionate), 2,2'-azobis(2,4,4-trimethylpentane), 1,1'-azobis(1-acetoxy-1-phenylethane), dimethyl 1,1'-azobis(1-cyclohexanecarboxylate), 4,4'-azobis(4-cyanopentanoic acid), 4,4'-azobis-4-cyanovaleric acid, etc.

(6) Fluoroalkyl group-containing azo polymerization initiator:

4,4'-Azobis(4-cyanopentanoic acid-2-(perfluoromethyl)ethyl), 4,4'-Azobis(4-cyanopentanoic acid-2-(perfluorobutyl)ethyl), 4,4'-Azobis(4-cyanopentanoic acid-2-(perfluorohexyl)ethyl), etc.

Among the above azo polymerization initiators, 2,2'-azobis(2-methylbutyronitrile) and dimethyl 2,2'-azobisisobutyrate are preferable from the viewpoint of dissolution into the plating bath and plating properties.

Meanwhile, when 2,2'-azobis(2-methylbutyronitrile) is used as the polymerization initiator C, the radical cleavage fragment derived from the polymerization initiator C located at the end of the polymer chain in the polymer becomes a 1-methyl-1-cyano-propyl group [-C(CH ₃ )(CN)-CH ₂ CH ₃ ].

The above polymerization initiator C is used in an amount of 5 to 200 mol%, preferably 15 to 200 mol%, more preferably 15 to 170 mol%, and even more preferably 50 to 100 mol%, based on the mole number of the monomer A.

<Method for producing high-branched polymers>

The high-branched polymer used in the present invention is obtained by polymerizing a polymerizable compound containing the monomer A and monomer B, and other monomers as needed, as described above, in the presence of a predetermined amount of polymerization initiator C relative to the monomer A.

As a polymerization method in the presence of a polymerization initiator C of the polymerizable compound containing the aforementioned monomers A, monomer B, and optionally other monomers, known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization are exemplified, and among these, solution polymerization or precipitation polymerization is preferred. In particular, from the perspective of molecular weight control, it is preferred to carry out the reaction by solution polymerization in an organic solvent.

Organic solvents used at this time include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane; halogenated compounds such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and orthodichlorobenzene; esters or ester-ethers such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; Examples thereof include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide, and mixed solvents of two or more thereof.

Preferred among these are aromatic hydrocarbons, halides, esters, ethers, ketones, alcohols, amides, etc., and particularly preferred are benzene, toluene, xylene, orthodichlorobenzene, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.

When the above polymerization reaction is carried out in the presence of an organic solvent, for example, the mass of the organic solvent relative to 1 mass part of the monomer A is usually 0.5 to 100 mass parts, and more preferably 1 to 10 mass parts.

The amount of organic solvent can be appropriately selected depending on the molecular weight of the target hyperbranched polymer. For example, when designing a hyperbranched polymer with a higher molecular weight, the amount of organic solvent can be reduced (resulting in a higher concentration of polymerizable compounds in the solvent). Conversely, when designing a hyperbranched polymer with a lower molecular weight, the amount of organic solvent can be increased (resulting in a lower concentration of polymerizable compounds in the solvent).

The polymerization reaction is carried out under atmospheric pressure, pressurized sealed condition, or reduced pressure, and is preferably carried out under atmospheric pressure due to the simplicity of the equipment and operation. Furthermore, it is preferably carried out under an inert gas atmosphere such as _N2 .

The polymerization temperature may be any temperature as long as it is below the boiling point of the reaction mixture, but from the viewpoint of polymerization efficiency and molecular weight control, it is preferably 50 to 200°C, more preferably 70 to 150°C.

More preferably, the polymerization reaction is carried out at the reflux temperature of the organic solvent under the reaction pressure, that is, it is preferable to carry out the polymerization reaction by dropping a solution containing the polymerizable compound, the polymerization initiator, and the organic solvent into the organic solvent maintained in a reflux state.

The reaction time cannot be uniformly specified because it varies depending on the reaction temperature, the type and ratio of polymerizable compounds (monomer A, monomer B, and other monomers as needed) and polymerization initiator C, the type of organic solvent used for polymerization, etc., but it is preferably 30 to 720 minutes, more preferably 40 to 540 minutes.

After the polymerization reaction is completed, the resulting high-branched polymer is recovered by any method, and post-processing such as washing is performed as needed. Methods for recovering the polymer from the reaction solution include methods such as reprecipitation.

The weight average molecular weight (hereinafter abbreviated as Mw) of the high-branched polymer used in the present invention thus obtained is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and most preferably 2,000 to 30,000, as converted to polystyrene by gel permeation chromatography (GPC).

Among the highly branched polymers used in the present invention, a particularly preferable example is a highly branched polymer composed of a polymer constituting a polymer chain including at least the structural parts represented by the above formula [1] and formula [2],

In equation [1],

R ₁ , R ₂ , R ₅ and R ₆ represent hydrogen atoms,

R ₃ and R ₄ represent hydrogen atoms or methyl groups,

A ₁ represents a phenylene group or a tricyclo[5.2.1.0 ^2,6 ]decane-4,8-diyl-di(methyleneoxycarbonyl) group,

In equation [2],

R ₇ , R ₈ and R ₉ represent hydrogen atoms,

R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a methyl group, or R ₁₀ and R ₁₁ become one to represent an n-propylene group,

A highly branched polymer can be exemplified, which is formed by loading a radical cleavage fragment of a polymerization initiator C selected from 2,2'-azobis(2-methylbutyronitrile) and dimethyl2,2'azobis(2-methylpropionate) at the end of the polymer chain.

<(b) Metal particles>

The (b) metal fine particles used in the present invention are not particularly limited, and examples of metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold (Au), and alloys thereof. The metal species may be one type or an alloy of two or more types. Among these, palladium fine particles are preferable. Meanwhile, oxides of the above metals may also be used as the metal fine particles.

The above metal fine particles are obtained by reducing metal ions, for example, by a method of irradiating a solution of a metal salt with light using a high-pressure mercury lamp, or by adding a compound having a reducing action (so-called reducing agent) to the solution. For example, by adding a solution of a metal salt to a solution in which the above-mentioned highly branched polymer has been dissolved and irradiating the solution with ultraviolet rays, or by adding a solution of a metal salt and a reducing agent to the solution, thereby reducing the metal ions, thereby forming a complex of the highly branched polymer and the metal fine particles, a coating composition comprising the highly branched polymer and the metal fine particles can be prepared.

Examples of the above 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.

The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal type to be contained in the obtained base agent. Examples of reducing agents that can be used include: boron hydride metal salts such as sodium borohydride and potassium borohydride; aluminum hydride salts such as lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum 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 polyols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], and ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; Examples include phosphines such as 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], and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [BINAP].

The average particle size of the above metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the metal fine particles to 100 nm or less, the reduction in surface area is minimal, resulting in sufficient catalytic activity. The average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.

In the coating composition of the present invention, the amount of the (a) hyperbranched polymer added is preferably 20 parts by mass or more and 10,000 parts by mass or less relative to 100 parts by mass of the (b) metal fine particles. By adding the (a) hyperbranched polymer to 100 parts by mass of the (b) metal fine particles, the metal fine particles can be sufficiently dispersed. In addition, if the amount is 20 parts by mass or less, the dispersibility of the metal fine particles is insufficient, and sediments or aggregates are likely to be generated. More preferably, it is 30 parts by mass or more. In addition, if the (a) hyperbranched polymer is added to 100 parts by mass of the (b) metal fine particles, the amount of Pd per unit area after coating becomes insufficient, and there is a concern that the deposition property of the plating may deteriorate.

<(c)amine compound>

As the (c) amine compound used in the electroless plating base of the present invention, a known one can be used, and examples thereof include aliphatic amines such as alkylamines and hydroxyalkylamines, amines having a cyclic substituent, aromatic amines (arylamines), and amine compounds having an alkoxysilyl group. Among these amine compounds, an amine compound having an alkoxysilyl group is preferable. Furthermore, in order to improve the storage stability of the plating base, it is preferable that the amino group of the amine compound is protected by a ketone (protected by an alkylidene group), and in the present invention, an amine compound in which the amino group is protected by an alkylidene group is also included in the (c) component. On the other hand, when using an amine compound protected by an alkylidene group as the (c) component, it is preferable to use a solvent of ketones, ethers, or esters as the solvent of the base described later, rather than an alcohol solvent that removes the protection by the alkylidene group.

In the present invention, by incorporating (c) an amine compound into an electroless plating agent, the effect of improving the dispersion stability of the metal fine particles, specifically a composite composed of metal fine particles and a highly branched polymer, described below, in the agent is obtained, and further, it contributes to the formation of a fine plating pattern. Meanwhile, since the amine compound protected by an alkylidene group has its alkylidene group deprotected by the electroless plating solution, an amine compound protected by an alkylidene group can be used as the (c) component.

The above alkylamines include ethylamine (CH ₃ CH ₂ NH ₂ ), propylamine (CH ₃ (CH ₂ ) ₂ NH ₂ ), butylamine (CH ₃ (CH ₂ ) ₃ NH ₂ ), pentylamine (CH ₃ (CH ₂ ) ₄ NH ₂ ), hexylamine (CH ₃ (CH ₂ ) ₅ NH ₂ ), heptylamine (CH ₃ (CH ₂ ) ₆ NH ₂ ), octylamine (CH ₃ (CH ₂ ) ₇ NH ₂ ), nonylamine (CH ₃ (CH ₂ ) ₈ NH ₂ ), decylamine (CH ₃ (CH ₂ ) ₉ NH ₂ ), undecylamine (CH ₃ (CH ₂ ) ₁₀ NH ₂ ), dodecylamine (CH ₃ (CH ₂ ) ₁₁ NH ₂ ), tridecylamine (CH ₃ (CH ₂ ) Primary amines such as tetradecylamine (CH ₃ (CH ₂ ) ₁₃ NH ₂ ), pentadecylamine (CH ₃ (CH ₂ ) ₁₄ NH ₂ ), hexadecylamine ₍ CH ₃ (CH ₂ ) ₁₅ NH ₂ ), heptadecylamine (CH ₃ (CH ₂ ) ₁₆ NH ₂ ), octadecylamine (CH ₃ (CH ₂ ) ₁₇ NH ₂ ), nonadecylamine (CH ₃ (CH ₂ ) ₁₈ NH ₂ ), icosylamine (CH ₃ (CH ₂ ) ₁₉ NH ₂ ), and structural isomers thereof; Secondary amines such as N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, _and N,N-dibutylamine; Tertiary amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine can be mentioned.

The above hydroxyalkylamines (alkanolamines) include methanolamine (OHCH ₂ NH ₂ ), ethanolamine (OH(CH ₂ ) ₂ NH ₂ ), propanolamine (OH(CH ₂ ) ₃ NH ₂ ), butanolamine (OH(CH ₂ ) ₄ NH ₂ ), pentanolamine (OH(CH ₂ ) ₅ NH ₂ ), hexanolamine (OH(CH ₂ ) ₆ NH ₂ ), heptanolamine (OH(CH ₂ ) ₇ NH ₂ ), octanolamine (OH(CH ₂ ) ₈ NH ₂ ), nonanolamine (OH(CH ₂ ) ₉ NH ₂ ), decanolamine (OH(CH ₂ ) ₁₀ NH ₂ ), undecanolamine (OH(CH ₂ ) ₁₁ NH ₂ ), and dodecanolamine (OH(CH ₂ ) ₁₂ NH ₂ ), tridecanolamine (OH(CH ₂ ) ₁₃ NH ₂ ), tetradecanolamine (OH(CH ₂ ) ₁₄ NH ₂ ), pentadecanolamine (OH(CH ₂ ) ₁₅ NH ₂ ), hexadecanolamine (OH(CH ₂ ) ₁₆ NH ₂ ), heptadecanolamine (OH(CH ₂ ) ₁₇ NH ₂ ), octadecanolamine (OH(CH ₂ ) ₁₈ NH ₂ ), nonadecanolamine (OH(CH ₂ ) ₁₉ NH ₂ ), eicosadecanolamine (OH(CH ₂ ) ₂₀ NH ₂ ), etc., primary amines; Secondary amines such as N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, and N-butylbutanolamine can be mentioned.

In addition, other aliphatic amines include alkoxyalkylamines such as methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, and butoxybutylamine.

As an example of an amine having a cyclic substituent, an amine compound represented by the formula R ₁₇ -R ₁₈ -NH ₂ is preferable.

In the above formula, R ₁₇ is a monovalent cyclic group having 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms, and may be any of an alicyclic group, an aromatic group, and a combination thereof. These cyclic groups may be substituted with any substituent, for example, an alkyl group having 1 to 10 carbon atoms. R ₁₈ represents a single bond or an alkylene group having 1 to 17 carbon atoms, preferably 1 to 3 carbon atoms.

In the present invention, preferred specific examples of the amine compound represented by the formula R ¹¹ -R ¹² -NH ₂ include compounds represented by the following formulas (A-1) to (A-10).

[Chemical Formula 3]

Specific examples of aromatic amines (arylamines) include aniline, N-methylaniline, o-, m-, or p-anisidine, o-, m-, or p-toluidine, o-, m-, or p-chloroaniline, o-, m-, or p-bromoaniline, o-, m-, or p-iodoaniline, etc.

Specific examples of amine compounds having an alkoxysilyl group include 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-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, trimethoxy[3-(methylamino)]propylsilane, 3-(N-allylamino)propyltrimethoxysilane, Examples of compounds include 3-(N-allylamino)propyltriethoxysilane, 3-(diethylamino)propyltrimethoxysilane, 3-(diethylamino)propyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, and 3-(phenylamino)propyltriethoxysilane.

In addition, among the alkylamines, hydroxyalkylamines, other aliphatic amines, amines having a cyclic substituent, aromatic amines (arylamines), and amine compounds having an alkoxysilyl group, which are given as specific examples above, amino compounds in which the amino group is protected by an alkylidene group, for example, by a ketone such as methyl ethyl ketone or methyl isobutyl ketone, may be mentioned.

The content of the (c) amine compound in the present invention is preferably 0.01 to 500 parts by mass, more preferably 0.1 to 300 parts by mass, and particularly 1 to 100 parts by mass, based on 100 parts by mass of the complex formed from the highly branched polymer and the metal fine particles described below (or the total mass of the highly branched polymer and the metal fine particles).

(c) If the content of the amine compound is less than the above numerical range, the dispersibility and solubility stabilization effect of the complex formed from the highly branched polymer and metal fine particles described later is not obtained, and if added in an amount greatly exceeding the above range (for example, 10 times the mass amount of the complex, etc.), not only may the plating bath be contaminated or destroyed, but the plating film may also have a poor appearance.

<Hajije>

The electroless plating agent of the present invention comprises (a) a highly branched polymer and (b) metal fine particles, and further comprises (c) an amine compound and further other components as needed. In the electroless plating agent of the present invention, it is preferable that the highly branched polymer and the metal fine particles form a complex, that is, it is preferable that the agent comprises a complex formed by the highly branched polymer and the metal fine particles.

Here, the complex is expressed as a complex in which the two coexist in a state of contact or proximity to metal particles and form a particle-like form due to the action of the amide group of the side chain of the highly branched polymer, in other words, a complex having a structure in which metal particles are attached or coordinated to the amide group of the highly branched polymer.

Here, the term "attached or coordinated structure" refers to a state in which some or all of the amide groups of the hyperbranched polymer interact with the metal particles. For example, when a palladium salt is employed as the metal atom, it is believed that the amide groups and the palladium salt form a structure as shown in (a) or (b) below (wherein L is a ligand). Accordingly, when palladium particles are employed as the metal particles, it is believed that the hyperbranched polymer forms a structure in which the Pd atoms in the surface layer interact with the amide groups, thereby surrounding the metal particles.

[Chemical Formula 4]

Accordingly, the "composite" in the present invention may include not only a composite in which metal fine particles and a highly branched polymer are combined to form a single composite as described above, but also a composite in which metal fine particles and a highly branched polymer do not form a bonding portion and exist independently (appearing to form a single particle in appearance).

Since the structural parts represented by formula [1], formula [2] and formula [3] included in the polymer chain of the (a) hyperbranched polymer of the present invention do not have an active proton that reduces a Pd atom or a site that crosslinks with a Pd atom, the (a) hyperbranched polymer of the present invention can stably form a complex with (b) metal fine particles by means of an amide group.

The formation of the complex of the (a) hyperbranched polymer and (b) metal fine particles is carried out simultaneously during the preparation of the substrate containing the hyperbranched polymer and the metal fine particles, and the method includes a method of synthesizing metal fine particles stabilized to a certain extent by lower ammonium ligands and then exchanging the ligands with the hyperbranched polymer, or a method of forming the complex by directly reducing metal ions in a solution of the hyperbranched polymer. In addition, as described above, the complex can also be formed by reducing metal ions by adding a solution of a metal salt to a solution in which the hyperbranched polymer is dissolved and irradiating the solution with ultraviolet rays, or by adding a solution of a metal salt and a reducing agent to the solution.

In the ligand exchange method, metal microparticles stabilized to a certain extent by the lower ammonium ligands that serve as raw materials can be synthesized by the method described in Journal of Organometallic Chemistry 1996, 520, 143-162, etc. The desired metal microparticle complex can be obtained by dissolving the hyperbranched polymer in the reaction mixture solution of the obtained metal microparticles and stirring at room temperature (approximately 25°C) or while heating.

The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving metal fine particles and highly branched polymers in concentrations exceeding the required concentration, but specific examples thereof include alcohols such as ethanol, n-propanol, and 2-propanol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile, and a mixture of these solvents, and tetrahydrofuran is preferable.

The temperature at which the reaction mixture of the metal fine particles and the high-branched polymer are mixed can be generally in the range of 0°C to the boiling point of the solvent, and is preferably in the range of room temperature (approximately 25°C) to 60°C.

Meanwhile, in the ligand exchange method, metal fine particles can be stabilized to a certain extent in advance by using a phosphine-based dispersant (phosphine ligand) in addition to an amine-based dispersant (lower ammonium ligand).

By the direct reduction method, a metal ion and a highly branched polymer are dissolved in a solvent and reduced with a first- or second-class alcohol such as methanol, ethanol, 2-propanol, or polyol, thereby obtaining the desired metal microparticle complex.

As the metal ion source used here, the metal salt described above can be used.

The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving a highly branched polymer having a metal ion and an amide group in a concentration higher than the necessary concentration, but specific examples thereof include alcohols such as methanol, ethanol, n-propanol, and 2-propanol; 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), N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide, and the like, and mixtures of these solvents. Preferably, alcohols, halogenated hydrocarbons, and cyclic ethers are used, and more preferably, ethanol, 2-propanol, chloroform, and tetrahydrofuran are used.

The temperature of the reduction reaction (mixing metal ions and highly branched polymers) can usually range from 0°C to the boiling point of the solvent, and is preferably in the range of room temperature (approximately 25°C) to 60°C.

Another direct reduction method is to obtain the desired metal microparticle complex by dissolving metal ions and a highly branched polymer in a solvent and reacting them under a hydrogen gas atmosphere.

As the metal ion source used here, the metal salts described above, or metal carbonyl complexes such as hexacarbonyl chromium [Cr(CO) ₆ ], pentacarbonyl iron [Fe(Co) ₅ ], octacarbonyl dicobalt [ _Co2 (CO) ₈ ], and tetracarbonyl nickel [Ni(CO) ₄ ] can be used. In addition, 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 capable of dissolving the metal ion hyperbranched polymer in a concentration higher than the required concentration, but specific examples thereof include alcohols such as ethanol and propanol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile, and mixtures of these solvents, and tetrahydrofuran is preferable.

The temperature at which the metal ion and the high-branched polymer are mixed can typically be in the range of 0°C to the boiling point of the solvent.

In addition, as a direct reduction method, the target metal microparticle complex can be obtained by dissolving a metal ion and a highly branched polymer in a solvent and causing a thermal decomposition reaction.

As the metal ion source used here, the metal salts described above, 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 can dissolve metal ions and highly branched polymers in concentrations higher than the required concentration, but specific examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; aromatic hydrocarbons such as benzene and toluene, and mixtures of these solvents, and toluene is preferable.

The temperature at which the highly branched polymer having a metal ion and an amide group is mixed can be generally in the range of 0°C to the boiling point of the solvent, and is preferably around the boiling point of the solvent, for example, 110°C (heated reflux) in the case of toluene.

The complex of the high-branched polymer and the metal fine particles thus obtained can be made into a solid form such as a powder through purification treatment such as re-precipitation.

The coating agent of the present invention comprises (a) a high-branched polymer and (b) metal fine particles (preferably a composite made of these), and further comprises (c) an amine compound and other components as needed. The coating agent may be in the form of a varnish used in forming the [base layer of electroless metal plating] described below.

Other additives

The adhesive of the present invention may additionally contain an appropriate amount of additives such as surfactants, various surface conditioners, and thickeners, as long as the effects of the present invention are not impaired.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-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; Examples thereof include fluorine-based surfactants such as F-Top (registered trademark) EF-301, EF-303, and EF-352 [all manufactured by Mitsubishi Material Electronics Co., Ltd.], Megapak (registered trademark) F-171, F-173, R-08, and R-30 [all manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430 and FC-431 [all manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) AG-710 [manufactured by Asahi Glass Co., Ltd.], and Surflon (registered trademark) S-382 [manufactured by AGC Seimi Chemical Co., Ltd.].

In addition, examples of the surface conditioner include silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; silicone-based surface conditioners such as BYK (registered trademark)-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 [all manufactured by BYK Chemical Japan Co., Ltd.];

Examples of the thickener include polyacrylic acids (including cross-linked ones) such as carboxyvinyl polymer (carbomer); vinyl polymers such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and polystyrene (PS); polyethylene oxides; polyesters; polycarbonates; polyamides; polyurethanes; polysaccharides such as dextrin, agar, carrageenan, alginic acid, gum arabic, guar gum, gum tragacanth, locust bean gum, starch, pectin, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose; and proteins such as gelatin and casein. In addition, each of the above polymers includes not only homopolymers but also copolymers. These thickeners may be used alone, or two or more may be used in combination.

The viscosity or rheological properties of the adhesive of the present invention can be adjusted by blending a thickener as needed, and the adhesive can be appropriately adopted or selected according to the application method or application site of the adhesive, etc., depending on the intended use.

These additives may be used alone or in combination of two or more. The amount of the additive used is preferably 0.001 to 50 parts by mass, more preferably 0.005 to 10 parts by mass, and still more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the composite formed from the high-branched polymer and the metal fine particles.

[Substrate of electroless metal plating]

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

Although not particularly limited to the above-mentioned substrate, a non-conductive substrate or a conductive substrate may 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, etc.; and paper, etc. These are suitably used in the form of sheets or films, and in this case, there is no particular limitation on the thickness.

In addition, as conductive materials, 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), various types of stainless steel, aluminum and aluminum alloys such as duralumin, iron and iron alloys, copper and copper alloys such as copper chromium, phosphor bronze, cupro-nickel, and beryllium copper, nickel and nickel alloys, and silver and silver alloys such as nickel silver 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 above-described material may be a three-dimensional molded body.

A specific method for forming a base layer for electroless metal plating from an electroless plating agent comprising the above (a) a high-branched polymer and (b) metal fine particles (preferably a composite made of these), and further comprising, if necessary, (c) an amine compound and other components, comprises first dissolving or dispersing the high-branched polymer and the metal fine particles (preferably a composite made of these) (and, if necessary, an amine compound and other components) in an appropriate solvent to form a varnish, and then applying this varnish to a substrate on which a metal plating film is to be formed using a spin coating method; a blade coating method; a dip coating method; a roll coating method; a bar coating method; a die coating method; a spray coating method; an inkjet method; penlithography such as fountain pen nanolithography (FPN), dip pen nanolithography (DPN), etc.; It is applied by a relief printing method such as letterpress, flexographic printing, relief printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), nanotransfer printing (nTP); an intaglio printing method such as gravure printing and engraving; a planographic printing method; a stencil printing method such as screen printing and mimeograph; an offset printing method, etc., and then a thin layer is formed by evaporating and drying the solvent.

Among these coating methods, spin coating, spray coating, inkjet, pen lithography, contact printing, μCP, NIL, and nTP are preferable. When using spin coating, it has the advantage of being able to apply in a short time, so it can be used even with highly volatile solutions, and it can also perform highly uniform coating. When using spray coating, it is possible to perform highly uniform coating with an extremely small amount of varnish, which is very advantageous industrially. When using inkjet, pen lithography, contact printing, μCP, NIL, and nTP, it is possible to efficiently form (drawing) fine patterns such as wiring, which is very advantageous industrially.

In addition, the solvent used herein is not particularly limited as long as it dissolves or disperses the complex and, if necessary, an amine compound and other components, but includes, for example, 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; Glycol ethers such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, 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), methyl tetrahydrofuran, 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 alone or as a mixture of two or more types of solvents. Furthermore, for the purpose of adjusting the viscosity of the varnish, glycols such as ethylene glycol, propylene glycol, and butylene glycol may be added. Meanwhile, as described above, when using an amine compound in which the amino group is protected by an alkylidene group as the (c) amine compound, it is preferable to avoid using an alcohol solvent that removes the protecting group, and to use ketones, ethers, esters, and the like as the solvent.

In addition, the concentration at which the solvent is dissolved or dispersed is arbitrary, but the concentration of the non-solvent component in the varnish [the concentration of all components excluding the solvent included in the adhesive (highly branched polymer and metal fine particles (preferably a complex composed of these), amine compounds and other components as needed, etc.)] is 0.05 to 90 mass%, preferably 0.1 to 80 mass%.

The drying method for the solvent is not particularly limited. For example, it can be evaporated using a hot plate or oven under an appropriate atmosphere, such as air, an inert gas such as nitrogen, or in a vacuum. This allows for the formation of a substrate layer with a uniform film surface. The sintering temperature is not particularly limited as long as the solvent can be evaporated, but is preferably 40 to 250°C.

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

By electroless plating the electroless metal plating base layer formed on the substrate obtained as described above, a metal plating film is formed on the base layer. The metal plating film thus obtained, and a metal film substrate comprising the electroless metal plating base layer and the metal plating film in that order on the substrate, are also objects of the present invention.

The electroless plating treatment (process) is not particularly limited and can be performed by any generally known electroless plating treatment. For example, a method of immersing the base layer of the electroless metal plating formed on the substrate in a conventionally known electroless plating solution (bath) is common.

The above electroless plating solution mainly contains metal ions (metal salts), a complexing agent, and a reducing agent, and is made by appropriately including a pH adjuster, a pH buffer, a reaction accelerator (second complexing agent), a stabilizer, a surfactant (for use in imparting gloss to a plating film, for use in improving wettability of a surface to be treated, etc.) according to other purposes.

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 above complexing agent and reducing agent can be appropriately selected depending on the metal ion.

In addition, the electroless plating solution may be a commercially available plating solution, for example, the electroless nickel plating chemicals (Melplate (registered trademark) NI series) and electroless copper plating chemicals (Melplate (registered trademark) CU series) manufactured by Meltex Co., Ltd.; the electroless nickel plating solutions (ICP Nicolone (registered trademark) series, Toppiena 650) manufactured by Okuno Pharmaceutical Industry Co., Ltd., the electroless copper plating solutions (OPC-700 Electroless Copper M-K, ATS Adcopper IW, Copper CT, OPC Copper (registered trademark) AF series, Copper HFS, Copper NCA), the electroless tin plating solution (Substar SN-5), the electroless gold plating solution (Flash Gold 330, Self Gold OTK-IT), the electroless silver plating solution (Mudeun Silver); Electroless palladium plating solution (Pallet II) and electroless gold plating solution (Deep G series, NC Gold series) from Kojima Chemical Co., Ltd.; Electroless silver plating solution (S-Dia AG-40) from Sasaki Chemical Co., Ltd.; Electroless nickel plating solution (Kanizen (registered trademark) series, Schumer (registered trademark) series, Schumer (registered trademark) Kani Black (registered trademark) series) and electroless palladium plating solution (S-KPD) from Japan Kanizen Co., Ltd.; Electroless copper plating solution (Q-Posite (registered trademark) Coppermix series, Circuposite (registered trademark) series), electroless palladium plating solution (Palamas (registered trademark) series), electroless nickel plating solution (Duraposite (registered trademark) series), electroless gold plating solution (Orolectroless (registered trademark) series), electroless tin plating solution (Tinposite (registered trademark) series) from Dow Chemical Co., Ltd. Electroless copper plating solutions (Thrucup (registered trademark) ELC-SP, Copper PSY, Copper PCY, Copper PGT, Copper PSR, Copper PEA, Copper PMK) manufactured by Uemura Industries, Ltd., and electroless copper plating solutions (Printgaunt (registered trademark) PV, Copper PVE) manufactured by Atotech Japan, Ltd. can be used appropriately.

The above electroless plating process can control the formation speed or film thickness of the metal film by adjusting the temperature, pH, immersion time, metal ion concentration, presence or absence of stirring or stirring speed, and presence or absence or supply speed of air or oxygen of the plating bath.

Example

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited thereto. In the examples, the physical properties of the samples were measured using the following device under the following conditions.

(1) Molecular weight measurement 1: GPC (gel permeation chromatography)

Device: HLC-8220GPC manufactured by Tosoh Co., Ltd.

Column: Shodex (registered trademark) KF-804L+KF-803L manufactured by Showa Denko Co., Ltd.

Column temperature: 40℃

Solvent: tetrahydrofuran

Detector: UV (254 nm), RI

(2) Molecular weight measurement 2: GPC (gel permeation chromatography)

Device: HLC-8220GPC manufactured by Tosoh Co., Ltd.

Column: Shodex (registered trademark) KF-804L+KF-803L manufactured by Showa Denko Co., Ltd.

Column temperature: 40℃

Solvent: DMF

Detector: UV (254 nm), RI

(3) ¹³ C NMR spectrum

Device: JNM-ECA700 manufactured by Japan Electronics Co., Ltd.

Solvent: CDCl ₃

Relaxant: chromium trisacetylacetonate (Cr(acac) ₃ )

Standard: CDCl ₃ (77.0 ppm)

(4) ICP luminescence analysis (inductively coupled plasma luminescence analysis)

Device: ICPM-8500 manufactured by Shimadzu Corporation

(5) TEM (transmission electron microscope) image

Device: H-8000 manufactured by Hitachi High-Technologies Co., Ltd.

(6) 5% weight loss temperature

Device: Rigakuze Shisiretsubi TG8120

Measurement conditions: Air atmosphere

Heating rate: 10℃ min (25~500℃)

Additionally, the abbreviations have the following meanings:

DCP: Tricyclo[5.2.1.0 ^2,6 ]decane dimethanol dimethacrylate [DCP manufactured by Shin-Nakamura Chemical Co., Ltd.]

DVB: Divinylbenzene [DVB-960 manufactured by Nippon-Tetsu Chemical Co., Ltd.]

NVP: N-vinylpyrrolidone [manufactured by Kanto Chemical Co., Ltd.]

NVA: N-vinylacetamide [manufactured by Showa Denko Co., Ltd.]

MCS: Methyl Cellosolve

DIPE: Diisopropyl ether

V-59: 2,2'-Azobis(2-methylbutyronitrile)

KBM-903: 3-Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM-9103: 3-Trimethoxysilyl-N-(1,3-dimethylbutylidene)propylamine (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Reference Example 1] Preparation of electroless copper plating solution

In a 1 L flask, 125 mL of Q-Posite (registered trademark, hereinafter the same) Copper Mix 328A [manufactured by Dow Chemical Company], 125 mL of Q-Posite Copper Mix 328L [manufactured by Dow Chemical Company], and 15 mL of Q-Posite Copper Mix 328C [manufactured by Dow Chemical Company] were added, and additionally, pure water was added to make the total volume of the solution 1 L.

[Reference Example 2] Preparation of electroless nickel plating solution

In a 1 L flask, 100 mL of Bluesumer (manufactured by Kanizen Co., Ltd.) was added, and additionally, pure water was added to make the total volume of the solution 500 mL.

[Polymerization Example 1: Preparation of Highly Branched Polymer 1 Using DVB, NVP, and V-59]

In a 300 mL reaction flask, 97.6 g of MCS was added, stirred, nitrogen was introduced for 5 minutes, and heated until the inner liquid refluxed (approximately 130°C).

In a separate 200 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 8.34 g (75 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as initiator C, and 68.3 g of MCS were charged, stirred, nitrogen was introduced for 5 minutes, and nitrogen replacement was performed, followed by cooling to 0°C in an ice bath.

Into the refluxing MCS in the 300 mL reaction flask mentioned above, the contents were added dropwise from the 100 mL reaction flask containing DVB, NVP, and V-59 over a period of 30 minutes using a dropping pump. After completion of the dropping, the mixture was stirred for an additional hour.

Next, this reaction solution was added to 975.62 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 12.79 g (yield 43.7%) of the target product (highly branched polymer 1) as a white powder.

The weight average molecular weight Mw of the obtained target product, measured in polystyrene conversion by GPC, was 8,900, and the polydispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 3.8.

[Polymerization Example 2: Preparation of Highly Branched Polymer 2 Using DVB, NVP, and V-59]

In a 200 mL reaction flask, 122.8 g of MCS was added, stirred, nitrogen was introduced for 5 minutes, and heated until the inner liquid refluxed (approximately 130°C).

In a separate 100 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 11.11 g (100 mmol) of NVP as monomer B, 19.23 g (100 mmol) of V-59 as initiator C, and 85.99 g of MCS were charged, stirred, nitrogen was introduced for 5 minutes, and nitrogen replacement was performed, followed by cooling to 0°C in an ice bath.

Into the refluxing MCS in the 200 mL reaction flask mentioned above, the contents were added dropwise from the 100 mL reaction flask containing DVB, NVP, and V-59 over a period of 30 minutes using a dropping pump. After completion of the dropping, the mixture was stirred for an additional hour.

Next, this reaction solution was added to 1,228 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 15.44 g (yield 41.9%) of the target product (highly branched polymer 2) as a white powder.

The weight average molecular weight Mw of the obtained target product, measured in polystyrene conversion by GPC, was 2,600, and the polydispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.8.

[Polymerization Example 3: Preparation of Highly Branched Polymer 3 Using DVB, NVP, and V-59]

In a 200 mL reaction flask, 106.8 g of MCS was added, stirred, nitrogen was introduced for 5 minutes, and heated until the inner liquid refluxed (approximately 130°C).

In a separate 100 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 11.11 g (100 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as initiator C, and 74.74 g of MCS were charged, stirred, nitrogen was introduced for 5 minutes, and nitrogen replacement was performed, followed by cooling to 0°C in an ice bath.

Into the refluxing MCS in the 200 mL reaction flask mentioned above, the contents were added dropwise from the 100 mL reaction flask containing DVB, NVP, and V-59 over a period of 30 minutes using a dropping pump. After completion of the dropping, the mixture was stirred for an additional hour.

Next, this reaction solution was added to 1,068 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 16.50 g (yield 51.5%) of the target product (highly branched polymer 3) as a white powder.

The weight average molecular weight Mw of the obtained target product, measured in polystyrene conversion by GPC, was 7,500, and the polydispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 2.6.

[Polymerization Example 4: Preparation of Highly Branched Polymer 4 Using DCP, NVP, and V-59]

Into a 200 mL reaction flask, 159.0 g of MCS was added, stirred, nitrogen was introduced for 5 minutes, and heated until the inner liquid refluxed (approximately 130°C).

In a separate 100 mL reaction flask, 16.6 g (50 mmol) of DCP as monomer A, 16.67 g (150 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as initiator C, and 111.28 g of MCS were charged, stirred, nitrogen was introduced for 5 minutes, and nitrogen replacement was performed, followed by cooling to 0°C in an ice bath.

Into the refluxing MCS in the 200 mL reaction flask mentioned above, the contents were added dropwise from the 100 mL reaction flask containing DCP, NVP, and V-59 over a period of 30 minutes using a dropping pump. After completion of the dropping, the mixture was stirred for an additional hour.

Next, this reaction solution was added to 1,590 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 23.0 g (yield 48.2%) of the target product (highly branched polymer 4) as a white powder.

The weight average molecular weight Mw of the obtained target product, measured in polystyrene conversion by GPC, was 10,200, and the polydispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 3.4.

[Polymerization Example 5: Preparation of Highly Branched Polymer 5 Using DVB, NVA, and V-59]

In a 200 mL reaction flask, 126.5 g of MCS was added, stirred, nitrogen was introduced for 5 minutes, and heated until the inner liquid refluxed (approximately 130°C).

In a separate 100 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 17.02 g (200 mmol) of NVA as monomer B, 14.42 g (75 mmol) of V-59 as initiator C, and 88.55 g of MCS were charged, stirred, nitrogen was introduced for 5 minutes, and nitrogen replacement was performed, followed by cooling to 0°C in an ice bath.

Into the refluxing MCS in the 200 mL reaction flask mentioned above, the contents were added dropwise from the 100 mL reaction flask containing DVB, NVA, and V-59 over a period of 30 minutes using a dropping pump. After completion of the dropping, the mixture was stirred for an additional hour.

Next, this reaction solution was added to 1,275 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 17.23 g (45.5% yield) of the target product (highly branched polymer 5) as a white powder.

The weight average molecular weight Mw of the obtained target product, measured in polystyrene conversion by GPC, was 9,300, and the polydispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 4.9. The ¹³ C NMR spectrum of the target product is shown in Figure 1.

[Polymerization Example 6: Preparation of Highly Branched Polymer 6 Using DVB, NVP, and V-59]

In a 200 mL reaction flask, 143.87 g of MCS was added, stirred, nitrogen was introduced for 5 minutes, and heated until the inner liquid refluxed (approximately 130°C).

In a separate 100 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 22.23 g (200 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as initiator C, and 100.71 g of MCS were charged, stirred, nitrogen was introduced for 5 minutes, and nitrogen replacement was performed, followed by cooling to 0°C in an ice bath.

Into the refluxing MCS in the 200 mL reaction flask mentioned above, the contents were added dropwise from the 100 mL reaction flask containing DVB, NVP, and V-59 over a period of 30 minutes using a dropping pump. After completion of the dropping, the mixture was stirred for an additional hour.

Next, this reaction solution was added to 1,439 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 24.30 g (yield 56.3%) of the target product (highly branched polymer 6) as a white powder.

The weight average molecular weight Mw of the obtained target product, as measured by GPC in polystyrene conversion, was 11,300, and the polydispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 3.6. The ¹³ C NMR spectrum of the target product is shown in Figure 2.

[Polymerization Example 7: Preparation of Highly Branched Polymer 7 Using DCP, NVP, and V-59]

Into a 200 mL reaction flask, 196.0 g of MCS was added, stirred, nitrogen was introduced for 5 minutes, and heated until the inner liquid refluxed (approximately 130°C).

In a separate 100 mL reaction flask, 16.60 g (50 mmol) of DCP as monomer A, 27.79 g (250 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as initiator C, and 137.22 g of MCS were charged, stirred, nitrogen was introduced for 5 minutes, and nitrogen replacement was performed, followed by cooling to 0°C in an ice bath.

Into the refluxing MCS in the 200 mL reaction flask mentioned above, the contents were added dropwise from the 100 mL reaction flask containing DCP, NVP, and V-59 over a period of 30 minutes using a dropping pump. After completion of the dropping, the mixture was stirred for an additional hour.

Next, this reaction solution was added to 1,960 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 28.6 g (yield 48.7%) of the target product (highly branched polymer 7) as a white powder.

The weight average molecular weight Mw of the obtained target product, measured in polystyrene conversion by GPC, was 12,800, and the polydispersity: Mw (weight average molecular weight) / Mn (number average molecular weight) was 3.0. The ¹³ C NMR spectrum of the target product is shown in Figure 3.

[Manufacturing Example: Synthesis of Pd Microparticle Complex (10g Scale)]

In order to make the Pd particle content (theoretical value) of the Pd fine particle-highly branched polymer composite 30 wt%, the composite was prepared in the following order. Meanwhile, as the high-branched polymer, the high-branched polymer 5 to the high-branched polymer 7 prepared above were used.

In a reaction flask equipped with a condenser, 6.36 g of palladium acetate [Pd(OAc) ₂ , manufactured by Kawaken Fine Chemical Co., Ltd.] and 63.56 g (volume A) of chloroform were charged and stirred until homogeneous. Separately, a solution of 7.0 g of a highly branched polymer dissolved in 70.00 g (volume B) of chloroform was added to the reaction flask containing the palladium acetate using a dropping funnel. The contents of the dropping funnel were then introduced into the reaction flask using 10.00 g (volume C) of chloroform and 95.71 g of ethanol. The mixture was stirred at 60°C for 6 hours under a nitrogen atmosphere.

After cooling to a temperature of 30°C, this solution was added to 1,196.33g of IPE and re-precipitated and purified. The precipitated polymer was filtered under reduced pressure and vacuum-dried at 50°C to obtain a complex of a highly branched polymer having an amide group in the side chain and Pd particles.

The composites having the Pd fine particle content (theoretical value) of 30 wt%, 40 wt%, 50 wt% or 60 wt% were prepared by changing the polymer to a highly branched polymer 6 (HB-DVB-NVP-V59) [complex 1 to complex 4], a highly branched polymer 7 (HB-DCP-NVP-V59) [complex 5 to complex 8], and a highly branched polymer 5 (HB-DBV-NVA-V59) [complex 9 to complex 12] using the component amounts shown in Table 1 below, and the yields of these composites were calculated.

In addition, the actual metal content in the obtained complex was measured by ICP emission analysis, and the 5% weight loss temperature of the complex was measured. In addition, from the TEM (transmission electron microscope) image, approximately 50 particles were selected, their particle diameters were measured, and the average value was calculated, which was used as the Pd particle diameter for each complex.

The obtained results are shown in Table 2.

[Table 1]

[Table 2]

[Examples 1 to 3: Preparation of electroless plating agent and examination of electroless plating]

20 mg of the complex 1 (Pd fine particle-highly branched polymer 6 complex), complex 5 (Pd fine particle-highly branched polymer 7 complex), or complex 9 (Pd fine particle-highly branched polymer 5 complex) obtained above and 80 mg of KBM-903 were mixed, and n-propyl alcohol (PrOH) was added to make the total amount 2 g, and stirred until uniform. After the solution became uniform, 8 g of n-propyl alcohol was additionally added, and the mixture was diluted to a total amount of 10 g, thereby preparing three types of electroless plating agents of Example 1 (containing complex 1), Example 2 (containing complex 5), and Example 3 (containing complex 9).

The electroless plating bases of Examples 1 to 3 were applied by spin coating (200 rpm for 5 seconds, 1,000 rpm for 25 seconds) onto a polyimide film (Kapton) attached to a glass substrate, respectively, and then the polyimide film was separated from the glass substrate, and the solvent was dried on a hot plate (120°C for 5 minutes), thereby forming an electroless metal plating base layer on the polyimide film.

These three films on which the electroless metal plating base layer was formed were each immersed in the electroless copper plating solution prepared in Reference Example 1 at 25°C for 5 minutes while slowly blowing air. Thereafter, the plating surface was washed with water and annealed on a hot plate (120°C, 5 minutes), thereby obtaining a plated substrate on which a metal plating film (copper plating) was formed on the electroless metal plating base layer.

The uniformity of the plating film and the substrate adhesion were evaluated for the metal plating film on each plating substrate obtained using the electroless plating agent of Examples 1 to 3.

Regarding film uniformity, it was visually evaluated according to the following criteria. In addition, regarding substrate adhesion, an 18 mm wide Sellotape (registered trademark) [CT-18S manufactured by Nichiban Co., Ltd.] was attached to the metal plating film portion on the obtained plated substrate, rubbed firmly with a finger to ensure a secure adhesion, and then the attached Sellotape (registered trademark) was peeled off in one go, and the condition of the metal plating film was visually evaluated according to the following criteria. The results are shown in Table 3.

<Evaluation of film uniformity>

○: A metal plating film with a metallic luster is deposited without any spots on the entire surface of the substrate on which the sublayer is formed.

△: The substrate surface is coated, but there are spots on the gloss.

×: The substrate is exposed, so it is not completely covered.

<Evaluation of substrate adhesion>

○: No peeling of the metal plating film is confirmed and it adheres to the substrate.

△: Partial peeling of metal plating film

×: Most (approximately 50% or more) of the metal plating film is peeled off and attached to Sellotape (registered trademark).

[Table 3]

[Examples 4 to 6: Preparation of electroless plating agent and examination of electroless plating]

Except that the same amount of KBM-9103 was used instead of KBM-903 and the same amount of methyl isobutyl ketone (MIBK) was used instead of n-propyl alcohol (PrOH) as a solvent, three kinds of electroless plating base agents of Example 4 (containing complex 1), Example 5 (containing complex 5), and Example 6 (containing complex 9) were prepared in the same manner as in Examples 1 to 3, and using these, an electroless metal plating base layer was formed on a polyimide film in the same manner as described above, and then, using the electroless copper plating solution prepared in Reference Example 1 in the same manner as described above, a plated substrate having a metal plating film (copper plating) formed on the electroless metal plating base layer was obtained, and the plating film uniformity and substrate adhesion were evaluated in the same manner as described above. The obtained results are shown together in Table 4.

[Table 4]

[Example 7: Preparation of an electroless plating agent and examination of electroless nickel plating]

As in Example 6, the electroless plating base agent of Example 7 [composite 9 (Pd fine particle-highly branched polymer 5 complex), amine compound: KB-9103, containing MIBK] was prepared, and an electroless metal plating base layer was formed on a polyimide film in the same manner as above. This film was immersed in the electroless nickel plating solution described in Reference Example 2, which was prepared in Reference Example 2 and heated to 85°C, for 3 minutes. Thereafter, the plating surface was washed with water and annealed on a hot plate (120°C, 5 minutes), thereby obtaining a plated substrate having a metal plating film (nickel plating) formed on the electroless metal plating base layer.

[Example 8: Preparation of an electroless plating agent and examination of electroless nickel plating]

In the above Example 6, an electroless plating agent was prepared without using the amine compound: KBM-9103. That is, 20 mg of the complex 9 (Pd fine particle-highly branched polymer 5 complex) obtained above was dissolved in methyl isobutyl ketone (MIBK) so that the total amount was 10 g, and the electroless plating agent of Example 8 was prepared.

Using this electroless plating agent, a polyimide film (Kapton) attached to a glass substrate was applied by spin coating (200 rpm for 5 seconds, 1,000 rpm for 25 seconds) as described above, and then the polyimide film was removed from the glass substrate, and the solvent was dried using a hot plate (120°C for 5 minutes), thereby forming an electroless metal plating base layer on the polyimide film.

The film on which the electroless metal plating base layer was formed was immersed in the electroless nickel plating solution described in Reference Example 2 at 85°C for 3 minutes. Thereafter, the plating surface was washed with water, and annealing was performed on a hot plate (120°C, 5 minutes), thereby obtaining a plated substrate on which a metal plating film (nickel plating) was formed on the electroless metal plating base layer.

For the plated substrates obtained in Examples 7 and 8, the plating film uniformity and substrate adhesion were evaluated in the same manner as above. The obtained results are also shown in Table 5.

[Table 5]

Claims (18)

As an electroless plating agent for forming a metal plating film by electroless plating on a substrate,
(a) A highly branched polymer comprising a polymerizable compound including monomer A, which is a divinyl compound or a di(meth)acrylate compound, monomer B having an amide group and at least one radically polymerizable double bond in the molecule, and a polymerization initiator C in an amount of 5 to 200 mol% based on the mole number of monomer A,
A highly branched polymer, comprising a highly branched polymer chain comprising at least a structural portion represented by the following formula [1] and formula [2] or formula [3], and further comprising a radical cleavage fragment of the polymerization initiator C mounted at the end of the polymer chain, and
(b) metal particles
The lower body including the lower body.

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R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent an alkyl 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,
A ₁ represents a single bond or divalent organic group derived from monomer A, which is a divinyl compound or a di(meth)acrylate compound,
R ₇ , R ₈ and R ₉ each independently represent an alkyl 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,
R ₁₀ and R ₁₁ each independently represent an alkyl group or phenyl 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, or R ₁₀ and R ₁₁ may form an alkylene group having 2 to 6 carbon atoms which 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 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 ₁₅ and R ₁₆ each independently represent an alkyl 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. In the first paragraph,
A composite comprising a metal particle (b) attached or coordinated to an amide group in the (a) high-branched polymer. delete delete In the first paragraph,
The above monomer A is a compound having an aromatic ring having 3 to 30 carbon atoms or an alicyclic ring having 3 to 30 carbon atoms. In paragraph 5,
The above monomer A is divinylbenzene or tricyclo[5.2.1.0 ^2,6 ]decane dimethanol di(meth)acrylate. In the first paragraph,
The above polymerization initiator C is an azo polymerization initiator. In the first paragraph,
The above polymerizable compound comprises 5 to 300 moles of the monomer B relative to the mole number of the monomer A. In the first paragraph,
The above A ₁ is a divalent organic group having an aromatic ring having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms. In the first paragraph,
The above (a) high-branched polymer is a high-branched polymer composed of a polymer that forms a polymer chain including at least the structural parts represented by the above formula [1] and formula [2],
In equation [1],
R ₁ , R ₂ , R ₅ and R ₆ represent hydrogen atoms,
R ₃ and R ₄ represent hydrogen atoms or methyl groups,
A ₁ represents a phenylene group or a tricyclo[5.2.1.0 ^2,6 ]decane-4,8-diyl-di(methyleneoxycarbonyl) group,
In equation [2],
R ₇ , R ₈ and R ₉ represent hydrogen atoms,
R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a methyl group, or R ₁₀ and R ₁₁ become one to represent an n-propylene group,
A polymer chain comprising a radical cleavage fragment of a polymerization initiator C selected from 2,2'-azobis(2-methylbutyronitrile) and dimethyl2,2'azobis(2-methylpropionate) at the end thereof.
No, not yet. In the first paragraph,
The above (b) metal fine particles are fine particles of at least one metal selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold (Au). In Article 11,
The above (b) metal particles are palladium particles. In the first paragraph,
The above (b) metal fine particles are fine particles having an average particle diameter of 1 to 100 nm. In the first paragraph,
Additionally, a haze agent containing (c) an amine compound. An electroless metal plating base layer, which is a layer made of an electroless plating agent as described in any one of claims 1, 2, and 5 to 14. A metal plating film formed on the base layer of the electroless metal plating described in Article 15. A metal film substrate comprising a substrate, an electroless metal plating base layer formed on the substrate as described in claim 15, and a metal plating film formed on the electroless metal plating base layer. A method for manufacturing a metal film substrate, comprising the following processes A and B.
Process A: A process of applying the electroless plating agent described in any one of claims 1, 2, and 5 to 14 onto a substrate, and providing an electroless metal plating base layer on the substrate.
Process B: A process of immersing a substrate having this base layer in an electroless plating bath and forming a metal plating film on this base layer.