KR20180113542A - An electroless plating plating solution containing a high branching polymer and metal fine particles - Google Patents

Abstract

[PROBLEMS] To provide a new base material used as a pretreatment step for electroless plating, which has a high heat resistance and can form a plating base layer which does not contain corrosive atoms and can realize a low cost in the production thereof .
[MEANS FOR SOLVING PROBLEMS] An electroless plating pretreatment agent for forming a metal plating film by electroless plating on a substrate, comprising (a) a monomer A having a synthetic double bond in two or more radicals in the molecule, Branched polymer composed of a polymerizable compound containing at least a monomer B having at least one radially polymerizable double bond and a polymerization initiator C in an amount of 5 to 200 mol% based on the number of moles of the monomer A, , A highly branched polymer having a highly branched polymer chain and a radical cleavage fragment of the polymerization initiator C mounted on the end of the polymer chain, and (b) fine metal particles.

Description

An electroless plating plating solution containing a high branching polymer and metal fine particles

The present invention relates to an electroless plating agent containing a high branching polymer (a high branching polymer) and metal fine particles.

In the electroless plating, a film having a uniform thickness can be obtained regardless of the type and the shape of the substrate by simply immersing the substrate in the plating solution, and a metal plating film can be formed also on an insulator material such as plastic, ceramics, glass, For example, it is widely used in decorative applications such as giving a sense of quality and aesthetics to resin molded articles such as automobile parts and wiring technology such as electronic shielding, printed boards and large-scale integrated circuits.

Normally, when a metal plating film is formed on a base material (plated body) by electroless plating, a pretreatment for enhancing the adhesion between the base material and the metal plating film is performed. Specifically, the surface to be treated is first roughened and / or hydrophilized by various etching means, and then an adsorption material for promoting the adsorption of the plating catalyst on the surface to be treated is supplied to the surface of the object to be treated And an activation process for adsorbing the plating catalyst on the surface to be treated. Typically, the sensitization treatment immerses the object to be treated in an acidic solution of tin chloride, whereby a metal (Sn ²⁺ ), which can act as a reducing agent, is adhered to the surface to be treated. Then, the object to be treated is immersed in the acidic solution of palladium chloride as the activation treatment with respect to the treated surface subjected to sensitization. Accordingly, the palladium ions in the solution are reduced by the metal (tin ion: Sn ²⁺ ) which is a reducing agent, and attached to the surface of the workpiece as the active palladium catalyst nuclei. After such pretreatment, the substrate is immersed in an electroless plating solution to form a metal plating film on the surface to be treated.

On the other hand, a highly branched polymer classified as a dendritic (dendritic) polymer is actively introducing a branch, and has a remarkable feature of having a large skeleton of pseudo spherical shape, . Further, there may be a case in which the terminal nodule is large. When a reactive functional group is added to the terminal group, the polymer has a highly reactive functional group. Therefore, for example, a high sensitivity capturing agent for a functional material such as a catalyst, a highly sensitive polyfunctional crosslinking agent, a dispersing agent for a metal or a metal oxide, And so on.

For example, there has been reported an example in which a composition containing a high branching polymer having an ammonium group and fine metal particles is used as a base agent (plating catalyst) for electroless plating. In the pretreatment step (roughening treatment) of a conventional electroless plating treatment There has been proposed a method for electroless plating which is intended to improve various aspects such as environment, cost and troublesome operability by avoiding the use of a chromium compound (chromic acid) which has become a problem and reducing the number of steps of pretreatment (Patent Document 1).

International Patent Application Publication No. 2012/141215 pamphlet

In the composition comprising the high branched polymer having the ammonium group and the metal fine particles proposed as the above-mentioned antireflection agent for electroless plating, when it is applied to the wiring technology in semiconductor manufacturing and the like, the heat resistance temperature of the high branched polymer contained therein is low Therefore, there is a fear that the branch polymer is decomposed by solder reflow or high-temperature treatment. Further, in this high branching polymer, a halogen is present as a counter anion of a quaternary ammonium group contained therein, and a sulfur atom may remain in the polymer in a normal state with the production of the high branching polymer. I am concerned. In addition, since the synthesis of this high branching polymer is carried out in multiple steps, the production cost is high, and the quaternary ammonium salt conventionally acts as a catalyst in a curing component using epoxy, isocyanate, etc., By using a high branching polymer containing an ammonium salt structure, problems arise in the storage stability at the time of making the varnish made of electroless plating plating.

As described above, in the electroless plating plating solution proposed so far, it is possible to impart plating with high heat resistance without containing corrosive atoms such as halogen atoms and sulfur atoms in addition to the plating performance as a plating base agent, The present invention is not limited to the electroless plating plating solution which has been sufficiently realized and includes the operability such as various performance such as having high dispersion stability,

An object of the present invention is to provide a method of manufacturing a plating base layer which has high heat resistance and which does not contain corrosive atoms and which can be used in a pretreatment step of electroless plating The purpose of this article is to provide a new restriction system.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to attain the above object and as a result, they have studied a high branching polymer containing an amide group and preferably a cyclic skeleton and not containing only a corrosive atom, combining this high branching polymer with metal fine particles , And found that a layer obtained by applying this on a substrate has not only plating ability but also high heat resistance as a base layer of electroless metal plating, and furthermore, there is no fear of corrosion, thereby completing the present invention.

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

(a) a polymerizable compound comprising at least monomer A having two or more radical double bonds in the molecule and monomer B having an amide group and at least one radical double intermolecular double bond, and a polymerizable compound having a number of moles of the monomer A As a high branched polymer composed of a polymer of a polymerization initiator C in an amount of 5 to 200 mol%

Wherein the polymer has a highly branched polymer chain comprising at least a structural moiety represented by the following formula [1] and formula [2] or formula [3], and at the end of the polymerization chain, A branched polymer prepared by incorporating a radical cleavage fragment, and

(b) metal fine particles

And the like.

[Chemical Formula 1]

(Wherein,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently 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 An alkyl group having 1 to 10 carbon atoms,

A ₁ represents a single bond or a divalent organic group,

R ₇ , R ₈ and R ₉ each independently represent an alkyl group having 1 to 10 carbon atoms which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond, ,

R ₁₀ and R ₁₁ each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond, , R ₁₀ and R ₁₁ may be taken together to 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 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.

As a second aspect, the present invention relates to the antifogging agent according to the first aspect, wherein the amide group in the (a) high branching polymer includes the composite for adhering or distributing the (b) metal fine particles.

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

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

In a fifth aspect, the monomer A is a compound having an aromatic ring having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.

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

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

In an eighth aspect, the polymerizable compound relates to the restraining agent according to any one of the first to seventh aspects, wherein the polymerizable compound comprises the monomer B in an amount of 5 to 300 moles relative to the number of moles of the monomer A.

In a ninth aspect, A ₁ represents an aromatic ring having 3 to 30 carbon atoms or a divalent organic group having an alicyclic group having 3 to 30 carbon atoms.

As a tenth aspect, there is provided a highly branched polymer wherein the (a) high branched polymer is composed of a polymer constituting at least a polymer chain including structural moieties represented by the formulas [1] and [2]

In the formula [1]

R ₁ , R ₂ , R ₅ and R ₆ represent a hydrogen atom,

R ₃ and R ₄ represent a hydrogen atom or a methyl group,

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

In formula [2]

R ₇ , R ₈ and R ₉ represent a hydrogen atom,

R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a methyl group, or R ₁₀ and R ₁₁ are combined to form an n-propylene group,

A radical cleavage fragment of a polymerization initiator C selected from 2,2'-azobis (2-methylbutyronitrile) and dimethyl 2,2 'azobis (2-methylpropionate) is loaded at the end of the polymerization chain Made,

And relates to a restraint system described in the first aspect.

As an eleventh aspect, there is provided a method for producing a metal fine particle, wherein the metal fine particle (b) is at least one selected from the group consisting of Fe, Co, Ni, Cu, Pd, Ag, Wherein the fine particles are at least one kind of metal selected from the group consisting of platinum (Pt) and gold (Au).

In a twelfth aspect, the metal particle (b) is a paradium microparticle.

In a thirteenth aspect, the present invention relates to the antifogging agent according to any one of the first to twelfth aspects, wherein the (b) fine metal particles are fine particles having an average particle diameter of 1 to 100 nm.

As a fourteenth aspect, the present invention relates to a restraining agent according to any one of the first to thirteenth aspects, further comprising (c) an amine compound.

As a fifteenth aspect, the present invention relates to an undercoat layer of electroless metal plating, which is a layer made of an electroless plating plating solution as described in any one of the first to fourteenth aspects.

As a sixteenth aspect, the present invention relates to a metal plating film formed on a base layer of electroless metal plating according to the fifteenth aspect.

In a seventeenth aspect, the present invention relates to a metal film base comprising a base material, a base layer of the electroless metal plating described in the fifteenth aspect formed on the base material, and a metal plating film formed on the base layer of the electroless metal plating .

As an eighteenth aspect, the present invention relates to a method for producing a metal film base material, which comprises the steps A and B described below.

Step A: A step of applying the electroless plating plating treatment agent described in any one of the first aspect to the 14th aspect on a substrate and providing a base layer of electroless metal plating on the substrate,

Step B: A step of immersing the base material having the base layer in an electroless plating bath to form a metal plating film on the base layer.

The base coat of the present invention can be easily formed into a base layer of electroless plating only by coating on a base material. Further, according to the present invention, it is possible to form a base layer for plating which has excellent plating performance and high heat resistance and is free from corrosion of the substrate. In addition, the anticorrosion agent of the present invention can be easily varnished in various compositions and can have high dispersion stability.

Further, since the high branching polymer used in the undercoating 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 substrate and to reduce the manufacturing cost.

Further, the base layer of the electroless metal plating formed from the electroless plating base material of the present invention can easily form a metal plating film only by immersing in an electroless plating bath, and is provided with a substrate, a foundation layer, and a metal plating film Can easily be obtained.

That is, by forming the ground layer on the substrate using the electroless plating plating solution of the present invention, a metal plating film having excellent adhesion with the substrate and having heat resistance can be formed.

Brief Description of the Drawings Fig. 1 is a diagram showing ¹³ C NMR spectra of the highly branched polymer 5 (DVB, NVA, V-59) obtained in Polymerization Example 5.
2 is a diagram showing a ¹³ C NMR spectrum of the highly branched polymer 6 (DVB, NVP, V-59) obtained in Polymerization Example 6. Fig.
3 is a diagram showing the ¹³ C NMR spectrum of the high branching polymer 7 (DCP, NVP, V-59) obtained in Polymerization Example 7.

Hereinafter, the present invention will be described in detail.

The anticorrosion agent of the present invention is a restraint agent containing (a) a high branching polymer having the specific structural moiety mentioned above, (b) metal fine particles, and optionally (c) an amine compound.

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

< (a) High branching polymer &

The high branching polymer (hereinafter, also referred to as an amide group-containing high branching polymer) used in the undercoating of the present invention is a polymer obtained by polymerizing a monomer A having a synthetic double bond in two or more radicals in a molecule and a monomer A having an amide group and at least one radical Is a highly branched polymer composed of a polymerizable compound containing at least monomer B having a synthetic double bond and a polymerization initiator C in an amount of 5 to 200 mol% based on the number of moles of the monomer A. The high branching polymer is a so-called initiator fragment mounted (IFIRP) type high branching polymer, and has a fragment (radical cleavage fragment) of the polymerization initiator C used at the end of the polymerization reaction.

The term "highly branched polymer" in the present invention includes not only high molecular weight polymers of the monomers A and B but also oligomers of a low molecular weight polymer. That is, the highly branched polymer of the present invention may be identified as a &quot; branched polymer &quot;.

The highly branched polymer of the present invention comprises a structural part formed by a polymerization reaction of a structural part represented by the following formula [1], that is, a synthetic double bond among at least two radicals contained in the monomer A, Or a structural part represented by the formula [3], that is, a structural part formed by the polymerization reaction of a synthetic double bond in the radical of the monomer B, and a polymer chain having a highly branched polymer chain And a radical cleavage fragment of Polymerization Initiator C is mounted on the end.

(2)

(Wherein,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently 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 An alkyl group having 1 to 10 carbon atoms,

A ₁ represents a single bond or a divalent organic group,

R ₇ , R ₈ and R ₉ each independently represent an alkyl group having 1 to 10 carbon atoms which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond, ,

R ₁₀ and R ₁₁ each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond, , R ₁₀ and R ₁₁ may be taken together to 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 which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond.

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

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

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, The alkyl group and the like may be interrupted by a bond of the alkyl group, or may be bonded to the bonding end of the alkyl group or the like (for example, an oxyalkylene group).

Examples of the divalent organic group include an aliphatic group having 1 to 20 carbon atoms, an aromatic 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 more. These aliphatic groups, aromatic groups, alicyclic groups and heterocyclic groups may have substituents. The aliphatic group, the aromatic ring, the alicyclic group and the heterocyclic group may contain at least one bond selected from the group consisting of an ether bond, an amide bond and an ester bond.

The aliphatic group may be linear or branched, may have one or more unsaturated bonds, and may include, for example, an alkylene group having 1 to 20 carbon atoms.

Examples of the aromatic ring in the aromatic ring include benzene, naphthalene, fluorene, phenanthrene, and anthracene.

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

Examples of the heterocycle in the heterocyclic group include pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, pyrrole, pyrazole, imidazole, pyrrolidine, pyrazolidine, imidazolidine, Pyrimidines, pyrimidines, pyridines, pyridines, pyrimidines, pyran, thiophene, thiopyran, isoxazole, isoxazolidine, morpholine, isothiazole, isothiazolidine, thiomorpholine, benzoimidazole, benzofuran, Sol, triazine, quinone, and the like.

Among these, A ₁ is preferably 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 highly branched polymer can be prepared in one step by polymerizing a polymerizable compound containing at least monomer A and monomer B to be described later in the presence of a predetermined amount of polymerization initiator C.

[Monomer A]

In the present invention, the monomer A having a synthetic double bond in two or more radicals in the molecule is preferably a vinyl group or a (meth) acryloyl group having either or both of a vinyl group and a di (meth) Acrylate compound. Among them, the monomer A is preferably a compound having an aromatic ring having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms, from the viewpoint of improvement in heat resistance.

In the present invention, the (meth) acrylate compound means both of an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

As the monomer A usable in the present invention, for example, the following organic compounds shown in (A1) to (A7) are exemplified.

(A1) Vinyl-based hydrocarbons:

(A1-1) aliphatic vinyl-based hydrocarbons; Butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene, etc.

(A1-2) alicyclic vinyl-based hydrocarbons; Cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc.

(A1-3) aromatic vinyl-based hydrocarbons; Examples of the organic solvent include divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine

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

(A2-1) vinyl esters; (Meth) acrylate, divinyl benzene, divinyl benzene, divinyl butyrate, divinyl butyrate, divinyl butyrate, divinyl butyrate,

(A2-2) allyl esters; Diaryl 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, tetramethallyloxyethane, etc.

(A2-5) vinyl ketones; Divinyl ketone, diallyl ketone, etc.

(A3) (meth) acrylates:

Acrylates such as 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, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy- 3-methacryloyloxypropane, (Meth) acryloyloxyethoxy) phenyl] fluorene, undecylenoxyethylene glycol (2-hydroxyethyl) (Meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, (Meth) acrylate, aromatic urethane di (meth) acrylate, aliphatic urethane di (meth) acrylate, etc.

(A4) Vinyl compound having polyalkylene glycol chain:

Di (meth) acrylate, polyethylene glycol (molecular weight 300, etc.) di (meth) acrylate, polypropylene glycol

(A5) Nitrogen-based vinyl compound:

(Meth) acrylate, diallyl isocyanurate, diallyl cyanurate, ethoxy isocyanuric acid di (meth) acrylate, ethoxy isocyanuric acid tri (meth) acrylate, methylene bis (meth) Maleimide etc.

(A6) Silicon Vinyl compound:

(Methyl) (phenyl) silane, diphenyl divinyl silane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1 , 1,3,3-tetraphenyldisilazane, diethoxyvinylsilane, etc.

(A7) Fluorine Vinyl compound:

Divinyl perfluorobutane, 1,4-divinyl perfluorobutane, 1,6-divinyl perfluorohexane, 1,6-divinyldodecafluorohexane, 1,8-di Vinyl perfluorooctane, 1,8-divinyl hexadecafluorooctane, etc.

Of these, preferred are the aromatic vinyl-based hydrocarbon compounds of the above-mentioned (A1-3) group, vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the (A2) group, (meth) A vinyl-based compound having a polyalkylene glycol chain of the group (A4), and a nitrogen-containing vinyl compound of the group (A5).

Particularly preferred are divinylbenzene belonging to the group (A1-3), diallyl phthalate belonging to the group (A2), ethylene glycol di (meth) acrylate belonging to the group (A3), 1,3-adamantanedimethanol di (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate and methylene bis (meth) acrylamide belonging to the group (A5). Among them, divinylbenzene, ethylene glycol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate are preferable, and in particular, divinylbenzene or tricyclodecane dimethanol di (meth) acrylate is preferable. desirable.

These monomers A may be used singly or in combination of two or more.

[Monomer B]

In the present invention, the monomer B is not particularly limited as long as it is a compound having an amide group in the molecule and a synthetic double bond in at least one radical, but preferably a vinyl group or a (meth) acryloyl group It is preferable to be a compound having at least one of them. On the other hand, when the monomer B is a compound having a (meth) acryloyl group as a synthetic double bond in the radical, the carbonyl group [-C (= O) -] included in the (meth) acryloyl group is a carbonyl group And may have a structure that overlaps.

Examples of such a monomer B include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl (meth) acrylamide, N- (Meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (Meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl , N-isobutoxyethyl (meth) acrylamide, and the like.

These monomers B may be used singly or in combination of two or more.

In the present invention, the copolymerization ratio of the monomer A and the monomer B is preferably from 0.05 mol to 20 mol, particularly preferably from 0.1 mol to 1 mol, based on 1 mol of the monomer A from the viewpoints of reactivity and plating ability Mol to 10 mol.

[Other monomers]

The polymerizable compound may contain, as the other monomers together with the monomer A and the monomer B, a monomer D having a synthetic double bond in at least one radical in the molecule and not having an amide group only.

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

Among them, vinyl ether group-containing (meth) acrylate compounds such as 2- (2-vinyloxyethoxy) ethyl acrylate and the like; 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 preferred.

In the present invention, when the polymerizable compound contains the monomer D, the compounding ratio is preferably 0.05 to 3.0 moles of the monomer D relative to 1 mole of the monomer A from the viewpoints of reactivity and surface modifying effect, Particularly preferably from 0.1 mol to 1.5 mol.

[Polymerization initiator C]

As the polymerization initiator C in the present invention, an azo-based polymerization initiator is preferably used. Examples of the azo-based polymerization initiator include the following compounds (1) to (6).

(1) Azonitrile compound:

Azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobisisobutyronitrile, Azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoyl azo) isobutyronitrile;

(2) The azoamide compound:

Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'- Azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [N- (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide Amide) and the like;

(3) Cyclic azoamidine compound:

Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'- Azo bis [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 and the like;

(4) azoamidine compound:

Azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, and the like; 2,2'-azobis (2-methylpropionamidine) dihydrochloride;

(5) Others:

Dimethyl 2,2'-azobisisobutylate [dimethyl 2,2-azobis (2-methylpropionate), 2,2'-azobis (2,4,4-trimethylpentan), 1,1 ' Azobis (1-acetoxy-1-phenylethane), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate), 4,4'- azobis (4-cyanopentanoic acid) 4'-azobis-4-cyanovaleric acid and the like.

(6) Fluoroalkyl group-containing azo type polymerization initiator:

Azobis (4-cyanopentanoic acid-2- (perfluorobutyl) ethyl), 4,4'-azobis (4-cyanopentanoic acid- 4,4'-azobis (4-cyanopentanoic acid-2- (perfluorohexyl) ethyl) and the like.

Among the azo-based polymerization initiators, 2,2'-azobis (2-methylbutyronitrile) and dimethyl 2,2'-azobisisobutylate are preferable from the viewpoints of elution into a plating bath and plating ability.

On the other hand, when 2,2'-azobis (2-methylbutyronitrile) is used as the polymerization initiator C, the radical scavenging fragment derived from the polymerization initiator C located at the end of the polymer chain in the polymer is 1- - is a propyl group _{[-C (CH 3) (CN} ) -CH 2 CH 3] - cyano.

The 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 still more preferably 50 to 100 mol%, based on the number of moles of the monomer A Mol%.

&Lt; Production method of high branching polymer &

As described above, the highly branched polymer used in the present invention is obtained by polymerizing a polymerizable compound containing the monomer A and the monomer B and, if necessary, other monomer, in the presence of a predetermined amount of the polymerization initiator C with respect to the monomer A .

Examples of the polymerization method in the presence of the above-mentioned monomer A, monomer B and other monomer-containing polymerizable compound in the presence of the polymerization initiator C include known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, Among them, solution polymerization or precipitation polymerization is preferable. Particularly, from the viewpoint of molecular weight control, it is preferable to conduct the reaction by solution polymerization in an organic solvent.

Examples of the organic solvent include 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 products such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene 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; 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 of these.

Particularly preferred among these are aromatic hydrocarbons, halogenated products, esters, ethers, ketones, alcohols and amides. Particularly preferred are benzene, toluene, xylene, orthodichlorobenzene, ethyl acetate, butyl acetate, propylene glycol Methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isopropanol, n- Isobutanol, tert-butanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

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

The blending amount of the organic solvent can be appropriately selected according to the molecular weight of the target high-molecular-weight polymer. For example, in the case of designing a higher branching polymer having a higher molecular weight, the amount of the organic solvent (the concentration of the polymerizable compound in the solvent becomes a higher concentration) becomes low. On the contrary, when a high molecular weight polymer having a low molecular weight is designed, (The concentration of the polymerizable compound in the solvent becomes low).

The polymerization reaction is carried out under atmospheric pressure, in a pressure-tightly closed state or under a reduced pressure, and is preferably carried out under atmospheric pressure from the simplicity of the apparatus and operation. It is also preferable to perform the reaction in an inert gas atmosphere such as N ₂ .

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

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

The reaction time varies depending on the reaction temperature, the type and ratio of the polymerizable compound (monomer A, monomer B, and other monomers as required) and polymerization initiator C, the type of organic solvent used for polymerization, and so on. But is preferably 30 to 720 minutes, and more preferably 40 to 540 minutes.

After completion of the polymerization reaction, the obtained highly branched polymer is recovered by an arbitrary method, and post-treatment such as washing is carried out if necessary. As a method of recovering the polymer from the reaction solution, a method such as re-precipitation can be mentioned.

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

An example of the highly branched polymer used in the present invention is a highly branched polymer composed of a polymer constituting at least a polymer chain containing structural moieties represented by the above formulas [1] and [2]

In the formula [1]

R ₁ , R ₂ , R ₅ and R ₆ represent a hydrogen atom,

R ₃ and R ₄ represent a hydrogen atom or a methyl group,

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

In formula [2]

R ₇ , R ₈ and R ₉ represent a hydrogen atom,

R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a methyl group, or R ₁₀ and R ₁₁ are combined to form an n-propylene group,

A radical cleavage fragment of a polymerization initiator C selected from 2,2'-azobis (2-methylbutyronitrile) and dimethyl 2,2 'azobis (2-methylpropionate) is loaded at the end of the polymerization chain Branched polymer obtained by polymerizing a polymerizable monomer.

< (b) Metal fine particles >

The metal fine particles (b) used in the undercoating of the present invention are not particularly limited and examples of the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium Silver (Ag), tin (Sn), platinum (Pt), gold (Au), and alloys thereof, and may be one kind of these metals or two or more kinds of alloys. Among them, preferable metal fine particles include palladium fine particles. On the other hand, as the metal fine particles, an oxide of the above metal may be used.

The metal fine particles can be obtained by, for example, a method of irradiating a solution of a metal salt with a high-pressure mercury lamp, or a method of adding a compound having a reducing action (so-called reducing agent) to the solution to reduce metal ions. For example, metal ions are reduced by adding a solution of a metal salt to a solution of the high branching polymer and irradiating the solution with ultraviolet rays, or adding a solution of a metal salt and a reducing agent to the solution, And a metal fine particle are formed on the surface of the substrate, a restraining agent containing a high branching polymer and fine metal particles can be prepared.

(Dba) ₂ [dba = dibenzylideneacetone], Pt (cod) ₂ [cod = (dba)], 1, _{5-cyclooctadiene], Pt (CH 3) 2} (cod), chloride, palladium acetate, palladium (Pd (OC (= O) CH 3) 2), nitrate, palladium, Pd ₂ (dba) _{3 · CHCl 3, Pd (dba)} 2, chloride, rhodium acetate, rhodium chloride, ruthenium acetate, ruthenium, Ru (cod) (cot) [cot = cyclooctadiene triene], iridium chloride, acetic acid, iridium, Ni (cod) _2, etc. .

The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select a reducing agent depending on the metal species to be contained in the obtained base agent. Examples of the reducing agent that can be used include borohydride metal salts such as sodium borohydride and potassium borohydride; Aluminum hydrides 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 polyol; Tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA] and ethylenediamine acetic acid [EDTA]; Hydroxylamine; Triphenylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane, triphenylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, (Diphenylphosphino) propane [DPPP], 1,1'-bis (diphenylphosphino) ferrocene [DPPF], and 2,2'-bis And phosphine such as 1,1'-binaphthyl [BINAP].

The average particle diameter of the metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the metal fine particles to 100 nm or less, the surface area is less decreased and sufficient catalytic activity is obtained. The average particle diameter is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.

The addition amount of the above-mentioned (a) high branched polymer in the undercoat of the present invention is preferably 20 parts by mass or more and 10,000 parts by mass or less based on 100 parts by mass of the metal fine particles (b). (a) the addition amount of the (a) high branch polymer relative to 100 parts by mass of the metal fine particles (b) is 20 parts by mass or more, the metal fine particles can be sufficiently dispersed, and if it is 20 parts by mass or less, Is insufficient, so that precipitates and agglomerates are liable to be generated. More preferably, it is at least 30 parts by mass. Further, when (a) 10,000 parts by mass or more of the (a) high branching polymer is added to 100 parts by mass of the metal fine particles (b), the amount of Pd per unit area after coating becomes insufficient.

< (c) Amine compound >

As the amine compound (c) used in the electroless plating treatment agent of the present invention, known ones can be used, and examples thereof include aliphatic amines such as alkyl amines and hydroxyalkyl amines, amines having cyclic substituents, Aromatic amine (arylamine), and amine compound having an alkoxysilyl group. Among these amine compounds, amine compounds having an alkoxysilyl group are preferable. The amino group of the amine compound is preferably protected by a ketone (protected by an alkylidene group) from the viewpoint of improving the storage stability of the plating solution, and in the present invention, the amino group is protected by an alkylidene group Amine compounds are also included in component (c). On the other hand, when the amine compound protected by the alkylidene group as the component (c) is used, the base solvent to be described later is not an alcohol solvent which releases the protection by the alkylidene group, but includes ketones, It is preferable to use a solvent of the same type.

In the present invention, by mixing the amine compound (c) with an electroless plating base agent, the effect of improving the dispersion stability in the base metal fine particles, specifically the base metal of the composite of the metal fine particles and the high branch polymer described later is obtained Contributes to formation of a fine plating pattern. On the other hand, an amine compound protected by an alkylidene group can be used as an amine compound protected by an alkylidene group as a component (c) since the protection of the alkylidene group is released by an electroless plating solution.

In the alkyl amines, amine (CH ₃ CH ₂ NH _2), propylamine _{(CH 3 (CH 2) 2} NH 2), tributylamine _{(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) , nonyl amine _{(CH 3 (CH 2) 8} NH 2), decylamine _{(CH 3 (CH 2) 9} NH 2), undecyl amine _{(CH 3 (CH 2) 10} NH 2), dodecylamine (CH _{3 (CH 2) 11 NH 2)} , tridecyl amine _{(CH 3 (CH 2) 12} NH 2), tetradecyl amine _{(CH 3 (CH 2) 13} NH 2), pentadecyl amine (CH ₃ (CH _{2) 14} NH _2), hexadecyl amine _{(CH 3 (CH 2) 15} NH 2), heptadecyl amine _{(CH 3 (CH 2) 16} NH 2), octadecylamine _{(CH 3 (CH 2) 17} NH 2), na decylamine _{(CH 3 (CH 2) 18} NH 2), a primary amine such as Ikoma chamber amine _{(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; And tertiary amines such as trimethylamine, triethylamine, tripropylamine and tributylamine.

Examples of the hydroxyalkylamines (alkanolamines) include methanol amine (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} ), pentanol amine _{(OH (CH 2) 5 NH} 2), hexanol amine _{(OH (CH 2) 6 NH} 2), heptanol amine _{(OH (CH 2) 7 NH} 2 ) octanol amine _{(OH (CH 2) 8 NH} 2), nonanol amine _{(OH (CH 2) 9 NH} 2), decanol amine _{(OH (CH 2) 10 NH} 2), undecanoic kanol amine (OH ( CH _{2) 11} NH _2), dodecanol amine _{(OH (CH 2) 12 NH} 2), tridecanoic olamine _{(OH (CH 2) 13 NH} 2), tetradecane olamine _{(OH (CH 2) 14 NH} 2 ), pentadecane olamine _{(OH (CH 2) 15 NH} 2), hexadecane olamine _{(OH (CH 2) 16 NH} 2), heptanoic decanol amine _{(OH (CH 2) 17 NH} 2), octadecanol Primary amines such as amine (OH (CH ₂ ) ₁₈ NH ₂ ), nonadecanolamine (OH (CH ₂ ) ₁₉ NH ₂ ) and eicosadecanolamine (OH (CH ₂ ) ₂₀ NH ₂ ); N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, Such as N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, Amines and the like.

Examples of other aliphatic amines include aliphatic amines such as methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethyl And alkoxyalkylamines such as amine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, and butoxybutylamine.

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

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

(3)

Specific examples of the aromatic amines (aryl amines) include aniline, N-methylaniline, o-, m-, or p-anisidine, o-, m-, or p-toluidine, o-, m-, Chloroaniline, o-, m-, or p-bromoaniline, o-, m-, or p-iodoaniline.

Specific examples of the amine compound 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) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis- [3- (trimethoxysilyl) (3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, trimethoxy [3- (methylamino)] propylsilane, 3- 3- (diethylamino) propyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3 (diethylamino) propyltrimethoxysilane, 3- - (phenylamino) propyltriethoxysilane, and the like. The.

In the amine compounds having an alkylamine, hydroxyalkylamine, other aliphatic amines, cyclic substituents, aromatic amines (arylamines), or alkoxysilyl groups, which are specifically exemplified above, And an amino compound protected with an alkylidene group by a ketone such as ketone or methyl isobutyl ketone.

The content of the amine compound (c) in the undercoat of the present invention is preferably 0.01 part by mass or less per 100 parts by mass of the complex (or the total mass of the high branch polymer and the metal fine particles) formed from the above- To 500 parts by mass, more preferably 0.1 part by mass to 300 parts by mass, and particularly 1 part by mass to 100 parts by mass.

When the content of the amine compound (c) is less than the above-mentioned range, the effect of stabilizing the dispersibility and solubility of the composite formed from the above-mentioned highly branched polymer and the metal fine particles can not be obtained. (For example, a 10-fold amount of the composite, etc.), the plating bath may be contaminated or destroyed, and the plating film may be defective in appearance.

<Forbid>

The electroless plating pretreatment agent of the present invention comprises the above (a) high branched polymer and (b) fine metal particles, and further contains (c) an amine compound and further other components as necessary. In the electroless plating subsystem of the present invention, it is preferable that the above-mentioned highly branched polymer and the above-mentioned metal fine particles form a complex, that is, the above-mentioned base metal includes a composite formed by the above- Do.

The term "complex" as used herein means that the amide group of the high branching polymer forms a particulate form in coexistence with or in contact with the metal fine particles by the action of the amide group of the side chain of the high branching polymer. In other words, Is referred to as a composite having a structure for attaching or draining.

Here, the "structure for attaching or draining" refers to a state in which a part or all of the amide group of the high branching polymer interacts with the metal fine particles. For example, when a palladium salt is employed as a metal atom, it is considered that the amide group and the palladium salt form the structure shown in the following (a) or (b) (L in the formula is a ligand). Accordingly, in the case where the fine particles of palladium are employed as the metal fine particles, it is considered that the Pd atoms in the surface layer interact with the amide groups, thereby forming a structure in which the highly branched polymer surrounds the metal fine particles.

[Chemical Formula 4]

Therefore, in the &quot; composite &quot; in the present invention, not only the metal fine particles and the high branching polymer are combined to form a single composite, but also the metal fine particles and the high branching polymer do not form bonding portions, And may be independently present (apparently, one appearing to form one particle).

The structural moieties represented by the formulas [1], [2] and [3] included in the polymer chain of the (a) high-molecular-weight polymer of the present invention are all active protons for reducing Pd atoms, The (a) high branching polymer of the present invention can stably form a complex with (b) the metal fine particles by the amide group.

The formation of the composite of the above-mentioned (a) high-branched polymer and (b) metal fine particles is carried out at the same time when preparing a restraining agent comprising a high branching polymer and fine metal particles, There is a method of exchanging a ligand by a highly branched polymer after synthesizing stabilized metal fine particles or a method of forming a complex by directly reducing metal ions in a solution of a high branched polymer. As described above, by reducing the metal ion by adding a solution of a metal salt to a solution obtained by dissolving the above-mentioned branched polymer and irradiating it with ultraviolet rays, or by adding a solution of a metal salt and a reducing agent to this solution Complex can be formed.

In the ligand exchange method, the metal fine particles stabilized to a certain degree by the lower ammonium ligand to be a raw material can be synthesized by a method described in Jounal of Organometallic Chemistry 1996, 520, 143-162 and the like. The aimed metal fine particle complex can be obtained by dissolving the above-mentioned highly branched polymer in the reaction mixture solution of the obtained metal fine particles and then stirring at room temperature (about 25 캜) or heating.

The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the high branching polymer in a required concentration or more, and 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, butyronitrile and the like, and mixtures of these solvents, preferably tetrahydrofuran.

The temperature for mixing the reaction mixture of fine metal particles and the high branching polymer is usually from 0 占 폚 to the boiling point of the solvent, preferably from room temperature (approximately 25 占 폚) to 60 占 폚.

On the other hand, in the ligand exchange method, metal fine particles can be stabilized to some extent in advance even by using a phosphine-based dispersing agent (phosphine ligand) in addition to an amine-based dispersing agent (a lower ammonium ligand).

As a direct reduction method, a desired metal fine particle complex is obtained by dissolving a metal ion and a higher branching polymer in a solvent and reducing the solution to a primary or secondary alcohol such as methanol, ethanol, 2-propanol, or a polyol .

As the metal ion source used herein, the above-mentioned metal salt can be used.

The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving a high branching polymer having a metal ion and an amide group in a required concentration or more. Specific examples thereof include alcohols such as methanol, ethanol, n-propanol, Ryu; Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; Amides such as N, N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP); Sulfoxides such as dimethyl sulfoxide and the like, and mixtures of these solvents. Preferred examples of the solvent include alcohols, halogenated hydrocarbons and cyclic ethers. More preferred are ethanol, 2-propanol, chloroform , Tetrahydrofuran, and the like.

The temperature of the reduction reaction (mixing the metal ion with the high branching polymer) may be in the range of usually 0 占 폚 to the boiling point of the solvent, preferably in the range of room temperature (approximately 25 占 폚) to 60 占 폚.

In another direct reduction method, a desired metal fine particle complex can be obtained by dissolving a metal ion and a higher branching polymer in a solvent and reacting in a hydrogen gas atmosphere.

The above-mentioned metal salt and has a metal ion source used here, hexacarbonyl chromium [Cr (CO) _6], penta carbonyl nilcheol [Fe (Co) _5], octa-carbonyldiimidazole cobalt [Co ₂ (CO) ₈ ], Tetracarbonyl nickel [Ni (CO) ₄ ], and the like can be used. Oval 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-modified polymer at a required concentration or higher, and 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, butyronitrile and the like, and mixtures of these solvents, preferably tetrahydrofuran.

The temperature at which the metal ion and the high branching polymer are mixed is usually in the range of 0 占 폚 to the boiling point of the solvent.

In addition, as a direct reduction method, metal ions and a high branching polymer are dissolved in a solvent and subjected to a thermal decomposition reaction to obtain a target metal fine particle complex.

As the metal ion source to be used here, the above-mentioned metal salt, metal carbonyl complex or other metal complex such as 0 metal, metal oxide such as silver oxide can be used.

The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving a metal ion and a higher branching polymer in a required concentration or more. 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. Toluene is preferably used.

The temperature at which the metal ion and the amide group-containing high branching polymer are mixed can be usually from 0 占 폚 to the boiling point of the solvent, preferably from near the boiling point of the solvent, for example, at 110 占 폚 (refluxing in the case of toluene) to be.

The composite of the high branching polymer and the metal fine particles thus obtained can be subjected to a purification treatment such as reprecipitation to be in the form of solid such as powder.

The antiperspirant of the present invention comprises (c) an amine compound and other components as required, including (a) a high branching polymer and (b) fine metal particles (preferably a composite thereof) , And this abrasive may be in the form of a varnish to be used in forming the below-described [base layer of electroless metal plating].

<Other additives>

As long as the effect of the present invention is not impaired, the anticorrosion agent of the present invention may further contain additives such as surfactants, various surface modifiers, and thickening agents.

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 octyl phenyl ether and polyoxyethylene nonyl phenyl 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; EF-303, EF-352 (manufactured by Mitsubishi Material Electronics Co., Ltd.), Megafac (registered trademark) F-171, and F-173 , Novec (registered trademark) FC-430, FC-431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard (registered trademark) And fluorine surfactants such as AG-710 (manufactured by Asahi Glass Co., Ltd.) and Surflon (registered trademark) S-382 [manufactured by AGC Seiyam Chemical Co., Ltd.].

Examples of the surface conditioner include silicone leveling agents such as Shinetsu Silicone KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.); Based surface control agents such as BYK (registered trademark) -302, 307, 322, 323, 330, 333, 375, 375 and 378 (manufactured by Big Chem Japan) .

Examples of the thickening agent include polyacrylic acids (including crosslinked ones) such as carboxyvinyl polymer (carbomer); Vinyl polymers such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and polystyrene (PS); Polyethylene oxides; Polyester; Polycarbonate; Polyamide; Polyurethane; Polysaccharides such as dextrin, agar, carrageenan, alginic acid, gum arabic, guar gum, tragacanth gum, locust gum gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose; Gelatin, casein, and the like. In addition, each of the polymers includes a homopolymer as well as a copolymer. These thickeners may be used singly or in combination of two or more.

The base agent of the present invention can adjust the viscosity and rheology properties of the base agent by blending a thickener as required, and can be appropriately employed and selected in accordance with the application thereof such as a method of application of the base agent and application areas.

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

[Base layer of electroless metal plating]

The above-mentioned electroless plating plating solution of the present invention can be applied to a substrate to form a base layer of electroless metal plating. The base layer of this electroless metal plating is also the subject of the present invention.

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

Non-conductive substrates include, for example, glass, ceramics and the like; (Polyethylene naphthalate) resin, PET (polyethylene terephthalate) resin, PEEK (polyetheretherketone, polyetheretherketone), polyetherketone, polyetherketone Ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin and the like; Paper, and the like. They are suitably used in the form of sheet or film, and the thickness in this case is not particularly limited.

Examples of the conductive substrate include ITO (tin doped indium oxide), ATO (antimony doped tin oxide), FTO (fluorine doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide) In addition, various kinds of metals such as stainless steel, aluminum and aluminum alloys such as duralumin, iron and iron alloys, copper and copper alloys such as crude oil, phosphor bronze, white copper and beryllium copper, nickel and nickel alloys, And the like.

Furthermore, a substrate on which a thin film is formed with the conductive base material on the non-conductive substrate is also usable.

The substrate may be a three-dimensional molded body.

(C) an electroless plating plating solution containing (a) a high branching polymer and (b) fine metal particles (preferably a composite thereof) As a specific method for forming the undercoating layer of the metal plating, first, the above-mentioned precursor polymer and the metal fine particles (preferably a composite made of these) (and, if necessary, an amine compound and other components) are dissolved or dispersed in an appropriate solvent The varnish is formed into a varnish by a spin coating method on a substrate on which a metal plating film is formed; Blade coating method; Dip coating method; Roll coating method; Bar-coat method; Die coating method; Spray coat method; Ink jet method; Pen lithography such as fountain pen nanolithography (FPN) and deep pen nanolithography (DPN); Such as letterpress printing, flexographic printing, resin engraving printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), and nano transfer printing (nTP); Concave printing methods such as gravure printing and engraving; Flat plate printing method; Screen printing methods such as screen printing and spooling boards; Offset printing or the like, and then the solvent is evaporated and dried to form a thin layer.

Of these coating methods, spin coating, spray coating, inkjet, pen lithography, contact printing, μCP, NIL and nTP are preferred. In the case of using the spin coat method, since it can be applied in a short time, a solution having high volatility can be used, and there is an advantage that coating with high uniformity can be performed. When the spray coat method is used, it is possible to perform coating with high uniformity with a very small amount of varnish, which is industrially very advantageous. In the case of using the ink jet method, the pen lithography, the contact printing, the μCP, the NIL, and the nTP, it is possible to efficiently form (draw) a fine pattern, for example, wiring, and is industrially very advantageous.

The solvent used herein is not particularly limited as long as it dissolves or disperses the complex and, if necessary, the amine compound and other components, 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; 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, tri Propylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, Glycol ethers such as diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tripropylene glycol dimethyl ether; Glycol esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate (PGMEA); Ethers such as tetrahydrofuran (THF), methyltetrahydrofuran, 1,4-dioxane, and diethyl ether; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone; aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; Halogenated aliphatic hydrocarbons such as 1,2-dichloroethane and chloroform; Amides such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF) and N, N-dimethylacetamide; Dimethyl sulfoxide and the like can be used. These solvents may be used alone, or two or more kinds of solvents may be mixed. Furthermore, for the purpose of adjusting the viscosity of the varnish, glycols such as ethylene glycol, propylene glycol and butylene glycol may be added. On the other hand, when an amine compound in which an amino group is protected with an alkylidene group is used as the amine compound (c), the use of an alcohol solvent which releases the protecting group is avoided and ketones, ethers, It is convenient to use.

The concentration to be dissolved or dispersed in the solvent may be arbitrary, but the concentration of the non-solvent component in the varnish [the total components excluding the solvent included in the base resin (the combination of the high branch polymer and the metal fine particles The concentration of the amine compound and other components, etc., according to the concentration of the catalyst) is 0.05 to 90% by mass, preferably 0.1 to 80% by mass.

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

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

The base layer of the electroless metal plating formed on the substrate thus obtained is subjected to electroless plating to form a metal plating film on the base layer. The metal plating film thus obtained, and the metal film base provided in the order of the base layer of electroless metal plating and the metal plating film on the substrate are also objects of the present invention.

The electroless plating treatment (process) is not particularly limited and can be carried out by any generally known electroless plating process. For example, the electroless plating solution known in the art can be used to coat the plating solution (bath) A method of immersing the base layer of the electroless metal plating formed on the substrate is generally used.

The electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent. The electroless plating solution contains a pH adjuster, a pH buffer, a reaction promoter (second complexing agent), a stabilizer, a surfactant Application of gloss, application for improving the wettability of the surface to be treated, etc.).

Examples of the metal used for the metal plating film formed by the electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and alloys thereof. do.

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

The electroless plating solution may be a commercially available plating solution. Examples of the electroless plating solution include electroless nickel plating solution (Mel Plate (registered trademark) NI series) manufactured by Meltex Co., Ltd., electroless copper plating solution ) CU series); Electroless copper plating solution (OPC-700 electroless copper MK, ATS AddCapper IW, copper CT, etc.), electroless nickel plating solution (ICP NIKOLON (registered trademark) series, OPC Copper (registered trademark) AF series, Dong HFS, Dong NCA), electroless annotation amount (Substar SN-5), electroless gold amount (flash gold 330, self gold OTK-IT) Muden Silver); Radium salt amount (Pallet II), electroless gold plating amount (Deep G series, NC Gold series) manufactured by Kojima Chemical Co., Ltd.; Electroless silver plating amount (S-DIAG AG-40) manufactured by Sasaki Chemical Co., Ltd.; (Electroless nickel plating solution) (manufactured by Nippon Kanzen Co., Ltd.), electroless nickel plating solution (Kanzen (registered trademark) series, Schumer (registered trademark) series and Schumer (registered trademark) -PPD); (Registered trademark) series electroless copper plating solution (manufactured by Dow Chemical Co., Ltd.), electroless nickel plating solution (electroless copper plating solution) (Electrolytic (registered trademark) series), electroless gold plating (Aurolectores (registered trademark) series), electroless tin plating (tin foil (registered trademark) series); (ThruCup (registered trademark) ELC-SP, copper PSY, copper PCY, copper PGT, copper PSR, copper PEA, copper PMK) manufactured by Uemura Industries Co., Ltd., (PrintGen (registered trademark) PV, copper PVE) can be used as the electroless copper plating solution.

The electroless plating step may be carried out by adjusting the temperature and pH of the plating bath, the immersion time, the metal ion concentration, the presence or absence of stirring, the stirring speed, the supply / Can be controlled.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the examples, the physical properties of the samples were measured using the following apparatus under the following conditions.

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

Device: HLC-8220GPC manufactured by Tosoh Corporation

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

Column temperature: 40 DEG C

Solvent: tetrahydrofuran

Detector: UV (254 nm), RI

(2) Measurement of molecular weight 2: GPC (gel permeation chromatography)

Device: HLC-8220GPC manufactured by Tosoh Corporation

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

Column temperature: 40 DEG C

Solvent: DMF

Detector: UV (254 nm), RI

(3) ¹³ C NMR spectrum

Device: JNM-ECA700 manufactured by JEOL Ltd.

Solvent: CDCl ₃

Relaxation reagent: trisacetylacetonate chromium (Cr (acac) ₃ )

Standard: CDCl ₃ (77.0 ppm)

(4) ICP emission analysis (inductively coupled plasma emission spectrometry)

Device: ICPM-8500 manufactured by Shimadzu Corporation

(5) TEM (Transmission Electron Microscope) image

Device: Hitachi Hi-Technologies Co., Ltd. H-8000

(6) 5% weight reduction temperature

Device: Rigakujisa Shisa Thermal balance TG8120

Measurement conditions: air atmosphere

Heating rate: 10 ° C (25 to 500 ° C)

In addition, the weak symbols indicate the following meanings.

DCP: tricyclo [5.2.1.0 ^2,6 ] decanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Industry Co., Ltd.)

DVB: divinylbenzene (DVB-960, manufactured by Shin-Nittsu Chemical Co., Ltd.)

NVP: N-vinylpyrrolidone (manufactured by Kanto Kagaku Co., Ltd.)

NVA: N-vinylacetamide [manufactured by Showa Denko K.K.]

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

To a 1 L flask was added 125 mL of KUPOJET (registered trademark; hereinafter the same), CAPERMIX 328A (manufactured by DOW CHEMICAL CO., LTD.), 125 mL of KUPOZITCH KAPERMIX 328L (manufactured by DOW CHEMICAL CO., LTD.) And 15 mL of KUPOZIT CHAPTERMIX 328C , And pure water was further added to make the total amount of the solution to 1 liter.

[Reference Example 2] Preparation of electroless nickel plating solution

To a 1 L flask, 100 mL of Blue Schumer (manufactured by Kanzhen Co., Ltd.) was added, and further pure water was added to make the total amount of the solution to 500 mL.

[Polymerization Example 1: Preparation of highly branched polymer 1 using DVB, NVP and V-59]

97.6 g of MCS was added to a 300 mL reaction flask, nitrogen was introduced for 5 minutes while stirring, and the internal solution was heated to reflux (approximately 130 캜).

(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 into a separate 200 mL reaction flask, Nitrogen gas was introduced for a minute, and nitrogen substitution was carried out, and cooling was carried out in an ice bath to 0 ° C.

From the 100 mL reaction flask charged with DVB, NVP, and V-59 into the refluxed MCS in the 300 mL reaction flask described above, the contents were dripped for 30 minutes using a dropping pump. After completion of dropwise addition, the mixture was further stirred for 1 hour.

Then, 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 vacuum-dried to obtain 12.79 g (yield: 43.7%) of a white powder as a target product (highly branched polymer 1).

The weight average molecular weight Mw of the obtained target product as measured by GPC in terms of polystyrene was 8,900, and the degree of dispersion: 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]

122.8 g of MCS was added to a 200 mL reaction flask, nitrogen was introduced for 5 minutes with stirring, and the internal solution was heated to reflux (approximately 130 캜).

(100 mmol) of NVP as monomer B, 19.23 g (100 mmol) of V-59 as initiator C and 85.99 g of MCS as a monomer B were charged into a separate 100 mL reaction flask and 5 Nitrogen gas was introduced for a minute, and nitrogen substitution was carried out, and cooling was carried out in an ice bath to 0 ° C.

From the 100 mL reaction flask charged with DVB, NVP, and V-59 into the refluxed MCS in the 200 mL reaction flask described above, the content was dropped over 30 minutes using a dropping pump. After completion of dropwise addition, the mixture was further stirred for 1 hour.

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

The target product had a weight average molecular weight Mw of 2,600 and a polydispersity Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.8 as measured by GPC in terms of polystyrene.

[Polymerization Example 3: Preparation of highly branched polymer 3 using DVB, NVP and V-59]

106.8 g of MCS was added to a 200 mL reaction flask, nitrogen was introduced for 5 minutes while stirring, and the internal solution was heated to reflux (approximately 130 캜).

(100 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as initiator C and 74.74 g of MCS as a monomer B were charged into a separate 100 mL reaction flask and 5 Nitrogen gas was introduced for a minute, and nitrogen substitution was carried out, and cooling was carried out in an ice bath to 0 ° C.

From the 100 mL reaction flask charged with DVB, NVP, and V-59 into the refluxed MCS in the 200 mL reaction flask described above, the content was dropped over 30 minutes using a dropping pump. After completion of dropwise addition, the mixture was further stirred for 1 hour.

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

The weight average molecular weight Mw of the obtained product measured by GPC in terms of polystyrene was 7,500 and the degree of dispersion 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, nitrogen was introduced for 5 minutes while stirring, and the internal solution was heated to reflux (approximately 130 캜).

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 in a separate 100 mL reaction flask, Nitrogen gas was introduced for a minute, and nitrogen substitution was carried out, and cooling was carried out in an ice bath to 0 ° C.

From the 100 mL reaction flask charged with DCP, NVP and V-59 into the refluxed MCS in the 200 mL reaction flask described above, the content was dropped over 30 minutes using a dropping pump. After completion of dropwise addition, the mixture was further stirred for 1 hour.

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

The weight average molecular weight Mw of the obtained target product as measured by GPC in terms of polystyrene was 10,200 and the degree of dispersion 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]

Into a 200 mL reaction flask, 126.5 g of MCS was added, nitrogen was introduced for 5 minutes while stirring, and the internal solution was heated to reflux (approximately 130 캜).

(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 into a separate 100 mL reaction flask, Nitrogen gas was introduced for a minute, and nitrogen substitution was carried out, and cooling was carried out in an ice bath to 0 ° C.

From the 100 mL reaction flask charged with DVB, NVA and V-59 into the refluxed MCS in the 200 mL reaction flask described above, the content was dropped by dropping pump over 30 minutes. After completion of dropwise addition, the mixture was further stirred for 1 hour.

Then, the reaction solution was added to 1,275 g of hexane to precipitate the polymer in a slurry state. This slurry was filtrated under reduced pressure and vacuum dried to obtain 17.23 g (yield: 45.5%) of the objective white powder (highly branched polymer 5).

The weight average molecular weight Mw of the obtained product measured by GPC in terms of polystyrene was 9,300 and the degree of dispersion Mw (weight average molecular weight) / Mn (number average molecular weight) was 4.9. The &lt; ¹³ &gt; C NMR spectrum of the target product is shown in Fig.

[Polymerization Example 6: Preparation of highly branched polymer 6 using DVB, NVP and V-59]

Into a 200 mL reaction flask, 143.87 g of MCS was added, nitrogen was introduced for 5 minutes while stirring, and the internal solution was heated to reflux (approximately 130 캜).

(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 into a separate 100 mL reaction flask, Nitrogen gas was introduced for a minute, and nitrogen substitution was carried out, and cooling was carried out in an ice bath to 0 ° C.

From the 100 mL reaction flask charged with DVB, NVP, and V-59 into the refluxed MCS in the 200 mL reaction flask described above, the content was dropped over 30 minutes using a dropping pump. After completion of dropwise addition, the mixture was further stirred for 1 hour.

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

The weight average molecular weight Mw of the obtained product measured by GPC in terms of polystyrene was 11,300 and the degree of dispersion 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 Fig.

[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 charged, nitrogen was introduced for 5 minutes while stirring, and the internal solution was heated to reflux (approximately 130 캜).

16.75 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 in a separate 100 mL reaction flask, Nitrogen was introduced for 5 minutes, and nitrogen replacement was carried out, followed by cooling to 0 캜 in an ice bath.

From the 100 mL reaction flask charged with DCP, NVP and V-59 into the refluxed MCS in the 200 mL reaction flask described above, the content was dropped over 30 minutes using a dropping pump. After completion of dropwise addition, the mixture was further stirred for 1 hour.

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

The weight-average molecular weight Mw of the obtained target product as measured by GPC in terms of polystyrene was 12,800, and the degree of dispersion: 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 Fig.

[Production Example: Synthesis of Pd fine particle complex (10 g scale)]

The composite was prepared in the following procedure so that the Pd fine particle content (theoretical value) in the Pd fine particle-modified polymer composite was 30 wt%. On the other hand, high branch polymer 5 to high branched polymer 7 prepared as described above were used as the high branched polymer.

6.36 g of palladium acetate [Pd (OAc) ₂ , manufactured by Kawaken Fine Chemicals Co., Ltd.] and 63.56 g (amount of chloroform) were added to a reaction flask equipped with a condenser and stirred until homogeneous. Separately, a solution prepared by dissolving 7.0 g of the higher branched polymer in 70.00 g (amount of B) of chloroform was added to the reaction flask to which the palladium acetate was added using a dropping funnel. The dropping funnel was introduced into the reaction flask using 10.00 g (C amount) of chloroform and 95.71 g of ethanol. This mixture was stirred for 6 hours at 60 占 폚 in a nitrogen atmosphere.

After cooling to a liquid temperature of 30 캜, this solution was added to 1,196.33 g of IPE, followed by reprecipitation. The precipitated polymer was filtered under reduced pressure and vacuum-dried at 50 占 폚 to obtain a complex of a high branching polymer having an amide group in the side chain and Pd particles.

The polymer having the Pd fine particle content (theoretical value) of 30 wt%, and 40 wt%, 50 wt% or 60 wt% as described above was polymerized by using the amount of the components shown in Table 1 below. V59) [Composite 1 to Composite 4], Highly branched polymer 7 (HB-DCP-NVP-V59) [Composites 5 to 8], Highly branched polymer 5 ], And the yields of these complexes were calculated.

The actual metal content in the resulting composite was measured by ICP emission spectroscopy and the 5% weight reduction temperature of the composite was measured. From the TEM (transmission electron microscope) image, about 50 particles in the image were selected, and their particle diameters were measured to calculate an average value, which was regarded as the Pd particle diameter in each composite.

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-modified polymer 6 complex), 5 (Pd fine particle-modified polymer 7 complex) or composite 9 (Pd fine particle-modified polymer 5 complex) and 80 mg of KBM-903 N-propyl alcohol (PrOH) was added thereto so that the total amount became 2 g, and the mixture was stirred until homogeneous. After the solution became homogeneous, 8 g of n-propyl alcohol was further added to dilute the mixture to a total amount of 10 g, and the mixture was stirred at room temperature for 1 hour to prepare a solution containing Example 1 (containing Compound 1), Example 2 (containing Compound 5) 9) were prepared.

The electroless plating plating solutions of Examples 1 to 3 were applied to a polyimide film (capton) attached to a glass substrate by spin coating (200 rpm for 5 seconds and 1,000 rpm for 25 seconds) The polyimide film was removed from the glass substrate, and the solvent was dried on a hot plate (at 120 DEG C for 5 minutes) to form a base layer of electroless metal plating on the polyimide film.

These three types of films each having the base layer of the electroless metal plating were immersed in an electroless copper plating solution prepared in Reference Example 1 at 25 캜 for 5 minutes while air was slowly sprayed. Thereafter, the surface to be plated was washed with water and annealed (120 DEG C, 5 minutes) on a hot plate to obtain a plated substrate having a metal plating film (copper plating) formed on the base layer of electroless metal plating.

The plating film uniformity and substrate adhesion were evaluated for the metal plating films on the respective plating substrates obtained by using the electroless plating plating solutions of Examples 1 to 3 above.

The film uniformity was visually evaluated according to the following criteria. With regard to the substrate adhesion, Cellotape (registered trademark) (CT-18S, manufactured by Nichiban Co., Ltd.) having a width of 18 mm was stuck to the metal plating film portion on the obtained plating substrate, Cellotape (registered trademark) was peeled at once and the state of the metal plating film was visually evaluated according to the following criteria. The results are shown together in Table 3.

&Lt; Evaluation of Film Uniformity &

A: A metal plating film having a metallic luster was deposited on the entire surface of the substrate on which the base layer was formed,

△: The surface of the substrate is coated, but the gloss is uneven.

X: Not completely covered due to exposure of the substrate

&Lt; Evaluation of substrate adhesion &

?: No peeling of the metal plating film was observed,

DELTA: Partly peeling off the metal plating film

X: Most (about 50% or more) of the metal plating films were peeled off and adhered to Cellotape (registered trademark)

[Table 3]

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

Except that KBM-9103 was used in an equivalent amount instead of KBM-903 and methyl isobutyl ketone (MIBK) was used in place of n-propyl alcohol (PrOH) as a solvent in the same amounts as in Examples 1 to 3, (Containing the complex 1), Example 5 (containing the complex 5), and Example 6 (containing the complex 9) were prepared and electroless plating was carried out on the polyimide film as described above Subsequently, a plating substrate on which a metal plating film (copper plating) was formed on the base layer of the electroless metal plating using the electroless copper plating solution prepared in Reference Example 1 was obtained in the same manner as described above , And the uniformity of the plating film and the 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 electroless plating plating agent and examination of electroless nickel plating]

(Containing Pd fine particles-high branching polymer 5 complex), amine compound: KB-9103, containing MIBK] of Example 7 was prepared in the same manner as in Example 6, and similarly to the above, on the polyimide film And the underlayer of the electroless metal plating was formed. This film was prepared in Referential Example 2 and immersed in the electroless nickel plating solution described in Reference Example 2 heated at 85 캜 for 3 minutes. Thereafter, the surface to be plated was washed with water and annealed (120 DEG C, 5 minutes) on a hot plate to obtain a plated substrate on which a metal plating film (nickel plating) was formed on the base layer of electroless metal plating.

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

In Example 6, an electroless plating plating solution was prepared without using the amine compound KBM-9103. That is, 20 mg of the composite 9 (Pd fine particles-high branching polymer 5 composite) obtained above was dissolved in methyl isobutyl ketone (MIBK) so that the total amount was 10 g to prepare an electroless plating base material of Example 8.

The above electroless plating plating agent was applied on a polyimide film (capton) attached to a glass substrate in the same manner as above using a spin coat (200 rpm for 5 seconds and 1,000 rpm for 25 seconds), and then the polyimide film The film was peeled off from the glass substrate, and the solvent was dried with a hot plate (at 120 DEG C for 5 minutes) to form a base layer of electroless metal plating on the polyimide film.

The film on which the base layer of the electroless metal plating was formed was immersed in an electroless nickel plating solution described in Reference Example 2 at 85 캜 for 3 minutes. Thereafter, the surface to be plated was washed with water and annealed (120 DEG C, 5 minutes) on a hot plate to obtain a plated substrate on which a metal plating film (nickel plating) was formed on the base layer of electroless metal plating.

The plated substrates obtained in Examples 7 and 8 were evaluated for plating film uniformity and substrate adhesion as described above. The obtained results are shown together in Table 5.

[Table 5]

Claims (18)

An electroless plating pretreatment agent for forming a metal plating film by electroless plating on a substrate,
(a) a polymerizable compound comprising at least monomer A having two or more radical double bonds in the molecule and monomer B having an amide group and at least one radical double intermolecular double bond, and a polymerizable compound having a number of moles of the monomer A As a high branched polymer composed of a polymer of a polymerization initiator C in an amount of 5 to 200 mol%
Wherein the polymer has a highly branched polymer chain comprising at least a structural moiety represented by the following formula [1] and formula [2] or formula [3], and at the end of the polymerization chain, A branched polymer prepared by incorporating a radical cleavage fragment, and
(b) metal fine particles
&Lt; / RTI &gt;
[Chemical Formula 1]

(Wherein,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently 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 An alkyl group having 1 to 10 carbon atoms,
A ₁ represents a single bond or a divalent organic group,
R ₇ , R ₈ and R ₉ each independently represent an alkyl group having 1 to 10 carbon atoms which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond, ,
R ₁₀ and R ₁₁ each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond, , R ₁₀ and R ₁₁ may be taken together to 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 which may contain at least one bond selected from the group consisting of a hydrogen atom, an ether bond, an amide bond and an ester bond. The method according to claim 1,
Wherein the amide group in the (a) high branching polymer comprises a composite for adhering or spreading the (b) fine metal particles. 3. The method according to claim 1 or 2,
Wherein the monomer A is a compound having either or both of a vinyl group and a (meth) acryloyl group. The method of claim 3,
Wherein the monomer A is a divinyl compound or a di (meth) acrylate compound. 5. The method of claim 4,
Wherein the monomer A is a compound having an aromatic ring having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms. 6. The method of claim 5,
Wherein the monomer A is divinylbenzene or tricyclo [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate. 7. The method according to any one of claims 1 to 6,
Wherein the polymerization initiator C is an azo-based polymerization initiator. 8. The method according to any one of claims 1 to 7,
Wherein the polymerizable compound comprises the monomer B in an amount of 5 to 300 moles relative to the number of moles of the monomer A. The method according to claim 1,
A ₁ represents an aromatic group having 3 to 30 carbon atoms or a divalent organic group having an alicyclic group having 3 to 30 carbon atoms. The method according to claim 1,
Wherein the (a) high branching polymer is a high branching polymer composed of a polymer constituting at least a polymer chain including structural moieties represented by the formulas [1] and [2]
In the formula [1]
R ₁ , R ₂ , R ₅ and R ₆ represent a hydrogen atom,
R ₃ and R ₄ represent a hydrogen atom or a methyl group,
A ₁ represents a phenylene group or a tricyclo [5.2.1.0 ^2,6 ] decane-4,8-diyl-di (methyleneoxycarbonyl) group,
In formula [2]
R ₇ , R ₈ and R ₉ represent a hydrogen atom,
R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a methyl group, or R ₁₀ and R ₁₁ are combined to form an n-propylene group,
A radical cleavage fragment of a polymerization initiator C selected from 2,2'-azobis (2-methylbutyronitrile) and dimethyl 2,2 'azobis (2-methylpropionate) is loaded at the end of the polymerization chain Made,
Do not. 11. The method according to any one of claims 1 to 10,
Wherein the metal fine particles (b) are selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Au). &Lt; / RTI &gt; 12. The method of claim 11,
Wherein the metal fine particles (b) are palladium fine particles. 13. The method according to any one of claims 1 to 12,
Wherein the metal fine particles (b) are fine particles having an average particle diameter of 1 to 100 nm. 14. The method according to any one of claims 1 to 13,
Further comprising (c) an amine compound. An undercoat layer of electroless metal plating, which is a layer made of the electroless plating plating solution as set forth in any one of claims 1 to 14. A metal plating film formed on the base layer of the electroless metal plating according to claim 15. And a metal plating film formed on the base layer of the electroless metal plating, the base layer of the electroless metal plating according to claim 15 formed on the base material, and a metal plating film formed on the base layer of the electroless metal plating. A process for producing a metal film base comprising the steps A and B described below.
A step: a step of applying the electroless plating plating agent according to any one of claims 1 to 14 on a base material and providing a base layer of electroless metal plating on the base material,
Step B: A step of immersing the base material having the base layer in an electroless plating bath to form a metal plating film on the base layer.

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