TW201800609A - Electroless plating primer containing highly-branched polymer and metal fine particle - Google Patents

Abstract

To provide a new primer that can be used for an electroless plating pretreatment process, the primer having high heat resistance and being capable of forming a plating base layer containing no corrosive atoms. Further, the primer can also achieve cost reduction in manufacturing thereof. An electroless plating primer for forming a metal plating film by performing electroless plating treatment on a base, containing (a) a multibranched polymer comprising a polymer of: a polymerizable compound containing at least a monomer A having two or more radically polymerizable double bonds in the molecule and a monomer B having an amide group and at least one radically polymerizable double bond in the molecule; and a polymerization initiator C of an amount of 5-200 mol% based on the mole number of the monomer A, wherein the polymer has a multibranched polymer chain and a radical cleaved fragment of the polymerization initiator C is incorporated in a terminal of the polymer chain, and (b) a metal particulate.

Description

Electroless plating primer containing highly branched polymer and metal particles

The present invention relates to an electroless plating primer containing a highly branched polymer (highly branched polymer) and metal particles.

Electroless plating is because the base material is only immersed in the plating solution, regardless of the type or shape of the base material, and a uniform thickness film is obtained. Even on non-conductive materials such as plastics, ceramics, and glass, metal plating can be formed. Therefore, for example, it is widely used in various fields such as decorative applications that impart high-grade or beautiful appearance to resin molded articles such as automobile parts, or electromagnetic shielding, printed circuit boards, and large-scale integrated circuit wiring.

Generally, when a metal plating film is formed on a substrate (substrate) by electroless plating, a pretreatment for improving the adhesion between the substrate and the metal plating film is performed. Specifically, first, the surface to be processed is roughened and / or hydrophilized by various etching methods, and secondly, an adsorption substance that promotes the adsorption of the plating catalyst to the surface to be processed is supplied to the surface to be processed. The sensitization treatment and the activation treatment for adsorbing the plating catalyst to the surface to be treated. Typically, the sensitization treatment is performed by immersing the object to be treated in an acidic solution of stannous chloride, whereby a metal (Sn ²⁺ ) capable of acting as a reducing agent is attached to the surface to be treated. The sensitized surface to be treated is then immersed in an acidic solution of palladium chloride as an activation treatment. As a result, the palladium ion in the solution is reduced by the metal (tin ion: Sn ²⁺ ) of the reducing agent, and the active palladium catalyst core adheres to the surface to be treated. After the pretreatment in this way, it was 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 polymer is actively introduced into branches. As a significant feature, it has a large spherical skeleton that simulates a spherical shape, and has excellent dispersion stability. In addition, the number of terminal groups is large. When a reactive functional group is added to this terminal group, since the polymer becomes a reactive functional group having a very high density, it can be expected to be a high-sensitivity capture agent or a high-sensitivity multifunctional cross-linking agent as a functional substance such as a catalyst. , Metal or metal oxide dispersant or coating agent application.

For example, it is reported that a composition containing a highly branched polymer having an ammonium group and metal fine particles is used as a primer for electroless plating (plating catalyst), and an electroless plating primer is proposed, which avoids the use of The chromium compound (chromic acid), which is a problem in the pre-treatment step (roughening treatment) of the electroless plating process, and the number of steps of the pre-treatment are reduced, and various improvements such as environmental or cost aspects and complicated operability are sought (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: International Patent Application Publication No. 2012/141215

In the case of a composition including a highly branched polymer having an ammonium group and metal fine particles proposed as a primer for the above-mentioned electroless plating, when this is applied to wiring technology such as semiconductor manufacturing, it contains The high-branched polymer has a low heat resistance temperature, and it may be decomposed for solder reflow or high-temperature processing. In addition, in the high-branched polymer, halogen exists as a counter anion of the quaternary ammonium group contained therein, and in the process of the high-branched polymer, sulfur atoms may remain in the polymer. Anxiety of substrate corrosion due to them. In addition, the high-branched polymer is expensive to produce because it is synthesized in multiple stages, and quaternary ammonium salts have been used as catalysts in conventional hardening components such as epoxides and isocyanates. A highly branched polymer with a quaternary ammonium salt structure. When the varnish of an electroless plating primer is prepared, its storage stability is prone to problems.

In this way, in the electroless plating primers proposed so far, in addition to the plating performance of the plating primer, there are no corrosive atoms such as halogen atoms or sulfur atoms, and it is possible to give a plate having high heat resistance. It can be easily varnished into a variety of compositions, and has various properties of high dispersion stability. Yes, it also includes operability that can be easily manufactured with a small number of procedures, and a fully realized electroless plating primer has not yet been proposed.

The present invention is directed to such a problem, and an object thereof is to provide a new undercoating agent which can form a plating undercoating layer having high heat resistance and containing no corrosive atoms, and furthermore, its manufacturing cost can also achieve low cost. It can be used as a pretreatment step for electroless plating.

In order to achieve the above-mentioned object, the present inventors intensively reviewed, and as a result, they reviewed a highly branched polymer containing amidino group and a better cyclic skeleton, but no corrosive atoms, and found that combining the high branched polymer with A layer of metal fine particles, which is obtained by coating this material on a substrate, is not only used as an undercoat for electroless metal plating, but also has high heat resistance and a layer without the risk of corrosion. invention.

That is, the present invention is, as a first aspect, an undercoating agent which is an electroless plating undercoating agent for forming a metal plating film on a substrate by an electroless plating treatment, and includes: A polymerizable compound comprising a monomer A having two or more radical polymerizable double bonds in a molecule, and a monomer B having an amidino group and at least one radical polymerizable double bond in the molecule, and The molar number of the monomer A is a high-branched polymer of a polymer of the polymerization initiator C in an amount of 5 to 200 mole%. The polymer has at least the following formula [1] and formula [ 2] or a highly branched polymer composed of a structural part represented by the formula [3], which is a highly branched polymer chain, and a radical cleavage fragment of the aforementioned polymerization initiator C is incorporated at the end of the polymer chain , And (b) metal particles;

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, and may contain at least one selected from the group consisting of an ether bond, a amine bond, and an ester bond. An alkyl group having 1 to 10 carbon atoms in the bond, A ₁ represents a single bond or a divalent organic group, R ₇ , R _8, and R ₉ each independently represent a hydrogen atom, and may contain a group selected from the group consisting of an ether bond, a amine bond, and an ester. An alkyl group having 1 to 10 carbon atoms in at least one bond of a group formed by a bond, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom and may be selected from the group consisting of an ether bond, a amine bond, and an ester bond. A group of at least one bond having an alkyl group or phenyl group having 1 to 10 carbon atoms, or R ₁₀ and R ₁₁ may be formed together to form a group selected from the group consisting of an ether bond, a amine bond, and an ester bond. R ₂ , R _13, and R ₁₄ each independently represent a hydrogen atom, and may contain a group selected from the group consisting of an ether bond, a amine bond, and an ester bond. An alkyl group having 1 to 10 carbon atoms with at least one bond, R ₁₅ and R ₁₆ each independently represent a hydrogen atom, and may contain at least one bond selected from the group consisting of an ether bond, a amine bond, and an ester bond Alkyl group having 1 to 10 carbon atoms).

As a second aspect, the primer according to the first aspect includes a complex comprising the (a) amine group in the high-branched polymer and the (b) metal fine particles attached or coordinated.

As a third aspect, the primer according to the first aspect or the second aspect, wherein the monomer A is a compound having any one or both of a vinyl group and a (meth) acrylfluorenyl group.

As a fourth aspect, the primer according to the third aspect, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound.

As a fifth aspect, the primer according to the fourth aspect, wherein the monomer A is a compound having an aromatic ring group having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.

As a sixth aspect, the primer according to the fifth aspect, wherein the monomer A is divinylbenzene or tricyclic [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate.

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

As an eighth aspect, the primer as described in any one of the first to seventh aspects, wherein the polymerizable compound contains a single amount of the primer compound. For the mole number of the body A, the aforementioned monomer B is in an amount of 5 to 300 mole%.

As a ninth aspect, the primer according to the first aspect, wherein the A ₁ represents a divalent organic group having an aromatic ring group having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.

As a tenth aspect, the primer according to the first aspect, wherein the (a) high-branched polymer is composed of a polymer chain including at least a structural portion represented by the formulas [1] and [2]. Polymer is a highly branched polymer. In the formula [1], R ₁ , R ₂ , R ₅ and R ₆ represent hydrogen atoms, R ₃ and R ₄ represent hydrogen atoms or methyl groups, and A ₁ represents phenylene. Or tricyclic [5.2.1.0 ^2,6 ] decane-4,8-diyl-bis (methoxycarbonyl)), in the 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 taken} together to represent an orthopropenyl group, which is incorporated at the end of the polymer chain by 2,2'-azobis (2-methylbutane Nitrile) and dimethyl 2,2'-azobis (2-methylpropionate) selected from the radical cleavage fragments of the polymerization initiator C.

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

As a twelfth aspect, the primer according to the eleventh aspect, wherein the (b) metal fine particles are palladium fine particles.

As a thirteenth aspect, the primer according to any one of the first to twelfth aspects, wherein the (b) metal fine particles are fine particles having an average particle diameter of 1 to 100 nm.

As a fourteenth aspect, the primer according to any one of the first to thirteenth aspects further contains (c) an amine compound.

According to a fifteenth aspect, an undercoat layer for electroless metal plating is a layer formed of the electroless plating primer as described in any one of the first to fourteenth aspects.

As a sixteenth aspect, a metal plating film is formed on the undercoat layer of electroless metal plating as described in the fifteenth aspect.

As a seventeenth aspect, a metal coating substrate includes a base material, an undercoat layer for electroless metal plating as described in the fifteenth aspect, and a primer layer formed on the electroless metal plating formed on the base material. Metal coating on top of the layer.

As an eighteenth aspect, a method for producing a metal film substrate includes the following steps A and B; Step A: applying the electroless plating primer as described in any one of the first to the fourteenth aspects; The step of disposing on a substrate and providing an undercoat layer for electroless metal plating on the substrate, step B: immersing the substrate provided with the undercoat layer in an electroless plating bath, and The step of forming a metal plating film on the coating.

The undercoating agent of the present invention can be easily applied to an electrolytic plating undercoating layer by only applying it to a substrate. In addition, according to the present invention, it is possible to form an electroplated undercoat layer having excellent plating performance and high heat resistance without the risk of substrate corrosion. In addition, the primer of the present invention can be easily varnished with various compositions, and has a high dispersion stability.

In addition, since the highly branched polymer used in the primer of the present invention can be easily prepared in a small number of procedures, the manufacturing steps of the plating primer can be simplified and the manufacturing cost can be reduced.

In addition, the electroless metal plating undercoat layer formed by the electroless plating primer of the present invention can easily form a metal plating film only by being immersed in an electroless plating bath, and can easily be provided with a substrate and an undercoat layer. As well as metal coated substrates.

That is, by using the electroless plating primer of the present invention to form an undercoat layer on a substrate, a heat-resistant metal plating film having excellent adhesion to the substrate can be formed.

FIG. 1 shows a ¹³ C NMR spectrum of the highly branched polymer 5 (DVB, NVA, V-59) obtained in Polymerization Example 5. FIG.

FIG. 2 is a graph showing a ¹³ C NMR spectrum of the highly branched polymer 6 (DVB, NVP, V-59) obtained in Polymerization Example 6. FIG.

FIG. 3 shows a ¹³ C NMR spectrum of the highly branched polymer 7 (DCP, NVP, V-59) obtained in Polymerization Example 7. FIG.

Implementation of the invention

Hereinafter, the present invention will be described in detail.

The primer of the present invention is a primer containing (a) the above-mentioned highly branched polymer having a specific structural portion and (b) metal fine particles and optionally (c) an amine compound.

The primer of the present invention is suitable as a catalyst for forming a metal plating film on a substrate by electroless plating treatment.

<(a) Highly branched polymer>

The high-branched polymer (hereinafter, also referred to as a high-branched polymer containing a fluorenamine group) used in the primer of the present invention is composed of at least two radically polymerizable double bonds in the molecule. The polymerizable compound of monomer A and monomer B having an amidino group and at least one radically polymerizable double bond in the molecule, in an amount of 5 to 200 mole% relative to the mole number of the monomer A A highly branched polymer of the polymer of the polymerization initiator C. The aforementioned high-branched polymer is a so-called initiator fragment incorporation (IFIRP) type high-branched polymer, and has a fragment (radical cleaved fragment) of a polymerization initiator C used in the polymerization reaction at its end.

The "high-branched polymer" in the present invention is not only a high-molecular-weight polymer of the above-mentioned monomers A and B, but also includes As oligomers of low molecular weight polymers. That is, the highly branched polymer of the present invention can also be understood as a "branched polymer".

The highly branched polymer of the present invention has a structure formed by a polymerization reaction including at least two radical polymerizable double bonds contained in the aforementioned monomer A, which has at least a structural portion represented by the following formula [1]. Part, and a structural part represented by the following formula [2] or formula [3], that is, a highly branched polymer chain composed of a structural part formed by a polymerization reaction of the radically polymerizable double bond of the aforementioned monomer B, In addition, a polymer obtained by incorporating a radical cleavage fragment of a polymerization initiator C at the end of the polymer chain.

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, and may contain at least one selected from the group consisting of an ether bond, a amine bond, and an ester bond. An alkyl group having 1 to 10 carbon atoms in the bond, A ₁ represents a single bond or a divalent organic group, R ₇ , R _8, and R ₉ each independently represent a hydrogen atom, and may contain a group selected from the group consisting of an ether bond, a amine bond, and an ester. An alkyl group having 1 to 10 carbon atoms in at least one bond of a group formed by a bond, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom and may be selected from the group consisting of an ether bond, a amine bond, and an ester bond. A group of at least one bond having an alkyl group or phenyl group having 1 to 10 carbon atoms, or R ₁₀ and R ₁₁ may be formed together to form a group selected from the group consisting of an ether bond, a amine bond, and an ester bond. R ₂ , R _13, and R ₁₄ each independently represent a hydrogen atom, and may contain a group selected from the group consisting of an ether bond, a amine bond, and an ester bond. An alkyl group having 1 to 10 carbon atoms with at least one bond, and R ₁₅ and R ₁₆ each independently represent a hydrogen atom, and may contain at least one bond selected from the group consisting of an ether bond, a amine bond, and an ester bond Alkyl group having 1 to 10 carbon atoms).

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 include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, and neopentyl. Group, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, 1-adamantyl, benzyl, phenethyl and the like.

Examples of the aforementioned alkylene group having 2 to 6 carbon atoms include methylene, propylidene, butylidene, pentylyl, and hexylyl.

The alkyl group having 1 to 10 carbon atoms and the alkylene group having 2 to 6 carbon atoms may include at least one bond selected from the group consisting of their ether bond, amido bond, and ester bond. For example, the above-mentioned alkyl group or the like may be interrupted by such a bond, or may be bonded to a binding end of the above-mentioned alkyl group (for example, an oxyalkylene group or the like).

Examples of the divalent organic group include carbon atoms of 1 to 20 aliphatic groups, aromatic ring groups having 3 to 30 carbon atoms, alicyclic groups having 3 to 30 carbon atoms, heterocyclic groups having 3 to 30 carbon atoms, or one or more of these combination. These aliphatic groups, aromatic ring groups, alicyclic groups, and heterocyclic groups may have a substituent. Moreover, these aliphatic groups and aromatic ring groups. The alicyclic group and the heterocyclic group may include at least one bond selected from the group consisting of an ether bond, a amine bond, and an ester bond in the group.

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

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

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

、嘧啶、吡

、哌啶、哌

、吡咯、吡唑、咪唑、吡咯啶、吡唑啶、咪唑啶、呋喃、吡喃、噻吩、噻喃、異

唑、異

唑啶、嗎啉、異噻唑、異噻唑啶、硫代嗎啉、苯并咪唑、苯并呋喃、苯并噻吩、苯并噻唑、苯并

唑、三

、醌等。 Examples of the heterocyclic ring in the heterocyclic group include pyridine and

, Pyrimidine, pyridine

Piperidine

, Pyrrole, pyrazole, imidazole, pyrrolidine, pyrazidine, imidazole, furan, pyran, thiophene, thioan, iso

Azole, iso

Azodin, morpholine, isothiazole, isothiazole, thiomorpholine, benzimidazole, benzofuran, benzothiophene, benzothiazole, benzo

Azole, three

, Quinone and so on.

Among these, A _{1 is} preferably a divalent organic group having an aromatic ring group having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms.

The highly branched polymer can be polymerized by polymerizing a polymerizable compound containing at least the monomer A and the monomer B described below in the presence of a specified amount of a polymerization initiator C with respect to the monomer A, so that One-stage system Made.

[Monomer A]

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

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

Examples of the monomer A that can be used in the present invention include organic compounds shown in the following (A1) to (A7).

(A1) Ethylene-based hydrocarbons:

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

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

(A1-3) aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinyl (A2) vinyl esters such as vinyl carbazole, divinyl pyridine, allyl esters, vinyl ethers, allyl ethers, ethylene Ketones:

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

(A2-2) allyl esters; diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate, (meth) acrylate Propyl ester

(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, tetraallyloxy Butane, tetramethacryloxyethane, etc.

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

(A3) (meth) acrylates:

烷二醇 二(甲基)丙烯酸酯、2-羥基-1-丙烯醯氧基-3-甲基丙烯醯氧基丙烷、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀、十一烯氧基乙二醇二(甲基)丙烯酸酯、雙[4-(甲基)丙烯醯基苯硫基]硫化物、雙[2-(甲基)丙烯醯基硫乙基]硫化物、1,3-金剛烷二醇二(甲基)丙烯酸酯、1,3-金剛烷二甲醇二(甲基)丙烯酸酯、芳香族胺基甲酸酯二(甲基)丙烯酸酯、脂肪族胺基甲酸酯二(甲基)丙烯酸酯等 Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, two trimethylolpropane tetra (meth) acrylate, triglyceride Acrylate), pentaerythritol tetra (meth) acrylate, titanium alkoxide tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8- Octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclic [5.2.1.0 ^2,6 ] Decane dimethanol di (meth) acrylate, di

Alkanediol di (meth) acrylate, 2-hydroxy-1-propenyloxy-3-methylpropenyloxypropane, 2-hydroxy-1,3-di (meth) propenyloxypropane , 9,9-bis [4- (2- (meth) propenyloxyethoxy) phenyl] fluorene, undecenyloxyethylene glycol di (meth) acrylate, bis [4- ( (Meth) acrylfluorenylphenylthio] sulfide, bis [2- (meth) acrylfluorenylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1,3 -Adamantane dimethanol di (meth) acrylate, aromatic urethane di (meth) acrylate, aliphatic urethane di (meth) acrylate, etc.

(A4) A vinyl compound having a polyalkylene glycol chain:

Polyethylene glycol (molecular weight 300, etc.) di (meth) acrylate, polypropylene glycol (molecular weight 500, etc.) di (meth) acrylate, etc.

(A5) Nitrogen-containing vinyl compound:

Diallylamine, diallyl isocyanurate, diallyl isocyanate, ethoxylated isotricyanate di (meth) acrylate, ethoxylated isotricyanate (Meth) acrylate, methylene bis (meth) acrylamide, bismaleimide, etc.

(A6) Silicone-containing compound:

Dimethyldivinylsilane, divinyl (methyl) (phenyl) silane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilane Oxane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane, diethoxydivinylsilane, etc.

(A7) Fluorinated ethylene-based compound:

1,4-divinyl perfluorobutane, 1,4-divinyl octafluorobutane, 1,6-divinyl perfluorohexane, 1,6-divinyl dodecylfluorohexane, 1 , 8-Diethyl Alkenyl perfluorooctane, 1,8-divinyl hexafluorooctane, etc.

Of these, preferred are the aromatic vinyl hydrocarbon compounds of the group (A1-3), the vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the (A3) group, and the (A3) group. (Meth) acrylate, (A4) group of vinyl compounds having a polyalkylene glycol chain, and (A5) group of nitrogen-containing vinyl compounds.

Particularly preferred are divinylbenzenes belonging to the (A1-3) group, diallyl phthalates belonging to the (A2) group, ethylene glycol di (meth) acrylates belonging to the (A3) group, 1 , 3-adamantane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and methylene bis (meth) acrylamide belonging to the (A5) group. Among these, divinylbenzene, ethylene glycol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate are preferred, and vinylbenzene or tricyclodecanedi is particularly preferred. Methanol di (meth) acrylate.

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

[Monomer B]

In the present invention, the monomer B is not particularly limited as long as it is a compound having an amidino group and at least one radically polymerizable double bond in the molecule, but preferably has at least one vinyl group or (methyl) group. Either acrylyl is a compound of a radical polymerizable double bond. When the monomer B is a compound having a (meth) acrylfluorenyl group as a radical polymerizable double bond, it may also be a carbonyl group [-C (= O) contained in the (meth) acrylfluorenyl group. -] With 醯 Repeated structure of carbonyl group in amine group.

Examples of such a monomer B include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylacetamide, and N-methyl (methyl) Acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acryl Amidine, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (methyl) Propyl) acrylamide, N-ethoxymethyl (meth) acrylamine, N-butoxymethyl (meth) acrylamine, N-isobutoxymethyl (meth) acrylamine Amines, N-isobutoxyethyl (meth) acrylamide and the like.

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

In the present invention, the ratio of copolymerizing the monomer A and the monomer B is from the viewpoint of reactivity or plating property, and the monomer B is preferably 0.05 moles relative to 1 mole of the monomer A. Ears are ~ 20 moles, especially preferred is 0.1 moles ~ 10 moles.

[Other monomers]

In the aforementioned polymerizable compound, as the other monomer together with the aforementioned monomer A and the aforementioned monomer B, a monomer D having at least one radical polymerizable double bond in the molecule but not having an amidino group may be included. .

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

Among them, preferred are vinyl ether group-containing (meth) acrylate compounds such as 2- (2-vinyloxyethoxy) ethyl acrylate, and epoxy group-containing compounds such as propylene methacrylate. (Meth) acrylate compounds; (meth) acrylate compounds containing alkoxysilyl groups such as 3-methacryloxypropyltriethoxysilane; cyclohexylmaleimide, N- Maleimide compounds such as benzylmaleimide and the like.

In the present invention, when the polymerizable compound contains the aforementioned monomer D, the blending ratio thereof is preferably from the viewpoint of reactivity or surface modification effect, with respect to the aforementioned monomer A 1 mole. D is 0.05 mol to 3.0 mol, and particularly preferred is 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 compounds represented by the following (1) to (6).

(1) Azonitrile compounds:

2,2'-azobisisobutyrene, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1 , 1'-Azobis (1-cyclohexanecarbonitrile), 2,2'-Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (Aminomethylamino) Azo) isobutyronitrile, etc .;

(2) Azopine compound:

2,2'-Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propanamide}, 2,2'-azobis {2- Methyl-N- [2- (1-hydroxybutyl)] propane Amine}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propanamine], 2,2'-azobis [N- (2-propenyl) -2 -Methylpropionamine], 2,2'-Azobis (N-butyl-2-methylpropylamidamine), 2,2'-Azobis (N-cyclohexyl-2-methylpropyl) Lamine), etc .;

(3) Cyclic azophosphonium compound:

2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride 2,2'-azobis [2- (2-imidazolin-2-yl) propane] Disulfate dihydrate, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2'- Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (1-imino-1-pyrrolidinyl-2-methylpropane) dihydrochloride Wait;

(4) Azo compound:

2,2'-Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropaneamidine] tetrahydrate Wait;

(5) Others:

Dimethyl 2,2'-azobisisobutyrate [dimethyl 2,2-azobis (2-methylpropionate), 2,2'-azobis (2,4,4 -Trimethylpentane), 1,1'-azobis (1-acetamido-1-phenylethane), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate) Acid ester), 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis-4-cyanovaleric acid, and the like.

(6) Azo-based polymerization initiator containing fluoroalkyl group:

4,4'-azobis (4-cyanopentanoic acid-2- (perfluoromethyl) ethyl), 4,4'-azobis (4-cyanopentanoic acid-2- (all Fluorobutyl) ethyl), 4,4'-azobis (4-cyanopentanoic acid-2- (perfluorohexyl) ethyl) and the like.

Among the above-mentioned azo-based polymerization initiators, 2,2'-azobis (2-methylbutyronitrile) and dimethyl are preferred from the viewpoint of dissolution in a plating bath or plating properties. 2,2'-Azobisisobutyrate.

When 2,2'-azobis (2-methylbutyronitrile) is used as the polymerization initiator C, a radical derived from the polymerization initiator C at the end of the polymerization chain in the polymer is used. 1-methyl-segment split lines become -1-cyano - propyl _{[-C (CH 3) (CN} ) -CH 2 CH 3].

Relative to the mole number of the monomer A, the polymerization initiator C is used in an amount of 5 to 200 mole%, preferably 15 to 200 mole%, more preferably 15 to 170 mole%, especially It is preferably used in an amount of 50 to 100 mol%.

<Manufacturing method of highly branched polymer>

As described above, the highly branched polymer used in the present invention is a polymerizable compound containing the monomers A and B, and other monomers as desired, in a specified amount with respect to the monomer A. It is obtained by polymerization in the presence of a polymerization initiator C.

Examples of the polymerization method of the aforementioned polymerizable compound containing monomer A, monomer B, and other monomers as desired in the presence of a polymerization initiator C include well-known methods such as solution polymerization, dispersion polymerization, and precipitation. Among the polymerization and bulk polymerization, solution polymerization or precipitation polymerization is preferred. Especially from a viewpoint of molecular weight control, it is preferable to perform a reaction by solution polymerization in an organic solvent.

烷、甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、丙二醇單甲基醚等的醚類；丙酮、甲基乙基酮、甲基異丁基酮、二正丁基酮、環己酮等的酮類；甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇、2-乙基己基醇、苯甲醇、乙二醇等的醇類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等的醯胺類；二甲亞碸等的亞碸類、以及此等的2種以上之混合溶劑。 Examples of the organic solvent used at this time include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; and aliphatics such as n-hexane, n-heptane, mineral spirits, and cyclohexane. Or alicyclic hydrocarbons; halides such as methyl chloride, bromomethane, iodomethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene, etc .; ethyl acetate, butyl acetate Esters, ester ethers, such as esters, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate; diethyl ether, tetrahydrofuran 1,4-two

Ethers such as alkane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclic Ketones such as hexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like And other mixed solvents.

烷、甲基溶纖劑、丙二醇單甲基醚、甲基乙基酮、甲基異丁基酮、甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等。 Among these, aromatic hydrocarbons, halides, esters, ethers, ketones, alcohols, amidines, etc. are preferred, and benzene, toluene, xylene, o-dichlorobenzene, and acetic acid are particularly preferred. Ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, 1,4-bis

Alkane, methyl cellosolve, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, third butane Alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

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

The blending amount of the organic solvent can be appropriately selected according to the molecular weight of the high branched polymer of the object. For example, when designing a high-molecular-weight, high-branched polymer, the amount of organic solvent can be reduced (concentration of the polymerizable compound in the solvent becomes higher). Conversely, when designing a low-molecular-weight, high-branched polymer, the organic solvent can be increased (the solvent The concentration of the polymerizable compound in the mixture becomes lower).

The polymerization reaction is carried out at normal pressure, under pressure, or under reduced pressure. From the standpoint of simplicity of equipment and operation, it is preferably carried out at normal pressure. In addition, it is preferably performed in an inert gas environment such as N ₂ .

The polymerization temperature may be arbitrary as long as it is equal to or lower than the boiling point of the reaction mixture, but from the viewpoint of adjusting the polymerization efficiency and molecular weight, it is preferably 50 to 200 ° C, and more preferably 70 to 150 ° C.

The polymerization reaction is more preferably carried out at the reflux temperature of the organic solvent under the reaction pressure, that is, it is preferred that the solution containing the polymerizable compound, the polymerizable initiator, and the organic solvent is dropped to a reflux state after being dropped. In this organic solvent, a polymerization reaction is performed.

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 desired), the polymerization initiator C, and the type of organic solvent used in the polymerization. It cannot be specified in general, but it is preferably 30 to 720 minutes, and more preferably 40 to 540 minutes.

After the completion of the polymerization reaction, the obtained highly branched polymer is recovered by an arbitrary method, and after-treatments such as washing are performed if necessary. Examples of a method for recovering a polymer from a reaction solution include a method such as reprecipitation.

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

Among the highly-branched polymers used in the present invention, a particularly preferable example is a highly-branched polymer formed by a polymer constituting a polymer chain including at least the aforementioned structural part represented by the formula [1] and the formula [2]. Examples include: in the formula [1], R ₁ , R ₂ , R ₅ and R ₆ represent hydrogen atoms, R ₃ and R ₄ represent hydrogen atoms or methyl groups, and A ₁ represents phenylene or tricyclic [5.2] .1.0 ^2,6 ] decane-4,8-diyl-bis (methoxycarbonyl) group, in formula [2], R ₇ , R ₈ and R _{9 each} represent a hydrogen atom, and R ₁₀ and R ₁₁ each Independently represents a hydrogen atom or a methyl group, or R ₁₀ and R _{11 are} joined together to represent a normal propyl group, which is incorporated at the end of the polymer chain by 2,2'-azobis (2-methylbutyronitrile) and dimethyl A highly branched polymer obtained by radically cleaving a fragment of a polymerization initiator C selected from the group 2,2'-azobis (2-methylpropionate).

<(b) Metal particles>

The (b) metal fine particles used in the primer of the present invention are not particularly limited. Examples of the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and palladium. (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold (Au), and alloys thereof, may be used for this purpose One type of metal may be an alloy of two or more types. Among them, as the metal fine particles, palladium fine particles are mentioned. In addition, as the metal fine particles, an oxide of the aforementioned metal may be used.

The metal fine particles can be obtained by reducing a metal ion 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. For example, by adding a solution of a metal salt to a solution in which the above-mentioned high-branched polymer is dissolved, and irradiating ultraviolet rays thereto, or adding a solution of a metal salt and a reducing agent to the solution, metal ions can be reduced to form high A composite of a branched polymer and metal fine particles, while preparing a primer containing a high branched polymer and metal fine particles.

Examples of the metal salt include chloroauric acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, platinum chloride, chloroplatinic acid, and Pt (dba) ₂ [dba = dibenzylideneacetone] , Pt (cod) ₂ [cod = 1,5-cyclooctadiene], Pt (CH ₃ ) ₂ (cod), palladium chloride, palladium acetate (Pd (OC (= O) CH ₃ ) ₂ ), nitric acid Palladium, Pd ₂ (dba) ₃ . CHCl ₃ , Pd (dba) ₂ , rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru (cod) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni (cod) ₂ etc.

The reducing agent is not particularly limited, and various reducing agents can be used. The reducing agent is preferably selected according to the metal species and the like contained in the obtained primer. Examples of usable reducing agents include hydrogenated boron hydride metal salts such as sodium borohydride, potassium borohydride, and the like; hydrogenation of lithium aluminum hydride, potassium aluminum hydride, aluminum cesium hydride, aluminum beryllium, magnesium aluminum hydride, and calcium aluminum hydride. Aluminum salt Compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary alcohols such as methanol, ethanol, isopropanol, and polyols; trimethylamine, triethylamine, diisopropylethyl Tertiary amines such as amines, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; tri-n-propylphosphine, tri-n-butylphosphine, tricyclohexyl Phosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane [DPPE], 1,3-bis (diphenylphosphino) propane [ DPPP], 1,1'-bis (diphenylphosphino) ferrocene [DPPF], 2,2'-bis (diphenylphosphino) -1,1'-binaphtyl [BINAP], etc. Class, etc.

The average particle diameter of the metal fine particles is preferably 1 to 100 nm. Since the average particle diameter of the metal fine particles is 100 nm or less, the reduction in surface area is small, and sufficient catalyst 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 (a) highly branched polymer in the primer of the present invention is preferably 20 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the metal particles (b). With respect to (b) 100 parts by mass of the metal fine particles, the amount of the (a) highly branched polymer added is 20 parts by mass or more, so that the metal fine particles can be sufficiently dispersed. The dispersibility of the metal fine particles is insufficient, and precipitates or aggregates are liable to occur. It is more preferably 30 parts by mass or more. In addition, if 10,000 parts by mass or more of the (a) high-branched polymer is added to 100 parts by mass of the (b) metal fine particles, the amount of Pd per unit area after coating becomes insufficient, resulting in plating precipitation. Worry of reduction.

<(c) Amine compound>

As the (c) amine compound used in the electroless plating primer of the present invention, a known one can be used, and examples thereof include aliphatic amines such as alkylamines and hydroxyalkylamines, and cyclic substituents. Amines, aromatic amines (arylamines), and amine compounds having an alkoxysilyl group. Among these amine compounds, an amine compound having an alkoxysilyl group is preferred. From the viewpoint of improving the storage stability of the plating primer, the amine group of the amine compound is preferably protected by a ketone (protected by an alkylene group). In the present invention, the amine group is protected by an alkylene group. The amine compound or amine compound protected by the group is contained in the component (c). When the amine compound protected by an alkylene group is used as the component (c), the solvent for the primer described later is not an alcohol solvent capable of removing the protection of the alkylene group, but ketones, Solvents for ethers and esters.

In the present invention, by blending (c) an amine compound in an electroless plating primer, metal fine particles, a composite of metal fine particles and a highly branched polymer described later in detail are obtained in the primer. The effect of increasing the dispersion stability and contributing to the formation of fine plating patterns. In addition, since the amine compound protected by an alkylene group is protected by an electroless plating solution, the amine compound protected by an alkylene group can be used as the component (c).

Examples of the alkylamines include ethylamine (CH ₃ CH ₂ NH ₂ ), propylamine (CH ₃ (CH ₂ ) ₂ NH ₂ ), butylamine (CH ₃ (CH ₂ ) ₃ NH ₂ ), and pentylamine (CH ₃ (CH ₂ ) ₄ NH ₂ ), hexylamine (CH ₃ (CH ₂ ) ₅ NH ₂ ), heptylamine (CH ₃ (CH ₂ ) ₆ NH ₂ ), octylamine (CH ₃ (CH ₂ ) ₇ NH ₂ ), nonylamine (CH ₃ (CH ₂ ) ₈ NH ₂ ), decylamine (CH ₃ (CH ₂ ) ₉ NH ₂ ), undecylamine (CH ₃ (CH ₂ ) ₁₀ NH ₂ ), dodecylamine (CH ₃ (CH ₂ ) ₁₁ NH ₂ ), tridecylamine (CH ₃ (CH ₂ ) ₁₂ NH ₂ ), tetradecylamine (CH ₃ (CH ₂ ) ₁₃ NH ₂ ), pentaamine (CH ₃ (CH ₃ (CH 2 ₂ ) ₁₄ NH ₂ ), hexadecylamine (CH ₃ (CH ₂ ) ₁₅ NH ₂ ), heptaamine (CH ₃ (CH ₂ ) ₁₆ NH ₂ ), octadecylamine (CH ₃ (CH ₂ ) ₁₇ NH ₂ ), Undecylamine (CH ₃ (CH ₂ ) ₁₈ NH ₂ ), eicosylamine (CH ₃ (CH ₂ ) ₁₉ NH ₂ ), and structural isomers of these primary amines; N, N-di Secondary amines such as methylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine; trimethylamine, triethylamine, tripropylamine, tributylamine And other tertiary amines.

Examples of the hydroxyalkylamines (alkanolamines) include methanolamine (OHCH ₂ NH ₂ ), ethanolamine (OH (CH ₂ ) ₂ NH ₂ ), and propanolamine (OH (CH ₂ ) ₃ NH ₂ ), Butanolamine (OH (CH ₂ ) ₄ NH ₂ ), pentanolamine (OH (CH ₂ ) ₅ NH ₂ ), hexanolamine (OH (CH ₂ ) ₆ NH ₂ ), heptanolamine (OH ( CH ₂ ) ₇ NH ₂ ), octanolamine (OH (CH ₂ ) ₈ NH ₂ ), nonanolamine (OH (CH ₂ ) ₉ NH ₂ ), decanolamine (OH (CH ₂ ) ₁₀ NH ₂ ), Undecanolamine (OH (CH ₂ ) ₁₁ NH ₂ ), Dodecanolamine (OH (CH ₂ ) ₁₂ NH ₂ ), Tridecanolamine (OH (CH ₂ ) ₁₃ NH ₂ ), Tetradecanolamine ( OH (CH ₂ ) ₁₄ NH ₂ ), Pentadecanolamine (OH (CH ₂ ) ₁₅ NH ₂ ), Hexadecanolamine (OH (CH ₂ ) ₁₆ NH ₂ ), Heptadecanolamine (OH (CH ₂ ) ₁₇ NH ₂ ), stearylamine (OH (CH ₂ ) ₁₈ NH ₂ ), nonadecanylamine (OH (CH ₂ ) ₁₉ NH ₂ ), eicosanolamine (OH (CH ₂ ) ₂₀ NH ₂ ), etc. Primary amines; N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine , N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethyl base An alcohol amine, N- propyl alcohol amine, N- butyl alcohol amines like secondary amines.

Examples of other aliphatic amines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, and ethoxylate. Propylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, butylamine Alkoxyalkylamines such as oxybutylamine.

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

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

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

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

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) propyl] -1,2-ethanediamine, bis- [3- (trimethoxysilyl) propyl] amine, bis- [3- ( Triethoxysilyl) propyl) Amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxy Silyl, trimethoxy [3- (methylamino)] propylsilane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-allylamino) propyl Triethoxysilane, 3- (diethylamino) propyltrimethoxysilane, 3- (diethylamino) propyltriethoxysilane, 3- (phenylamino) propyl Compounds such as trimethoxysilane and 3- (phenylamino) propyltriethoxysilane.

In addition, specific examples of the alkylamines, hydroxyalkylamines, other aliphatic amines, amines having cyclic substituents, aromatic amines (arylamines), and alkoxy groups are given above. Examples of the silane-based amine compound include an amine-based amine compound protected by an alkylene group by a ketone such as methyl ethyl ketone or methyl isobutyl ketone.

The content of the (c) amine compound in the primer of the present invention is relative to the complex formed by the aforementioned high-branched polymer and metal fine particles (or the total mass of the aforementioned high-branched polymer and metal fine particles) described later. 100 parts by mass, preferably 0.01 to 500 parts by mass, more preferably 0.1 to 300 parts by mass, and particularly preferably 1 to 100 parts by mass.

(c) When the content of the amine compound is too small compared to the above numerical range, the dispersibility and solubility stabilization effect of the complex formed by the aforementioned high-branched polymer and metal fine particles, which will be described later, cannot be obtained. In the range (e.g., 10 times the amount of the above-mentioned composite, etc.), not only the plating bath is contaminated or destroyed, but also the appearance of the plating film is poor.

<Primer>

The electroless plating primer of the present invention includes the (a) highly branched polymer and (b) metal fine particles, and (c) an amine compound and other components as necessary. In the electroless plating primer of the present invention, it is preferred that the high-branched polymer and the metal fine particles form a composite, that is, the primer is preferably composed of the high-branched polymer and the metal fine particles. The complex formed.

The so-called complex here refers to the presence of the amine group on the side chain of the high-branched polymer, and the two coexist in a state of contact with or close to the metal fine particles to form a particulate form, in other words, to have metal fine particles A complex having a structure in which an amido group is attached or coordinated to the aforementioned high-branched polymer is shown.

The "attachment or coordination structure" as used herein refers to a state in which a part or all of the amidino group of the highly branched polymer interacts with the metal fine particles. For example, when a palladium salt is used as a metal atom, it is judged that the amido group and the palladium salt form a structure shown in (a) or (b) below (L in the formula is a ligand). Therefore, when palladium fine particles are used as the metal fine particles, it is judged that a structure in which a high-branched polymer surrounds the metal fine particles is formed by the interaction between the Pd atom on the surface layer and the amido group.

Therefore, in the "composite" of the present invention, not only the metal fine particles and the high-branched polymer are combined to form a composite body as described above, but also the metal fine particles and the high-branched polymer do not form a bonded portion, and are independent of each other. Existence (apparently, it can be regarded as one who forms one particle).

Since the structural part represented by the formula [1], the formula [2], and the formula [3] contained in the polymer chain of the (a) highly branched polymer of the present invention does not have an active proton that reduces Pd atoms or At the site where the Pd atom is crosslinked, the (a) highly branched polymer of the present invention can form a stable complex with the (b) metal fine particles through the amidine group.

The formation of the complex of (a) the high-branched polymer and (b) the metal fine particles is carried out at the same time when the undercoating agent containing the high-branched polymer and the metal fine particles is prepared. Metal particles that have been stabilized to a certain extent via lower ammonium ligands are formed by exchanging ligands with high-branched polymers or in solutions of high-branched polymers by directly reducing metal ions. Complex approach. As described above, by adding a solution of a metal salt to a solution in which the high-branched polymer is dissolved, ultraviolet rays are radiated to the solution, or a metal salt is added to the solution. Solution and reducing agent, etc., and metal ions can be reduced to form a complex.

In the ligand exchange method, metal particles that have been stabilized to a certain degree by a lower ammonium ligand as a raw material can be a method described in Jounal of Organometallic Chemistry 1996, 520, 143-162 and the like. By dissolving the aforementioned high-branched polymer in the reaction mixture solution of the obtained metal fine particles, the target metal fine particle composite can be obtained by stirring at room temperature (about 25 ° C) or heating.

The solvent to be used is not particularly limited as long as it can dissolve the metal fine particles and the high-branched polymer to a concentration higher than necessary, but specific examples thereof include ethanol, n-propanol, and 2-propanol. And other alcohols; halogenated hydrocarbons such as dichloromethane and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile, butyronitrile, and the like The solvent mixture is preferably tetrahydrofuran.

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

In the ligand exchange method, in addition to the amine-based dispersant (lower ammonium ligand), the use of a phosphine-based dispersant (phosphine ligand) can stabilize the metal fine particles to a certain degree in advance.

As a direct reduction method, the target metal can be obtained by dissolving a metal ion and a highly branched polymer in a solvent and reducing it with a primary or secondary alcohol such as methanol, ethanol, 2-propanol, or a polyol. Microparticle complex.

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

The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving metal ions and a high-branched polymer having an amidine group to a concentration higher than necessary, but specific examples include methanol, ethanol, and Alcohols such as propanol, 2-propanol; halogenated hydrocarbons such as dichloromethane, chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran; acetonitrile, butyronitrile, etc. Nitriles; N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), etc. amidines; dimethylene, etc. Examples of the solvent mixture include alcohols, halogenated hydrocarbons, and cyclic ethers. More preferred examples include ethanol, 2-propanol, chloroform, and tetrahydrofuran.

The temperature of the reduction reaction (mixing metal ions and high-branched polymer) may be generally in the range of 0 ° C to the boiling point of the solvent, and preferably in the range of room temperature (about 25 ° C) to 60 ° C.

As another direct reduction method, by dissolving metal ions and highly branched polymers in a solvent and reacting under a hydrogen environment, a target metal microparticle composite can be obtained.

As the metal ion source used herein, the above-mentioned metal salt, or chromium hexacarbonyl [Cr (CO) ₆ ], iron pentacarbonyl [Fe (Co) ₅ ], and dicobalta octacarbonyl [Co ₂ (CO) _{8 can be used.} ], Metal tetracarbonyl complexes such as nickel tetracarbonyl nickel [Ni (CO) ₄ ]. A zero-valent metal complex such as a metal olefin complex, a metal phosphine complex, or a metal nitrogen complex may also be used.

The solvent to be used is not particularly limited as long as it can dissolve metal ions and the high branched polymer to a concentration higher than necessary, but Specific examples include alcohols such as ethanol and propanol; halogenated hydrocarbons such as dichloromethane and chloroform; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran; acetonitrile and butyronitrile Tetrahydrofuran is preferably used as the mixed liquid of such nitriles and the like and these solvents.

Mixing metal ions with high branched polymer temperatures usually ranges from 0 ° C to the boiling point of the solvent.

As a direct reduction method, by dissolving metal ions and a high-branched polymer in a solvent and performing a thermal decomposition reaction, a target metal fine particle composite can be obtained.

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

The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving metal ions and the high-branched polymer to a concentration higher than necessary, but specific examples include methanol, ethanol, n-propanol, and isopropyl alcohol. Alcohols such as alcohols and glycols; halogenated hydrocarbons such as dichloromethane and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile As the mixed liquid of aromatic hydrocarbons such as benzene and toluene, and these solvents, toluene is preferably used.

The temperature at which the metal ions and the high-branched polymer having an amidine group are mixed can generally be in the range of 0 ° C to the boiling point of the solvent, preferably near the boiling point of the solvent, for example, 110 ° C (heated to reflux) in toluene.

The composite of the highly branched polymer and the metal fine particles obtained in this way can be subjected to a refining treatment such as reprecipitation to become a solid such as a powder. The form of things.

The primer of the present invention contains the aforementioned (a) highly branched polymer and (b) metal fine particles (preferably a complex formed by them), and further includes (c) an amine compound and other components as necessary, This primer may be in the form of a varnish used in the formation of the [undercoat layer for electroless metal plating] described later.

<Other additives>

The primer of the present invention is within a range that does not impair the effects of the present invention, and additives such as a surfactant, various surface modifiers, and a tackifier may be more suitably added.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; and Polyoxyethylene alkyl aryl ethers such as oxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene ‧ polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan Sorbitan fatty acid esters such as alkanol monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, etc .; poly Polyoxyethylene nonionics such as oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, etc. Series surfactants; Eftop (registered trademark) EF-301, same as EF-303, same as EF-352 [above, Mitsubishi Materials Electrochemical Corporation (Stock)], Megafac (registered trademark) F-171, same as F-173, Same as R-08, same as R-30 [above, DIC (stock) system], Novec (registered trademark) FC-430, same as FC-431 [above, Sumitomo 3M (stock) system], Asahi Guard (registered trademark) AG-710 [Asahi Glass (stock) system], Surflon ( (Registered trademark) S-382 [AGC Semichemical (manufactured)] and other fluorine-based surfactants.

Examples of the surface modifier include a silicone leveling agent such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Industry Co., Ltd.]; BYK (registered trademark) -302, same as 307, Polysilicone-based surface modifiers such as 322, 323, 330, 333, 370, 375, and 378 [above, manufactured by BYK Chemical Co., Ltd.].

Examples of the tackifiers include polyacrylics (including crosslinked ones) that form carboxyvinyl polymers (carbomers); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and polyvinyl acetate Polyvinyl polymers such as esters (PVAc), polystyrene (PS); polyethylene oxides; polyesters; polycarbonates; polyamines; polyurethanes; dextrin, agar, cara Gum, alginic acid, acacia gum, guar gum, tragacanth gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other polysaccharides; gelatin, Casein and other proteins. In addition, each of the polymers includes not only homopolymers but also copolymers. These thickeners may be used singly or in combination of two or more kinds.

The primer of the present invention can adjust the viscosity or rheological properties of the primer by blending a tackifier as needed. ‧ Choices are suitable for local use and other purposes.

These additives may be used singly or in combination of two or more kinds. The amount of the additive is preferably 0.001 to 50 parts by mass, more preferably 0.005 to 10 parts by mass, and even more preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the composite formed of the aforementioned high-branched polymer and metal fine particles. Parts by mass.

[Undercoat for electroless metal plating]

The above-mentioned electroless plating primer of the present invention can form an undercoat layer for electroless metal plating by coating on a substrate. This electroless metal plating undercoat is also the subject of the present invention.

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

Examples of the non-conductive substrate include glass, ceramics, and the like; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyimide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene terephthalate) resin, PEEK (polyetheretherketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, Epoxy resin, polyacetal resin, etc .; paper, etc. These are suitably used in the form of a sheet or a film, and the thickness at this time 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), and GZO. (Gallium-doped zinc oxide), There are also various aluminum alloys such as stainless steel, aluminum, and Dura aluminum, iron and iron alloys, copper and brass, phosphor bronze, copper, beryllium copper, and other copper alloys, nickel and nickel alloys, and silver alloys such as silver and nickel-silver. And other metals.

Furthermore, a substrate on which a thin film is formed on such a non-conductive substrate may be used.

The substrate may be a three-dimensional molded body.

As an electroless plating base coat containing the (a) highly branched polymer and (b) metal fine particles (preferably a complex formed by the above), (c) an amine compound and other components as necessary A specific method for forming an undercoat layer for electroless metal plating by using an agent, firstly, the aforementioned high-branched polymer and metal particles (preferably a complex formed by them) (with an amine compound and other components as needed) Dissolved or dispersed in a suitable solvent to form a varnish, by spin coating method; doctor blade coating method; dip coating method; roll coating method; rod coating method; die coating method; spraying method; inkjet method; ink Pen lithography such as pen nanolithography (FPN), dip pen nanolithography (DPN), etc .; letterpress printing, flexographic printing, resin letterpress printing, contact printing, microcontact printing (μCP), nano Letterpress printing methods such as imprint lithography (NIL), nano transfer printing (nTP), etc .; gravure printing methods such as gravure printing, engraving, etc .; lithographic printing methods; stencil printing methods such as screen printing, transcription, etc .; offset printing Method, etc., this varnish is applied to a substrate forming a metal plating film, and then ‧ drying agent was evaporated to form a thin layer.

Among these coating methods, spin coating, spraying, inkjet, pen lithography, contact printing, μCP, NIL, and nTP are preferred. When using the spin coating method, it can be applied for a short time, even if it is volatile A high solution is also available, and it has the advantage of being able to perform coating with high uniformity. When the spray method is used, a very small amount of varnish can be applied with high uniformity, which is very advantageous industrially. When inkjet method, pen lithography, contact printing, μCP, NIL, nTP are used, for example, fine patterns such as wiring can be efficiently formed (drawn), which is very advantageous industrially.

烷、二乙基醚等的醚類；醋酸乙酯、醋酸丁酯等的酯類；丙酮、甲基乙基酮(MEK)、甲基異丁基酮(MIBK)、環戊酮、環己酮等的酮類；正庚烷、正己 烷、環己烷等的脂肪族烴類；1,2-二氯乙烷、氯仿等的鹵化脂肪族烴類；N-甲基-2-吡咯啶酮(NMP)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺等的醯胺類；二甲亞碸等。此等溶劑係可單獨使用，也可混合2種類以上的溶劑。再者，以調整清漆的黏度為目的，亦可添加乙二醇、丙二醇、丁二醇等的二醇類。還有如前述，使用胺基經亞烷基保護的胺化合物作為(c)胺化合物時，避免使用能去除該保護基的醇溶劑，宜使用酮類、醚類、酯類等作為溶劑。 The solvent used herein is not particularly limited as long as it can dissolve or disperse the complex, the desired amine compound, and other components. For example, water can be used; benzene, toluene, xylene, and ethylbenzene. , Chlorobenzene, dichlorobenzene and other aromatic hydrocarbons; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n-hexanol, n-octanol, 2-octanol, 2-ethyl alcohol Alcohols such as methylhexanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, etc .; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether , Propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol Alcohol 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 Glycol ethers such as ethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tripropylene glycol dimethyl ether ; Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) glycol esters and the like; tetrahydrofuran (THF), methyltetrahydrofuran, 1,4-bis

Ethers such as alkane, diethyl ether; esters such as ethyl acetate, butyl acetate; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexane Ketones such as ketones; aliphatic hydrocarbons such as n-heptane, n-hexane, cyclohexane; halogenated aliphatic hydrocarbons such as 1,2-dichloroethane, chloroform; N-methyl-2-pyrrolidine Ketones (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide and other amidines; dimethylarsin and the like. These solvents may be used alone, or two or more 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. Also, as mentioned above, when using an amine compound having an amine group protected by an alkylene group as the (c) amine compound, avoid using an alcohol solvent capable of removing the protective group, and preferably use a ketone, ether, ester, or the like as a solvent.

In addition, the concentration dissolved or dispersed in the solvent is arbitrary, but the concentration of non-solvent components in the varnish [all components except the solvent contained in the primer (high-branched polymers and metal fine particles (preferably from The concentration of the complex formed by these), the desired amine compound and other components, etc.] is 0.05 to 90% by mass, preferably 0.1 to 80% by mass.

The drying method for the solvent is not particularly limited. For example, a hot plate or an oven can be used to evaporate under a suitable environment, that is, an inert gas such as the atmosphere, nitrogen, or a vacuum. Thereby, an undercoat layer having a uniform film-forming surface can be obtained. 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 coating, metal coating substrate]

A metal plating film is formed on the undercoat layer by subjecting the undercoat layer of the electroless metal plating formed on the substrate to the electroless plating as described above. The metal plating film thus obtained and non-electrolytic in order on the substrate The undercoat layer for metal plating and the metal film substrate for metal plating are also the objects of the present invention. The electroless plating process (step) is not particularly limited, and may be performed by any generally known electroless plating process. For example, a conventionally known electroless plating solution is generally used, and the plating solution (bath) is immersed in the plating solution (bath). Method for forming an undercoat layer of electroless metal plating on a substrate.

The aforementioned electroless plating solution mainly contains metal ions (metal salts), distorting agents, and reducing agents, and may suitably include a pH adjusting agent, a pH buffering agent, a reaction accelerator (second dissolving agent), and a stabilizer in combination with other applications. Surfactants (application of gloss to plated film, application of improving wettability of treated surface, etc.) and the like.

Here, examples of the metal used in the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, and they can be appropriately selected according to the purpose. select.

Moreover, the said dislocation agent and reducing agent can also be suitably selected according to a metal ion.

A commercially available plating solution can also be used as the electroless plating solution. For example, electroless nickel plating products (Melplate (registered trademark) NI series) and electroless copper plating products (Melplate (registered trademark) made by MELTEX) can be suitably used. ) CU series); electroless nickel plating solution (ICP Nicoron (registered trademark) series, Topiena 650), electroless copper plating solution (OPC-700 electroless copper MK, ATS Adcopper IW, the same CT, OPC copper (registered trademark) AF series, same HFS, same NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (Flashgold 330, (Selfold OTK-IT), electroless silver plating solution (Mudensilver); electroless palladium plating solution (Pallet II), electroless gold plating solution (Dip G series, NC Gold series) made by Kojima Chemical Co., Ltd .; Sasaki Chemicals Electroless silver plating solution (S-DIA AG-40) made by Japan (K-Gen); Electroless nickel plating solution made by KANIGEN (Japan) (Kanigen (registered trademark) series, Sumer (registered trademark) series, Sumer (registered trademark) ), Kaniblack (registered trademark) series), electroless palladium plating solution (S-KPD); electroless copper plating solution (Cuposit (registered trademark) Coppermix series, Circuposit (registered trademark) series) manufactured by DOW Chemical Co., Ltd. Palladium plating solution ((Paramasu (registered trademark) series), electroless nickel plating solution (Duraposit (registered trademark) series), electroless gold plating solution (Aurolectroless (registered trademark) series), electroless tin plating solution (Denposit (registered trademark) ) Series); electroless copper plating solution (Thrucup (registered trademark) ELC-SP, same PSY, same PCY, same PGT, same PSR, same PEA, and PMK), manufactured by Uemura Industrial Co., Ltd., ADTEC Japan (stock) Made of electroless copper plating solution (Printgant (registered trademark) PV, same as PVE).

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

Examples

Hereinafter, the present invention will be described more specifically by way of examples. The invention is not limited to this. In the examples, the measurement of the physical properties of the samples was performed under the following conditions using the following apparatus.

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

Installation: HLC-8220GPC made by Tosoh

Column: Shodex (registered trademark) KF-804L + KF-803L made by Showa Denko Corporation

Column temperature: 40 ℃

Solvent: Tetrahydrofuran

Detector: UV (254nm), RI

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

Installation: HLC-8220GPC made by Tosoh

Column: Shodex (registered trademark) KF-804L + KF-803L made by Showa Denko Corporation

Column temperature: 40 ℃

Solvent: DMF

Detector: UV (254nm), RI

(3) ¹³ C NMR spectrum

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

Solvent: CDCl ₃

Ease test: Cr (acac) ₃

Benchmark: CDCl ₃ (77.0ppm)

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

Device: ICPM-8500 manufactured by Shimadzu Corporation

(5) TEM (transmission electron microscope) image

Device: (share) Hitachi high-tech H-8000

(6) 5% weight reduction temperature

Device: (share) RIGAKU differential thermal balance TG8120

Measurement conditions: under air environment

Heating rate: 10 ℃ / min (25 ~ 500 ℃)

The abbreviations indicate the following meanings.

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

DVB: Divinylbenzene [Nippon Steel Chemical Co., Ltd. DVB-960]

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

NVA: N-vinylacetamide [manufactured by Showa Denko]

MCS: Methyl Cellosolve

DIPE: Diisopropyl ether

V-59: 2,2’-azobis (2-methylbutyronitrile)

KBM-903: 3-aminopropyltrimethoxysilane (made by Shin-Etsu Chemical Industry Co., Ltd.)

KBM-9103: 3-trimethoxysilyl-N- (1,3-dimethylbutylene) propylamine (made by Shin-Etsu Chemical Industry Co., Ltd.)

[Reference Example 1] Preparation of Electroless Copper Plating Solution

In a 1L flask, Cuposit (registered trademark, the same below) Coppermix 328A [DOW Chemical Co., Ltd.] 125mL, Cuposit Coppermix 328L [DOW Chemical Co., Ltd.] 125mL, and Cuposit were added. 15 mL of Coppermix 328C [manufactured by Dow Chemical Co., Ltd.] was added pure water to make the total solution 1L.

[Reference Example 2] Preparation of Electroless Nickel Plating Solution

In a 1 L flask, 100 mL of Bluesumer [manufactured by KANIGEN] was added, and pure water was further added to make the total amount of the solution 500 mL.

[Polymerization Example 1: Production of High Branch Polymer 1 Using DVB, NVP, V-59]

97.6 g of MCS was added to a 300 mL reaction flask, and nitrogen was flowed in for 5 minutes while stirring, and heated until the internal liquid refluxed (about 130 ° C).

In another 200 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 8.34 g (75 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as starter C, and MCS were added. 68.3g, nitrogen was flowed in for 5 minutes while stirring to perform nitrogen substitution, and cooled in an ice bath until 0 ° C.

In the refluxing MCS in the aforementioned 300 mL reaction flask, the contents were dropped from the aforementioned 100 mL reaction flask containing DVB, NVP, and V-59 using a drip pump for 30 minutes. After completion of the dropping, the mixture was stirred for 1 hour.

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

The obtained target substance had a weight average molecular weight Mw measured by GPC of polystyrene of 8,900, and a degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) of 3.8.

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

In a 200 mL reaction flask, 122.8 g of MCS was added, and nitrogen was flowed in for 5 minutes while stirring, and heated until the internal liquid refluxed (about 130 ° C).

In another 100 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 11.11 g (100 mmol) of NVP as monomer B, 19.23 g (100 mmol) of V-59 as starter C, and MCS were added. 85.99g, nitrogen was flowed in for 5 minutes while stirring to perform nitrogen substitution, and cooled in an ice bath until 0 ° C.

In the refluxing MCS in the aforementioned 200 mL reaction flask, the contents were dropped from the aforementioned 100 mL reaction flask containing DVB, NVP, and V-59 using a drip pump for 30 minutes. After completion of the dropping, the mixture was stirred for 1 hour.

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

The obtained target substance had a weight average molecular weight Mw measured by GPC of polystyrene of 2,600, and a degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.8.

[Polymerization Example 3: Production of High Branch Polymer 3 Using DVB, NVP, V-59]

In a 200 mL reaction flask, 106.8 g of MCS was added, and nitrogen was flowed in for 5 minutes while stirring, and heated until the internal liquid refluxed (about 130 ° C).

In another 100 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 11.11 g (100 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as starter C, and MCS were added. 74.74 g, nitrogen was flowed in for 5 minutes while stirring to perform nitrogen substitution, and cooled in an ice bath until 0 ° C.

In the refluxing MCS in the aforementioned 200 mL reaction flask, the contents were dropped from the aforementioned 100 mL reaction flask containing DVB, NVP, and V-59 using a drip pump for 30 minutes. After completion of the dropping, the mixture was stirred for 1 hour.

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

The obtained target substance had a weight average molecular weight Mw measured by GPC of polystyrene of 7,500, and a degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) of 2.6.

[Polymerization Example 4: Production of highly branched polymer 4 using DCP, NVP, V-59]

In a 200 mL reaction flask, 159.0 g of MCS was added, and nitrogen was flowed in for 5 minutes while stirring, and heated until the internal liquid refluxed (about 130 ° C).

In another 100 mL reaction flask, 16.6 g (50 mmol) of DCP as monomer A, 16.67 g (150 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as starter C, and MCS were added. 111.28 g, nitrogen gas was flowed in for 5 minutes while stirring to perform nitrogen substitution, and cooled in an ice bath until 0 ° C.

In the refluxing MCS in the aforementioned 200 mL reaction flask, the contents were dropped from the aforementioned 100 mL reaction flask to which DCP, NVP, and V-59 were added, using a drip pump for 30 minutes. After completion of the dropping, the mixture was stirred for 1 hour.

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

The obtained target substance had a weight average molecular weight Mw measured by GPC of polystyrene of 10,200, and a degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) of 3.4.

[Polymerization Example 5: Production of High Branch Polymer 5 Using DVB, NVA, V-59]

In a 200 mL reaction flask, 126.5 g of MCS was added, and nitrogen was flowed in for 5 minutes while stirring, and heated until the internal liquid refluxed (about 130 ° C).

In another 100 mL reaction flask, add 6.51 g (50 mmol) of DVB, 17.02 g (200 mmol) of NVA as monomer B, 14.42 g (75 mmol) of V-59 as starter C, and 88.55 g of MCS, and nitrogen was flowed in while stirring for 5 minutes to perform nitrogen substitution. Cool in an ice bath until 0 ° C

In the refluxing MCS in the aforementioned 200 mL reaction flask, the contents were dropped from the aforementioned 100 mL reaction flask containing DVB, NVA, and V-59 using a drip pump for 30 minutes. After completion of the dropping, the mixture was stirred for 1 hour.

Next, this reaction liquid was added to 1,275 g, and the polymer was precipitated in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 17.23 g (yield 45.5%) of the desired product (high-branched polymer 5) as a white powder.

The obtained target substance had a weight average molecular weight Mw measured by GPC of polystyrene of 9,300, and a degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) of 4.9. The ¹³ C NMR spectrum of the target is shown in FIG. 1.

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

In a 200 mL reaction flask, 143.87 g of MCS was added, and nitrogen was flowed in for 5 minutes while stirring, and heated until the internal liquid refluxed (about 130 ° C).

In another 100 mL reaction flask, 6.51 g (50 mmol) of DVB as monomer A, 22.23 g (200 mmol) of NVP as monomer B, and 14.42 g (75 mmol) of V-59 as starter C were added. And MCS 100.71g, nitrogen was flowed in for 5 minutes while stirring, and then replaced with nitrogen, and cooled in an ice bath until 0 ° C.

In the refluxing MCS in the aforementioned 200 mL reaction flask, the contents were dropped from the aforementioned 100 mL reaction flask containing DVB, NVP, and V-59 using a drip pump for 30 minutes. After completion of the dropping, the mixture was stirred for 1 hour.

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

The obtained target substance had a weight average molecular weight Mw measured by GPC of polystyrene of 11,300, and a degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) of 3.6. The ¹³ C NMR spectrum of the target is shown in FIG. 2.

[Polymerization Example 7: Production of highly branched polymer 7 using DCP, NVP, V-59]

In a 200 mL reaction flask, 196.0 g of MCS was added, and nitrogen was flowed in for 5 minutes while stirring, and heated until the internal liquid refluxed (about 130 ° C).

In another 100 mL reaction flask, 16.60 g (50 mmol) of DCP as monomer A, 27.79 g (250 mmol) of NVP as monomer B, 14.42 g (75 mmol) of V-59 as starter C, and MCS were added. 137.22 g, nitrogen gas was flowed in for 5 minutes while stirring to perform nitrogen substitution, and cooled in an ice bath until 0 ° C.

In the refluxing MCS in the aforementioned 200 mL reaction flask, the contents were dropped from the aforementioned 100 mL reaction flask to which DCP, NVP, and V-59 were added, using a drip pump for 30 minutes. After completion of the dropping, the mixture was stirred for 1 hour.

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

The obtained target substance had a weight average molecular weight Mw measured by GPC of polystyrene of 12,800, and a dispersion degree: Mw (weight average molecular weight) / Mn (number average molecular weight) of 3.0. The ¹³ C NMR spectrum of the target is shown in FIG. 3.

[Manufacturing example: Synthesis of Pd fine particle complex (10 g scale)]

The composite was prepared by the following procedure so that the Pd fine particle content (theoretical value) in the Pd fine particle-high branched polymer composite became 30% by weight. As the high-branched polymer, the above-prepared high-branched polymer 5 to high-branched polymer 7 were used.

In a reaction flask provided with a cooler, 6.36 g of palladium acetate [Pd (OAc) ₂ , manufactured by Kawaken Fine Chemicals Co., Ltd.] and 63.56 g (amount of chloroform) of chloroform were added and stirred until homogeneous. In addition, a solution in which 7.0 g of the highly branched polymer was dissolved in 70.00 g (amount of B) of chloroform was added to a reaction flask containing palladium acetate using a dropping funnel. In this dropping funnel, 10.00 g (amount of C) of chloroform and 95.71 g of ethanol were used to wash the reaction funnel. This mixture was stirred at 60 ° C for 6 hours under a nitrogen atmosphere.

After cooling to a liquid temperature of 30 ° C, this solution was added to 1,196.33 g of IPE, and the mixture was further refined. The precipitated polymer was filtered under reduced pressure and vacuum-dried at 50 ° C. to obtain a composite of a high-branched polymer having a fluorenyl group in a side chain and Pd particles.

Using the component amounts shown in Table 1 below, the polymers were replaced with highly branched polymer 6 (HB-DVB-NVP-V59) [complex 1 to complex 4], and high branch polymer 7 ( HB-DCP-NVP-V59) [complex 5 ~ complex 8], high branched polymer 5 (HB-DBV-NVA-V59) [complex 9 ~ complex 12] to adjust the content of Pd fine particles (theoretical value ) To become the aforementioned 30wt%, 40wt%, 50wt% or 60wt% composites, and calculate the yield of their composites.

The actual metal content in the obtained composite was measured by ICP emission analysis, and the 5% weight reduction temperature of the composite was measured. In addition, about 50 particles in the image were selected from a TEM (transmission electron microscope) image, the particle diameters of these particles were measured, and the average value was calculated as the Pd particle diameter in each composite.

The results obtained are shown in Table 2.

[Example 1 to Example 3: Preparation of primer for electroless plating and review of electroless plating]

The composite 1 (Pd fine particles-high branched polymer 6 complex), composite 5 (Pd fine particles-high branched polymer 7 complex) or composite 9 (Pd fine particles-high branched polymer) obtained above 5 complex) 20mg and KBM-903 80mg were mixed separately, n-propanol (PrOH) was added so that the total amount became 2g, and stirred until it became uniform. After the solution became homogeneous, 8 g of n-propanol was added and diluted to a total amount of 10 g. Examples 1 (containing complex 1), Example 2 (containing complex 5), and Example 3 (containing complex 9) were prepared. ) 3 kinds of electroless plating primer.

Using spin coating (5 seconds at 200 rpm and 25 seconds at 1,000 rpm), the electroless plating primers of Examples 1 to 3 described above were separately applied to the polyfluorene affixed to the glass substrate. After being coated on an amine film (Kapton), the polyimide film was removed from the glass substrate, and the solvent was dried on a hot plate (120 ° C, 5 minutes) to form an electroless metal plating base on the polyimide film. coating.

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

The metal plating film on each of the plated substrates obtained by using the electroless plating primers of Examples 1 to 3 was evaluated for the uniformity of the coating film and the substrate adhesion.

The film uniformity was evaluated visually according to the following criteria. Regarding the adhesiveness of the substrate, a cellophane tape (registered trademark) [registered trademark: CT-18S manufactured by NICHIBAN] was attached to the metal-plated portion of the obtained plated substrate, and it was rubbed strongly with a finger. After being firmly adhered, the adhered cellophane tape (registered trademark) was peeled off at one breath, and the state of the metal plating film was visually evaluated according to the following criteria. The results are shown in Table 3.

<Evaluation of film uniformity>

○: The entire surface is formed on the substrate on which the undercoat layer is formed, and the metallic plating system with metallic luster is deposited without unevenness.

△: Although coated on the substrate surface, uneven gloss

×: There is an exposed part of the substrate and it is not completely covered

<Evaluation of substrate adhesion>

○: No peeling of the metal plating film was observed, and the substrate was adhered to the substrate.

△: Partial peeling of the metal plating film

×: Most (about 50% or more) of the metal plating film was peeled off and adhered to the cellophane tape (registered trademark)

[Example 4 to Example 6: Preparation of primer for electroless plating and review of electroless plating]

Except that the same amount of KBM-9103 was used instead of KBM-903, and the same amount of methyl isobutyl ketone (MIBK) was used instead of n-propanol (PrOH) as a solvent, the same preparation and implementation were performed as in Examples 1 to 3. Three types of electroless plating primers for Example 4 (containing complex 1), Example 5 (containing complex 5), and Example 6 (containing complex 9). Using this, the same was applied to polyimide in the same manner as described above. An undercoat layer for electroless metal plating was formed on the film, and then the electroless copper plating solution prepared in Reference Example 1 was used in the same manner as described above to obtain a metal plating film (plating) on the undercoat layer for electroless metal plating. Copper) plated substrates were evaluated for plated film uniformity and substrate adhesion in the same manner as described above. Table 4 shows the results obtained together.

[Example 7; Preparation of electroless plating primer and review of electroless nickel plating]

In the same manner as in Example 6, the electroless plating primer of Example 7 [containing complex 9 (Pd fine particles-high branched polymer 5 complex), amine compound: KB-9103, MIBK] was prepared in the same manner as described above. Formation of an undercoat layer for electroless metal plating on a polyimide film. This film was prepared in Reference Example 2, and then immersed in the electroless nickel plating solution described in Reference Example 2 heated to 85 ° C for 3 minutes. Then, the plated surface was washed with water, and annealed (120 ° C, 5 minutes) on a hot plate to obtain a plated substrate with a metal plating film (nickel plating) formed on the undercoat layer of electroless metal plating. .

[Example 8: Preparation of primer for electroless plating and review of electroless nickel plating]

An amine compound: KBM-9103 was not used in Example 6 above, and an electroless plating primer was prepared. That is, 20 mg of the composite 9 (Pd microparticles-high-branched polymer 5 composite) obtained above was dissolved in methyl isobutyl ketone (MIBK) so that the total amount became 10 g. Plating primer.

Using this electroless plating primer, spin coating (5 seconds at 200 rpm and 25 seconds at 1,000 rpm) was applied in the same manner as described above, and applied to a polyimide film (Kapton) attached to a glass substrate. ), Remove the polyimide film from the glass substrate, and dry the solvent on a hot plate (120 ℃, 5 minutes), and an electroless metal plating undercoat layer was formed on the polyfluoreneimide film.

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

Regarding the plated substrates obtained in Examples 7 and 8, the plated film uniformity and substrate adhesion were evaluated in the same manner as described above. Table 5 shows the results obtained together.

Claims (18)

An undercoating agent, which is an electroless plating undercoating agent for forming a metal plating film on a substrate by an electroless plating treatment, and comprises: (a) at least two free radical polymerizations contained in a molecule Polymeric compound of monomer A having a monomeric double bond and monomer B having an amidino group and at least one radically polymerizable double bond in the molecule, and 5 to 200 relative to the mole number of the monomer A A highly branched polymer made of a polymer of the polymerization initiator C in an amount of Moore, the polymer having at least a structural part represented by the following formula [1] and formula [2] or formula [3] A highly branched polymer composed of a highly branched polymer chain and incorporating a free radical cleavage fragment of the aforementioned polymerization initiator C at the end of the polymer chain, and (b) metal fine particles;

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, and may contain at least one selected from the group consisting of an ether bond, a amine bond, and an ester bond. An alkyl group having 1 to 10 carbon atoms in the bond, A ₁ represents a single bond or a divalent organic group, R ₇ , R _8, and R ₉ each independently represent a hydrogen atom, and may contain a group selected from the group consisting of an ether bond, a amine bond, and an ester. An alkyl group having 1 to 10 carbon atoms in at least one bond of a group formed by a bond, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom and may be selected from the group consisting of an ether bond, a amine bond, and an ester bond. A group of at least one bond having an alkyl group or phenyl group having 1 to 10 carbon atoms, or R ₁₀ and R ₁₁ may be formed together to form a group selected from the group consisting of an ether bond, a amine bond, and an ester bond. R ₂ , R _13, and R ₁₄ each independently represent a hydrogen atom, and may contain a group selected from the group consisting of an ether bond, a amine bond, and an ester bond. An alkyl group having 1 to 10 carbon atoms with at least one bond, and R ₁₅ and R ₁₆ each independently represent a hydrogen atom, and may contain at least one bond selected from the group consisting of an ether bond, a amine bond, and an ester bond Alkyl group having 1 to 10 carbon atoms). The primer according to claim 1, comprising a complex of the aforementioned (a) amine group in the high-branched polymer and the aforementioned (b) metal fine particles attached or coordinated. The primer according to claim 1 or 2, wherein the aforementioned monomer A is a compound having any one or both of a vinyl group and a (meth) acrylfluorenyl group. The primer of claim 3, wherein the aforementioned monomer A is a divinyl compound or a di (meth) acrylate compound. The primer of claim 4, wherein the aforementioned monomer A is a compound having an aromatic ring group having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms. The primer of claim 5, wherein the aforementioned monomer A is divinylbenzene or tricyclic [5.2.1.0 ^2,6 ] decanedimethanol di (meth) acrylate. The primer according to any one of claims 1 to 6, wherein the aforementioned polymerization initiator C is an azo-based polymerization initiator. The primer according to any one of claims 1 to 7, wherein the polymerizable compound includes the monomer B in an amount of 5 to 300 mole% relative to the mole number of the monomer A. The primer of claim 1, wherein the aforementioned A ₁ represents a divalent organic group having an aromatic ring group having 3 to 30 carbon atoms or an alicyclic group having 3 to 30 carbon atoms. The primer of claim 1, wherein the (a) high-branched polymer is a high-scoring polymer formed by a polymer constituting a polymer chain including at least the aforementioned structural part represented by the formula [1] and the formula [2]. Branch polymer, in formula [1], R ₁ , R ₂ , R ₅ and R ₆ represent hydrogen atoms, R ₃ , R ₄ represent hydrogen atoms or methyl groups, and A ₁ represents phenylene or tricyclic [5.2.1.0 ^2,6 ] decane-4,8-diyl-bis (methoxycarbonyl) group. In formula [2], R ₇ , R ₈ and R _{9 each} represent a hydrogen atom, and R ₁₀ and R ₁₁ each independently represent A hydrogen atom or a methyl group, or R ₁₀ and R _{11 are taken} together to represent a normal propyl group, and the end of the polymer chain is incorporated with 2,2'-azobis (2-methylbutyronitrile) and dimethyl 2 , 2'-Azobis (2-methylpropionate) is selected from the radical cleavage fragments of the polymerization initiator C selected. The primer of any one of claims 1 to 10, wherein the (b) metal fine particles are selected from the group consisting of iron (Fe), cobalt (Co), and nickel Fine particles of at least one metal in the group consisting of (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), and gold (Au). The undercoating agent according to claim 11, wherein the (b) metal fine particles are palladium fine particles. The primer according to any one of claims 1 to 12, wherein the (b) metal fine particles are fine particles having an average particle diameter of 1 to 100 nm. The primer according to any one of claims 1 to 13, further comprising (c) an amine compound. An electroless metal plating undercoat layer is a layer formed by the electroless plating undercoating agent according to any one of claims 1 to 14. A metal plating film formed on an undercoat layer of electroless metal plating as claimed in claim 15. A metal coating base material includes a base material, an undercoat layer for electroless metal plating as defined in claim 15 on the base material, and a metal plating film formed on the undercoat layer for electroless metal plating. A method for manufacturing a metal-coated substrate, which includes the following steps A and B; Step A: applying an electroless plating primer as described in any one of claims 1 to 14 on the substrate, and Step of providing an undercoat layer for electroless metal plating on a substrate, step B: immersing a substrate provided with the undercoat layer in an electroless plating bath, and forming a metal plating film on the undercoat layer .