TWI888485B - Electroless plating base containing polymer and metal particles - Google Patents

Abstract

The present invention provides an electroless plating primer comprising a polymer and metal particles. A primer is an electroless plating primer for forming a metal coating film on a substrate by electroless plating treatment, and comprises (A) a copolymer comprising a constituent unit derived from a monomer a having at least one trifluoromethyl group and one free radical polymerizable double bond in the molecule and a constituent unit derived from a monomer b having a metal dispersing group and one free radical polymerizable double bond in the molecule, (B) metal particles, and (C) a solvent.

Description

Electroless plating base containing polymer and metal particles

The present invention relates to an electroless plating base agent comprising a polymer and metal particles.

Electroless plating only involves immersing the substrate in a plating solution, and a film of uniform thickness can be obtained regardless of the type or shape of the substrate. Since a metal-plated film can be formed even on non-conductive materials such as plastic, ceramic, and glass, it has been widely used in various fields such as giving a high-grade and beautiful decorative effect to resin molded bodies such as automotive parts, and in electromagnetic shielding, printed circuit boards, and wiring technology for large-scale integrated circuits. When a metal-plated film is formed on a substrate (the object to be plated) by electroless plating, a pre-treatment is usually performed to improve the adhesion between the substrate and the metal-plated film. Specifically, the surface to be treated is first roughened and/or hydrophilized by various etching methods. Then, a sensitization treatment (sensitization) is performed on the surface to promote the adsorption of the plating catalyst on the surface to be treated, and an activation treatment (activation) is performed on the surface to adsorb the plating catalyst on the surface to be treated. Typically, the sensitization treatment is to immerse the treated object in an acidic solution of stannous chloride, thereby allowing the metal (Sn ²⁺ ) that can function as a reducing agent to adhere to the treated surface. Then, for the sensitized surface to be treated, the treated object is immersed in an acidic solution of palladium chloride as an activation treatment. Thus, the palladium ions in the solution are reduced by the metal of the reducing agent (tin ions: Sn ²⁺ ) and attached to the treated surface as active palladium catalyst nuclei. After the previous treatment, the treated surface is immersed in the electroless plating solution to form a metal plating film on the treated surface.

In contrast, there have been reports of using a composition containing a highly branched polymer having an ammonium group and metal particles as a primer (plating catalyst) for electroless plating, and proposals have been made for an electroless plating primer that can avoid the use of chromium compounds (chromic acid) that have been a problem in the previous pre-treatment step (roughening treatment) of electroless plating, and can reduce the number of pre-treatment steps, and can achieve various improvements in terms of the environment, cost, and cumbersome operation (Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Specification of International Patent Application Publication No. 2012/141215

[Problems to be solved by the invention]

In order to impart other functions (such as adhesion, heat resistance, photosensitivity, dielectric properties, etc.) to the substrate, various compositions containing hyperbranched polymers and metal particles proposed as the above-mentioned electroless plating primers need to be added with other base resins having various functions. However, since other base resins that do not function as plating primers are contained, the above-mentioned base resins are significantly damaged and plating precipitation occurs. That is, the electroless plating primers containing hyperbranched polymers and metal particles proposed so far have the problem of reduced plating precipitation when other base resins that do not function as plating primers are added. The present invention is completed to solve the above-mentioned problems. The purpose is to provide a base agent that can form a base layer exhibiting excellent plating precipitation even when a base agent containing a base resin that imparts adhesion is used. Furthermore, the purpose of the present invention is to provide a novel base agent that can be used as a pre-treatment step before electroless plating and can achieve low cost in its production. [Means for solving the problem]

As a result of active research to achieve the above-mentioned purpose, the inventors of the present invention have discovered that polymers containing fluorine atoms, specifically polymers having trifluoromethyl groups and metal dispersibility groups in the molecule, have excellent metal dispersibility. The polymers are combined with metal particles and coated on a substrate to obtain a layer having excellent plating properties as a base layer for electroless metal plating, thereby completing the present invention.

That is, the first aspect of the present invention is a primer, which is an electroless plating primer for forming a metal-plated film on a substrate by electroless plating treatment, and includes (A) a copolymer, which includes a constituent unit derived from a monomer a having at least one trifluoromethyl group and one free radical polymerizable double bond in the molecule and a constituent unit derived from a monomer b having a metal dispersing group and one free radical polymerizable double bond in the molecule, (B) metal particles, and (C) a solvent. As a second aspect, it is a primer related to the first aspect, wherein the metal dispersing group in the aforementioned (A) copolymer includes a complex to which the aforementioned (B) metal particles are attached or coordinated. As a third aspect, the primer is related to the first aspect or the second aspect, wherein the monomer a is a compound having either a vinyl group or a (meth)acryloyl group. As a fourth aspect, the primer is related to the third aspect, wherein the monomer a is a compound represented by the following formula (1): (In formula (1), M represents a single bond, a carbonyloxy group, an amide group or a phenylene group, J represents a linear or branched alkyl group having 1 to 10 carbon atoms and having at least one trifluoromethyl group, and ^R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). As a fifth aspect, the primer according to the first aspect or the second aspect, wherein the monomer b is a compound having either a vinyl group or a (meth)acryloyl group. As a sixth aspect, the primer according to the fifth aspect, wherein the monomer b is a compound represented by the following formula (2) or (3), (In formula (2), _R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents O or N, _R2 exists only when L represents N, and represents that the hydrogen atom or _R1 and _R2, together with the atoms to which they are bonded, form a 4- to 6-membered cyclic amide. In formula (3), _R3 represents a hydrogen atom or a methyl group, _R4 represents a hydrogen atom or a branched alkyl group having 1 to 10 carbon atoms, a branched alkoxy group having 1 to 10 carbon atoms, or a branched alkoxyalkyl group having 1 to 10 carbon atoms, L represents O or N, _R5 exists only when L represents N, and represents that the hydrogen atom or _R4 and _R5 , together with the atoms to which they are bonded, form a 4- to 6-membered cyclic amide or a 4- to 6-membered cyclic imide). As a seventh aspect, it is a primer related to the sixth aspect, wherein the monomer b is N-vinylpyrrolidone, N-vinylacetamide or N-vinylformamide. As an eighth aspect, it is a primer related to any one of the first to seventh aspects, wherein the monomer mixture from which the copolymer (A) is obtained contains the monomer a in an amount of 5 to 500% by mole relative to the mole of the monomer b. As a ninth aspect, it is a primer related to any one of the first to eighth aspects, wherein the copolymer (A) further contains a constituent unit derived from a monomer c having a crosslinking group and one free radical polymerizable double bond in the molecule. As a tenth aspect, it is a primer related to the ninth aspect, wherein the monomer c is a compound having either a vinyl group or a (meth)acryloyl group. As an eleventh aspect, the base agent related to the tenth aspect, wherein the monomer c is a compound represented by the following formula (4): (In formula (4), X represents a single bond, a carbonyloxy group, an amide group or a phenylene group, Y represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, an alkyl ether group having 1 to 6 carbon atoms which may have a branch, an alkylene sulfide group having 1 to 6 carbon atoms or an alkylene sulfide group having 1 to 6 carbon atoms, Z represents a crosslinking group, and ^R7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) As a twelfth aspect, the base agent according to any one of the ninth aspect to the eleventh aspect, wherein the monomer mixture from which the copolymer (A) is obtained contains the monomer c in an amount of 5 to 300% by mole relative to the mole of the monomer b. As a 13th aspect, it is a primer related to any one of the 1st to 12th aspects, wherein the aforementioned (B) metal particles are particles of at least one metal selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold (Au). As a 14th aspect, it is a primer related to the 13th aspect, wherein the aforementioned (B) metal particles are palladium particles. As a 15th aspect, it is a primer related to any one of the 1st to 14th aspects, wherein the aforementioned (B) metal particles are particles having an average primary particle size of 1 to 100 nm. As a 16th aspect, it is related to the primer of any one of the 1st aspect to the 15th aspect, which contains a base resin having (D) a non-radical polymerizable crosslinking group. As a 17th aspect, it is related to the primer of any one of the 1st aspect to the 16th aspect, which further contains (E) a crosslinking agent. As an 18th aspect, it is related to an electroless metal-plated base layer, which is composed of a film containing the electroless metal-plated primer of any one of the 1st aspect to the 17th aspect. As a 19th aspect, it is related to a metal-plated film formed on the electroless metal-plated base layer of the 18th aspect. As a 20th aspect, it is related to a metal-coated substrate, which comprises a substrate, an electroless metal-plated base layer of the 18th aspect formed on the substrate, and a metal-plated film formed on the electroless metal-plated base layer. As a 21st aspect, it is related to a method for manufacturing a metal-coated substrate, which comprises the following (1) step and (2) step: (1) step: applying the electroless metal-plated primer of any one of the 1st aspect to the 17th aspect on the substrate to form the electroless metal-plated base layer on the substrate, (2) step: immersing the substrate with the base layer formed in an electroless plating bath to form a metal-plated film on the base layer. [Invention Effect]

The primer of the present invention can easily form a base layer for electroless metal plating by simply coating it on a substrate. According to the present invention, a plating base layer can be formed that has excellent adhesion to the substrate and does not affect the plating precipitation. Moreover, the primer of the present invention can be easily varnished with various compositions and can have high metal particle dispersion stability. Furthermore, since the polymer used in the primer of the present invention can be easily prepared with fewer processes, it can also simplify the manufacturing steps of the plating primer and reduce the manufacturing cost. Furthermore, the electroless metal-plated base layer formed by the electroless plating base agent of the present invention can easily form a metal-plated film simply by immersing it in an electroless plating bath, and a metal-coated base material having a base material and a base layer and a metal-plated film can be easily obtained. That is, even if the plating base agent of the present invention is formulated with a base resin that imparts adhesion, a base layer that exhibits excellent plating precipitation can still be formed on the base material.

The present invention is described in detail below. The primer of the present invention comprises (A) a copolymer having the above-mentioned specific constituent units, (B) metal particles and (C) a solvent, and other components as required. The primer of the present invention is suitable for use as a catalyst for forming a metal plating film on a substrate by electroless plating. Each component is described below. ＜(A) Copolymer＞

The component (A) is a copolymer comprising a constituent unit derived from a monomer a having a crosslinking group and one radical polymerizable double bond in the molecule and a constituent unit derived from a monomer b having a metal dispersing group and one radical polymerizable double bond in the molecule.

[Monomer a] Monomer a is a monomer having at least one trifluoromethyl group and one free radical polymerizable double bond in the molecule.

Specific examples of the monomer a include compounds represented by the following formula (1). (In formula (1), M represents a single bond, a carbonyloxy group, an amide group or a phenylene group, J represents a linear or branched alkyl group with 1 to 10 carbon atoms having at least one trifluoromethyl group, and ^R6 represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.) When M represents a carbonyloxy group or an amide group, the structure may be any of the following formulas (1-1) to (1-3), preferably the structure of formula (1-1).

Examples of J are perfluoromethyl (i.e., trifluoromethyl), perfluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, hexafluoroisopropyl, perfluorobutyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl or 2-(perfluorohexyl)ethyl. Among them, J is preferably 2,2,2-trifluoroethyl, hexafluoroisopropyl or 2-(perfluorohexyl)ethyl.

Specific examples of the monomer a are not particularly limited, but include the following: 2,2,2-trifluoroethyl acrylate, hexafluoro-2-propyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, and the like.

[Monomer b] In the present invention, monomer b is a compound having a metal dispersing group and one free radical polymerizing double bond in the molecule. The metal dispersing group is a group used to improve the dispersibility of the metal particles in the composition by interacting with the metal particles of the (B) component through adhesion and/or coordination, thereby allowing the metal particles to exist stably in the composition. Such metal dispersing groups are preferably a substituent having a carbonyl group and a nitrogen atom covalently bonded thereto, that is, a -C(=O)-N- site, and more specifically, a group selected from the group consisting of a group having an amide bond and a group having an imide bond. Preferably, the compound has one free radical polymerizing double bond, preferably a vinyl group or a (meth)acryloyl group. When monomer b is a compound having a (meth)acryloyl group as a free radical polymerizable double bond, the carbonyl group [-C(=O)-] contained in the (meth)acryloyl group may also have a structure that repeats with the carbonyl group in the amide group serving as a metal dispersing group.

Specific examples of the monomer b include compounds represented by the following formula (2) or (3). (In formula (2), _R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents O or N, _R2 exists only when L represents N, and represents that the hydrogen atom or _R1 and _R2 together with the atoms to which they are bonded form a 4- to 6-membered cyclic amide. In formula (3), _R3 represents a hydrogen atom or a methyl group, _R4 represents a hydrogen atom or a branched alkyl group having 1 to 10 carbon atoms, a branched alkoxy group having 1 to 10 carbon atoms, or a branched alkoxyalkyl group having 1 to 10 carbon atoms, L represents O or N, _R5 exists only when L represents N, and represents that the hydrogen atom or _R4 and _R5 together with the atoms to which they are bonded form a 4- to 6-membered cyclic amide or a 4- to 6-membered cyclic imide).

Examples of such monomers b include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-butyl(meth)acrylamide, N-isobutyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-octyl(meth)acrylamide, (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-methoxybutyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, N-isobutoxyethyl (meth)acrylamide, N-vinylphthalimide, N-vinylsuccinimide, etc.

Among them, as monomer b, based on the viewpoint of the coordination energy of the monomer to the metal, the monomer represented by formula (2) is preferred, and the monomer having an N-vinylamide group is more preferred. If the availability is taken into consideration, N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide are more preferred. These monomers b may be used alone or in combination of two or more.

[Monomer c] Component (A) also includes a copolymer containing, in addition to monomer a and monomer b, a constituent unit derived from monomer c having a crosslinking group and one free radical polymerizable double bond in the molecule. Examples of the crosslinking group include N-alkoxymethyl, N-hydroxymethyl, an epoxide group which may have a substituent Q, an alicyclic epoxide group which may have a substituent Q, and an oxacyclobutyl group which may have a substituent Q. Examples of the substituent Q include an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen, a phenyl group, and the like.

A specific example of the monomer c is a compound represented by the following formula (4). (In formula (4), X represents a single bond, a carbonyloxy group, an amide group or a phenylene group, Y represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, an alkyl ether group having 1 to 6 carbon atoms, an alkyl sulfide group having 1 to 6 carbon atoms or an alkyl sulfide ether group having 1 to 6 carbon atoms, Z represents an alkyl group having 1 to 10 carbon atoms and having a straight chain or branched structure and having at least one trifluoromethyl group, and ^R7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

The alkylene group having 1 to 6 carbon atoms represented by Y may be linear or branched, and specific examples thereof are not particularly limited, but examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and the like.

The oxyalkylene group having 1 to 6 carbon atoms may be linear or branched and is a group satisfying -OR ⁸ -. Specific examples of R ⁸ are the same as those of the above-mentioned alkylene group having 1 to 6 carbon atoms.

The alkyl ether group having 1 to 6 carbon atoms may be linear or branched, and is a group satisfying -R ⁹ -OR ⁹ -. Specific examples of R ⁹ are not limited, but are independently exemplified by methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, etc. However, the total number of carbon atoms of the two R ⁹ is 6.

The thioalkylene group having 1 to 6 carbon atoms may be linear or branched, and is a group satisfying -SR ⁸ -, and R ⁸ is as described above.

The sulfanyl ether group having 1 to 6 carbon atoms may be linear or branched, and is a group satisfying -R ⁹ -SR ⁹ -, wherein R ⁹ is as described above.

Specific examples of these monomers c are not limited, but the following are exemplified.

Examples of the monomer having one radical polymerizable double bond and further having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-hydroxymethylacrylamide.

The monomer having one radical polymerizable double bond and further having an N-hydroxymethyl group is not limited, but examples thereof include N-hydroxymethacrylamide and N-hydroxymethylmethacrylamide.

The monomer having one radical polymerizable double bond and further having an epoxy group is not limited, but examples thereof include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Among them, preferably used are glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. These can be used alone or in combination.

The monomer having one radical polymerizable double bond and further having an oxycyclobutyl group is not limited, but examples thereof include (meth)acrylates having an oxycyclobutyl group. Among these monomers, 3-(methacryloyloxymethyl)oxycyclobutane, 3-(acryloyloxymethyl)oxycyclobutane, 3-(methacryloyloxymethyl)-3-ethyloxycyclobutane, 3-(acryloyloxymethyl)-3-ethyloxycyclobutane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxycyclobutane, 3-(acryloyloxymethyl)-2-trifluoromethyloxycyclobutane, 3-(methacryloyloxymethyl)-2-phenyloxycyclobutane are preferred. alkane, 3-(acryloyloxymethyl)-2-phenyloxycyclobutane, 2-(methacryloyloxymethyl)oxycyclobutane, 2-(acryloyloxymethyl)ethyloxycyclobutane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxycyclobutane, 2-(acryloyloxymethyl)-4-trifluoromethyloxycyclobutane, preferably 3-(methacryloyloxymethyl)-3-ethyloxycyclobutane, 3-(acryloyloxymethyl)-3-ethyloxycyclobutane, etc. Among them, from the viewpoint of adhesion to the substrate, X is preferably a carbonyloxy group or a methylene group, and Z is preferably an epoxide group.

In the present invention, when producing the copolymer of component (A), other monomers may be used together with the monomer a, the monomer b and the monomer c. Examples of such other monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxymethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, methacrylic acid, 1,2-dimethyl- ... 8-ethyl-8-tricyclodecyl acrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxymethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinylnaphthalene, vinylanthracene and vinylbiphenyl, etc.

In the present invention, when producing the copolymer of component (A), by using the above-mentioned other monomers, it is also possible to impart resistance to plating liquids and the like to the obtained copolymer of component (A).

The method for obtaining the specific copolymer used in the present invention is not particularly limited, but it can be obtained by, for example, conducting a polymerization reaction at a temperature of 50°C to 110°C in a solvent in which the above-mentioned monomer a, the above-mentioned monomer b, the above-mentioned monomer c, and other monomers and polymerization initiators as desired coexist. At this time, the solvent used is not particularly limited as long as it can dissolve monomers with specific functional groups, monomers without specific functional groups used as desired, and polymerization initiators. A specific example is described in the <(C) solvent> described later. The specific copolymer obtained by the above-mentioned method is usually in the form of a solution dissolved in a solvent.

Furthermore, the solution of the specific copolymer obtained by the above method is put into diethyl ether or water in agitation to precipitate, and the resulting precipitate is filtered and washed, and then dried at room temperature or heated under normal pressure or reduced pressure to obtain a powder of the specific copolymer. By the above operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified specific copolymer is obtained. When the purification cannot be fully achieved by one operation, the obtained powder is dissolved in a solvent again, and the above operation can be repeated.

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

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

In the present invention, the ratio of the copolymerization of the monomer a and the monomer b is preferably 0.05 to 5 moles of the monomer a relative to 1 mole of the monomer b, and particularly preferably 0.1 to 3 moles. In the present invention, the ratio of the copolymerization of the monomer b and the monomer c is preferably 0.05 to 3 moles of the monomer c relative to 1 mole of the monomer b, and particularly preferably 0.1 to 1 mole, based on the viewpoint of reactivity or coating properties.

In the present invention, when the above-mentioned other monomers are used to produce the copolymer of component (A), the amount of the other monomers is 1 to 200% by mole relative to the total mole of the above-mentioned monomer a and monomer b, or relative to the total mole of the above-mentioned monomer a, monomer b and monomer c, and more preferably 10 to 100% by mole.

<(B) Metal particles> The (B) metal particles used as the base agent of the present invention are not particularly limited, but examples of metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold (Au) and alloys thereof. It can be one of these metals or an alloy of two or more. Among them, palladium particles are a preferred example of metal particles. In addition, oxides of the above metals can also be used as metal particles.

The metal particles can be obtained by reducing metal ions, for example, by irradiating a metal salt solution with a high-pressure mercury lamp or by adding a reducing compound (so-called reducing agent) to the solution. For example, a metal salt solution is added to a solution in which the above-mentioned component (A) polymer is dissolved and irradiated with ultraviolet rays, or a metal salt solution and a reducing agent are added to the solution to reduce metal ions, thereby forming a composite of the component (A) polymer and the metal particles while preparing a base agent containing the component (A) polymer and the metal particles.

Examples of the metal salt include chloroauric acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, platinoic acid chloride, Pt(dba) ₂ [dba=dibenzylideneacetone], Pt(cod) ₂ [cod=1,5-cyclooctadiene], Pt(CH ₃ ) ₂ (cod), palladium chloride, palladium acetate (Pd(OC(=O)CH ₃ ) ₂ ), palladium nitrate, Pd ₂ (dba) ₃・CHCl ₃ , Pd(dba) ₂ , rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru(cod)(cot)[cot=cyclooctadiene], iridium chloride, iridium acetate, Ni(cod) ₂ , and the like. The reducing agent is not particularly limited, and various reducing agents can be used. It is preferred to select the reducing agent according to the metal species contained in the obtained base agent. Examples of the reducing agent that can be used include metal borohydride salts such as sodium borohydride and potassium borohydride; aluminum hydride salts such as lithium aluminum hydride, potassium aluminum hydride, caerium aluminum hydride, magnesium aluminum hydride, and calcium aluminum hydride; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary alcohols such as methanol, ethanol, isopropyl alcohol, and polyols; trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], Tertiary amines such as ethylenediaminetetraacetic acid [EDTA]; hydroxylamines; phosphines such as tri-n-propylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis(diphenylphosphino)ethane [DPPE], 1,3-bis(diphenylphosphino)propane [DPPP], 1,1'-bis(diphenylphosphino)ferrocene [DPPF], 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [BINAP], etc.

The primary average particle size of the metal fine particles is preferably 1 to 100 nm. By setting the primary average particle size of the metal fine particles to 100 nm or less, a catalytic activity with sufficiently less surface area reduction can be obtained. The primary average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm. The primary average particle size can be measured as follows. [Measurement of primary average particle size] After dispersing metal fine particles in ethanol, dripping them onto a carbon support film and drying them to prepare a sample, the obtained sample can be subjected to a TEM device (manufactured by Hitachi: H-8000, accelerating voltage 200 kV) by a microscope method to determine the primary average particle size.

The amount of the copolymer of the component (A) added in the primer of the present invention is preferably 20 parts by mass or more and 10,000 parts by mass or less relative to 100 parts by mass of the metal particles (B). By setting the amount of the copolymer (A) added relative to 100 parts by mass of the metal particles (B) to be 20 parts by mass or more, the metal particles can be fully dispersed. If it is less than 20 parts by mass, the dispersibility of the metal particles is insufficient, and precipitates or agglomerates are easily generated. More preferably, it is 30 parts by mass or more. Furthermore, if 10,000 parts by mass or more of the copolymer (A) is added to 100 parts by mass of the metal particles (B), the amount of Pd per unit area after coating is insufficient, so there is a risk of reduced plating precipitation.

<Base> The electroless plating base of the present invention comprises the aforementioned (A) copolymer, (B) metal particles and (C) solvent, and further comprises other components as required. In the electroless plating base of the present invention, it is preferred that the copolymer of the aforementioned (A) component and the aforementioned (B) metal particles form a composite, that is, the aforementioned base preferably comprises a composite formed by the copolymer of the aforementioned (A) component and the aforementioned (B) metal particles.

The composite referred to here is a composite in which the metal dispersing groups of the side chains of the copolymer of the aforementioned component (A) coexist in a state of contact or proximity with metal particles, forming a particle-like morphology. In other words, it is a composite having a structure in which metal particles are attached or coordinated to the metal dispersing groups of the copolymer of the aforementioned component (A). The "attached or coordinated structure" referred to here means that part or all of the metal dispersing groups of the copolymer of the component (A) are in a state of interacting with metal particles, thereby forming a complex-like structure. Therefore, when palladium particles are used as metal particles, it is believed that the Pd atoms on the surface interact with the metal dispersing groups to form a structure in which the polymer of the component (A) surrounds the metal particles.

Therefore, the "composite" in the present invention includes not only the one in which the metal fine particles and the copolymer of the component (A) are bonded to form a composite, but also the one in which the metal fine particles and the copolymer of the component (A) are not bonded to each other but exist independently (appearing to form one particle).

The formation of the composite of the copolymer of the component (A) and the metal fine particles (B) is carried out simultaneously when preparing the base agent containing the copolymer of the component (A) and the metal fine particles. As the method, there are a method of synthesizing metal fine particles stabilized to a certain extent by a metal dispersing group and then exchanging ligands with the polymer of the component (A), or a method of forming the composite by directly reducing metal ions in a solution of the copolymer of the component (A). As mentioned above, a solution of a metal salt is added to a solution of the copolymer of the component (A) and the solution is irradiated with ultraviolet rays, or a solution of a metal salt and a reducing agent are added to the solution to reduce the metal ions, so that the composite can also be formed.

As a direct reduction method, the copolymer of metal ions and component (A) is dissolved in a solvent and reduced with a primary or secondary alcohol such as methanol, ethanol, 2-propanol, or a polyol, thereby obtaining the desired metal particle complex. As the metal ion source used here, the above-mentioned metal salt can be used. The solvent used is not particularly limited as long as it can dissolve metal ions and a polymer having a metal dispersible group at a required concentration or above. Specific examples include alcohols such as methanol, ethanol, n-propanol, and 2-propanol; halogenated hydrocarbons such as dichloromethane and chloroform; cyclic hydrocarbons such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran. Ethers; nitriles such as acetonitrile and butyronitrile; amides such as N,N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide and the like and a mixture of these solvents, preferably alcohols, halogenated hydrocarbons, cyclic ethers, more preferably ethanol, 2-propanol, chloroform, tetrahydrofuran, etc. The temperature of the reduction reaction (mixing the metal ions with the copolymer of component (A)) can usually be used in the range of 0°C to the boiling point of the solvent, preferably in the range of room temperature (about 25°C) to 100°C.

As another direct reduction method, the metal ion and the copolymer of component (A) are dissolved in a solvent and reacted in a hydrogen atmosphere to obtain the desired metal particle composite. As the metal ion source used here, the above-mentioned metal salt or metal carbonyl complexes such as hexacarbonyl chromium [Cr(CO) ₆ ], pentacarbonyl iron [Fe(CO) ₅ ], octacarbonyl dicobalt [Co ₂ (CO) ₈ ], and tetracarbonyl nickel [Ni(CO) ₄ ] can be used. In addition, zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used. The solvent used is not particularly limited as long as it can dissolve the copolymer of the metal ion and the component (A) at a required concentration or higher. 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; nitriles such as acetonitrile and butyronitrile, and mixtures of these solvents. A preferred example is tetrahydrofuran. The temperature for mixing the metal ion and the copolymer of the component (A) can generally be in the range of 0°C to the boiling point of the solvent.

In addition, as a direct reduction method, the target metal particle complex can be obtained by dissolving the copolymer of metal ions and component (A) in a solvent and performing a thermal decomposition reaction. The metal ion source used here can be the above-mentioned metal salt or metal carbonyl complex or other zero-valent metal complex, silver oxide, etc. The solvent used is not particularly limited as long as it can dissolve the metal ion and the copolymer of component (A) at a required concentration or above. Specific examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; halogenated hydrocarbons such as dichloromethane and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; aromatic hydrocarbons such as benzene and toluene, and a mixture of these solvents. A preferred example is toluene. The temperature for mixing the metal ion and the copolymer of component (A) having a metal dispersible group 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 (heating under reflux) in the case of toluene.

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

The primer of the present invention comprises the copolymer of the aforementioned component (A), (B) metal particles (preferably a composite formed thereby) and (C) a solvent, and may further contain other components as required. The primer may also be in the form of a varnish used in forming the [electroless metal plating base layer] described later.

The electroless plating primer of the present invention may contain a base resin of component (D) as desired. Component (D) is preferably a non-radical polymerizable crosslinking group having a group that undergoes a crosslinking reaction with the crosslinking group in component (A) by heat, preferably one described as component (B) in WO2014/171376. By adding such component (D), other functions of the obtained base layer (such as adhesion, heat resistance, photosensitivity, dielectric properties, etc.) may be further improved.

The content of the component (D) in the coating primer of the present invention is preferably 0 to 200 parts by mass, more preferably 0 to 150 parts by mass, based on 100 parts by mass of the total of the copolymer of the component (A) and the metal fine particles of the component (B). If the content of the component (D) is too large, the coating precipitation property may be reduced.

The electroless plating primer of the present invention may contain a crosslinking agent as component (E) as desired.

Examples of the crosslinking agent as the component (E) include epoxy compounds, hydroxymethyl compounds, blocked isocyanate compounds, phenolic plastic compounds, compounds having two or more trialkoxysilyl groups, compounds such as alkoxysilane compounds having an amino group, organic metal compounds having an alkoxy group and/or a chelate ligand, polymers of N-alkoxymethacrylamide, polymers of compounds having an epoxy group, polymers of compounds having an alkoxysilyl group, polymers of compounds having an isocyanate group, and polymers such as melamine formaldehyde resins.

Specific examples of the above-mentioned epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

Specific examples of the hydroxymethyl compound include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone, and 1,3-bis(hydroxymethyl)-4,5-dimethoxy-2-imidazolidinone. Examples of commercially available products include glycoluril compounds (trade names: CYMEL (registered trademark) 1170, POWDER LINK (registered trademark) 1174) manufactured by Mitsui Sitech Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65), butylated urea resins (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea/formaldehyde-based resins (highly condensed type, trade names: BECKAMINE (registered trademark) J-300S, P-955, and N) manufactured by DIC Co., Ltd.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Examples of commercially available products include Mitsui SITECH Co., Ltd. (trade name: CYMEL (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark) BX-4000, BX-37, BL-60, BX-55H), etc.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. Examples of commercially available products include methoxymethyl melamine compounds (trade names: CYMEL (registered trademark) 300, 301, 303, and 350) manufactured by Mitsui Sitech Co., Ltd., butoxymethyl melamine compounds (trade names: MYCOAT (registered trademark) 506 and 508) manufactured by Sanwa Chemical Co., Ltd., methoxymethyl melamine compounds (trade names: NIKALAC (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, and MX-035) manufactured by Sanwa Chemical Co., Ltd., and butoxymethyl melamine compounds (trade names: NIKALAC (registered trademark) MX-45, MX-410, and MX-302) manufactured by Sanwa Chemical Co., Ltd.

Furthermore, compounds obtained by condensing melamine compounds, urea compounds, glycoluril compounds and benzoguanamine compounds in which the hydrogen atoms of these amino groups are substituted with hydroxymethyl groups or alkoxymethyl groups may also be used. Examples include high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6,323,310. Examples of commercial products of the aforementioned melamine compounds include CYMEL (registered trademark) 303 (manufactured by Mitsui Sitech Co., Ltd.), and examples of commercial products of the aforementioned benzoguanamine compounds include CYMEL (registered trademark) 1123 (manufactured by Mitsui Sitech Co., Ltd.).

The so-called blocked isocyanate compound refers to an isocyanate compound having two or more isocyanate groups blocked by a suitable protective group in one molecule, and when exposed to high temperature during heat curing, the protective group (blocking part) is thermally decomposed and detached, causing a crosslinking reaction between the generated isocyanate group and the resin.

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

Examples of the polyfunctional isocyanate compound include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6-Bis(isocyanatomethyl)tetrahydrodicyclopentadiene, bis(isocyanatomethyl)dicyclopentadiene, bis(isocyanatomethyl)adamantane, 2,5-diisocyanatomethylnorbornene, norbornene diisocyanate, dicyclopentane triisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate ester, 1,3-bis(isocyanate methyl)benzene, dianisidine diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,6-bis(isocyanate methyl)decahydronaphthalene, bis(diisocyanate tolyl)phenylmethane, 1,1'-methylenebis(3-methyl-4-isocyanatebenzene), 1,3-bis(1-isocyanate-1-methylethyl)benzene, 1,4-bis(1-isocyanate-1-methylethyl)benzene, 4, 4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, bis(isocyanatemethyl)thiophene, bis(isocyanatemethyl)tetrahydrothiophene, and modified compounds thereof (e.g., isocyanurate form, urea form, ethylene glycol adduct, propylene glycol adduct, trihydroxymethylpropane adduct, ethanolamine adduct, polyester polyol adduct, polyether polyol adduct, polyamide adduct, polyamine adduct).

Examples of the end-capping agent include methanol, ethanol, isopropanol, n-butanol, pentanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononanol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, ethyl lactate, amyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, N,N-dimethylaminoethanol, N,N-diethylaminoethanol. , N,N-dibutylaminoethanol and other alcohols, phenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, chlorophenol, o-cresol, m-cresol, p-cresol, xylenol and other phenols, α-pyrrolidone, β-butyrolactam, β-propiolactamide, γ-butyrolactam, δ-valerolactamide, ε-caprolactam and other lactamides, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, diethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and other oximes, pyrazole, 3,5-dimethylformamide Pyrazoles such as 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, thiols such as butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, benzene mercaptan, etc., active methylene compounds such as malonic acid diester, acetylacetate, malonic acid dinitrile, acetylacetone, methylene disulfide, diphenylmethane, ditert-pentanoylmethane, acetone dicarboxylic acid diester, dibutylamine, Amines such as diisopropylamine, di-tert-butylamine, di(2-ethylhexyl)amine, dicyclohexylamine, benzylamine, diphenylamine, aniline, carbazole, etc., imidazoles such as imidazole, 2-ethylimidazole, etc., imines such as methyleneimine, ethyleneimine, polyethyleneimine, propyleneimine, etc., amides such as acetoaniline, acrylamide, acetamide, dimeramide, etc., amides such as succinimide, maleimide, phthalimide, etc., urea compounds such as urea, thiourea, ethylurea, etc. It may also be an internally blocked type of isocyanate dimer bond (dimerization of isocyanate groups).

Examples of commercially available products of the aforementioned multifunctional blocked isocyanate compounds include the following products. TAKENATE [registered trademark] B-815N, same as B-830, same as B-842N, same as B-846N, same as B-870, same as B-870N, same as B-874, same as B-874N, same as B-882, same as B-882N, same as B-5010, same as B-7005, same as B-7030, same as B-7075 (all manufactured by Mitsui Chemicals Co., Ltd.).

DURANATE [registered trademark] ME20-B80S, same as MF-B60B, same as MF-B60X, same as MF-B90B, same as MF-K60B, same as MF-K60X, same as SBN-70D, same as 17B-60P, same as 17B-60PX, same as TPA-B80E, same as TPA-B80X, same as E402-B80B, same as E402-B80T, same as K6000 (all manufactured by Asahi Kasei Chemicals Co., Ltd.), CORONATE [registered trademark] 2503, same as 2507, same as 2512, same as 2513, same as 2515, same as 2520, same as 2554, same as BI-301, same as AP-M, MIRIONATE MS-50 (all manufactured by TOSOH Co., Ltd.).

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

SUMIJOULE [registered trademark] BL-3175, same as BL-4165, same as BL-4265, same as BL-1100, same as BL-1265, DESMODUR [registered trademark] TPLS-2957, same as TPLS-2062, same as TPLS-2078, same as TPLS-2117, same as BL-3475, DESMOTHERM [registered trademark] 2170, same as 2265 (all manufactured by Sumika Bayer Carbamate Co., Ltd.).

TRIXENE BI-7641, same as BI-7642, same as BI-7986, same as BI-7987, same as BI-7950, same as BI-7951, same as BI-7960, same as BI-7961, same as BI-7963, same as BI-7981, same as BI-79 82. Same as BI-7984, same as BI-7986, same as BI-7990, same as BI-7991, same as BI-7992, same as BI-7770, same as BI-7772, same as BI-7779, same as DP9C/214 (the above is Baxenden Chemicals Co., Ltd.).

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

In addition, as the aforementioned multifunctional blocked isocyanate compound, a homopolymer or copolymer obtained by free radical polymerization of a (meth)acrylate having a blocked isocyanate group can be cited. Here, the so-called copolymer refers to a polymer obtained by polymerizing two or more monomers. The copolymer can be a copolymer obtained by polymerizing two or more (meth)acrylates having a blocked isocyanate group, or a copolymer obtained by polymerizing a (meth)acrylate having a blocked isocyanate group and other (meth)acrylates. Examples of commercially available products of such (meth)acrylates having blocked isocyanate groups include CURRANTS [registered trademark] manufactured by Showa Denko K.K. MOI-BM, AOI-BM, MOI-BP, AOI-BP, MOI-DEM, MOI-CP, MOI-MP, MOI-OEt, MOI-OBu, and MOI-OiPr.

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

Specific examples of the phenolic plastic compound include the following compounds, but the phenolic plastic compound is not limited to the following compound examples.

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

Specific examples of alkoxysilane compounds having an amino group include N,N'-bis[3-(trimethoxysilyl)propyl]-1,2-ethylenediamine, N,N'-bis[3-(triethoxysilyl)propyl]-1,2-ethylenediamine, N-[3-(trimethoxysilyl)propyl]-1,2-ethylenediamine, N-[3-(triethoxysilyl)propyl]-1,2-ethylenediamine, bis{3-(trimethoxysilyl)propyl}amine, bis{3-(triethoxysilyl)propyl}amine, 3-(amino)propyl)amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, trimethoxy{3-(methylamino)propylsilane, 3-(N-allylamino)propyltrimethoxysilane, 3-(N-allylamino)propyltriethoxysilane, 3-(diethylamino)propyltrimethoxysilane, 3-(diethylamino)propyltriethoxysilane, 3-(anilino)propyltrimethoxysilane and 3-(anilino)propyltriethoxysilane.

Specific examples of the organometallic compound having an alkoxy group and/or a chelate ligand include compounds such as diisopropoxyethylaluminum acetoacetate, diisopropoxyaluminum acetoacetate, triacetoacetate, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraoctyltitanium, diisopropoxybis(acetoacetate)titanium, tetraacetoacetate, tetra(n-propoxy)zirconium, tetra(n-butoxy)zirconium, and tetra(acetoacetate)zirconium.

Furthermore, examples of the above-mentioned polymer of N-alkoxymethylacrylamide include polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

Specific examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of such polymers is 1,000 to 200,000, preferably 3,000 to 150,000, and more preferably 3,000 to 50,000.

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

Specific examples of such polymers include poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), copolymers of glycidyl methacrylate and methyl methacrylate, copolymers of 3,4-epoxycyclohexylmethyl methacrylate and methyl methacrylate, copolymers of glycidyl methacrylate and styrene, etc. The weight average molecular weight of such polymers is 1,000 to 200,000, preferably 3,000 to 150,000, and more preferably 3,000 to 50,000.

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

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

These crosslinking agents may be used alone or in combination of two or more.

The content of the component (E) in the coating primer of the present invention is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, based on 100 parts by mass of the total of the copolymer of the component (A) and the metal fine particles of the component (B).

<Other additives> The base agent of the present invention may be further added with additives such as surfactants, various surface conditioners, and thickeners as long as the effects of the present invention are not impaired.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, and sorbitan trioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, and sorbitan trioleate. Polyoxyethylene nonionic surfactants such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, etc.; EFTOP (registered trademark) EF-301, EF-303, EF-352 [all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.], MEGFAC (registered trademark) F-171, F-173, R-08, R-30 [all manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430, FC-431 [all manufactured by Sumitomo 3M Co., Ltd.], Asahi Fluorine-based surfactants such as Guard (registered trademark) AG-710 [manufactured by Asahi Glass Co., Ltd.] and SURFLON (registered trademark) S-382 [manufactured by AGC Semichemical Co., Ltd.].

In addition, as the above-mentioned surface conditioner, there can be cited polysilicone leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; polysilicone surface conditioners such as BYK (registered trademark) -302, 307, 322, 323, 330, 333, 370, 375, and 378 [all manufactured by BYK Chemical Co., Ltd. of Japan], etc.

Examples of the above-mentioned thickener include polyacrylic acid (including crosslinked ones) such as carboxyvinyl polymer (carbomer); vinyl polymers such as polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polystyrene (PS); polyethylene oxides; polyesters; polycarbonates; polyamides; polyurethanes; polysaccharides such as dextrin, agar, carrageenan, alginic acid, gum arabic, guar gum, tragacanth gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; proteins such as gelatin and casein, etc. In addition, the above-mentioned polymers include not only homopolymers but also copolymers. These thickeners can be used alone or in combination of two or more. The base agent of the present invention can adjust the viscosity or rheological properties of the base agent by mixing a thickener as needed, and can be appropriately used and selected according to the application method or application place of the base agent and its purpose.

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

[Electroless metal-plated base layer] The electroless metal-plated base agent of the present invention can be applied to a substrate to form an electroless metal-plated base layer. This electroless metal-plated base layer is also the subject of the present invention.

As the aforementioned substrate, there is no particular limitation, and a non-conductive substrate or a conductive substrate can be preferably used. As the non-conductive substrate, for example, glass, ceramics, etc.; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene terephthalate) resin, PEEK (polyetheretherketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, LCP (liquid crystal polymer) resin, etc.; paper, etc. These can be used appropriately in the form of sheets or films, and the thickness is not particularly limited at this time. In addition, as a conductive substrate, for example, ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), various stainless steels, aluminum and aluminum alloys such as duralumin, iron and iron alloys, copper and brass, phosphor bronze, white copper and copper alloys such as cobalt, nickel and nickel alloys, and silver and silver alloys such as nickel-silver can be cited. Furthermore, a substrate having a thin film formed on the above-mentioned non-conductive substrate using such a conductive substrate can also be used. Furthermore, the substrate may be a three-dimensional molded body.

As a specific method for forming an electroless metal-plated base layer from an electroless plating base containing the copolymer of the above-mentioned component (A), (B) metal particles (preferably a composite formed by the above-mentioned components) and (C) a solvent, and further, if necessary, (D) a base resin, (E) a crosslinking agent and other components, firstly, the above-mentioned component (A) polymer and (B) metal particles (preferably a composite formed by the above-mentioned components) (and, if necessary, (D) a base resin, (E) a crosslinking agent and other components) are dissolved or dispersed in the (C) solvent to form a varnish, and then the varnish is applied by a spin coating method, a doctor blade coating method or a dip coating method; Roll coating method; rod coating method; die coating method; jet coating method; inkjet method; pen lithography such as ink pen nanolithography (FPN) and dip pen nanolithography (DPN); letterpress printing methods such as letterpress printing, flexographic printing, resin relief printing, contact printing, micro contact printing (μCP), nanoimprint lithography (NIL), nano transfer printing (nTP); gravure printing methods such as gravure printing and engraving; lithographic printing method; stencil printing methods such as screen printing and transcription; offset printing method, etc., the varnish is applied to the substrate on which the metal coating film is formed, and then the solvent is evaporated and dried to form a thin layer. Among these coating methods, rod coating, flexographic printing, gravure printing, rotary coating, jet coating, inkjet coating, pen lithography, contact printing, μCP, NIL and nTP are preferred. When using the rotary coating method, since coating can be performed in a short time, even highly volatile solutions can be used, and it has the advantage of being able to perform highly uniform coating. When using the jet coating method, highly uniform coating can be performed with a very small amount of varnish, which is very advantageous in industry. When using the inkjet method, pen lithography, contact printing, μCP, NIL, and nTP, for example, fine patterns such as wiring can be efficiently formed (drawn), which is very advantageous in industry.

<(C) Solvent> The solvent used here is not particularly limited as long as it can dissolve or disperse the polymer of the above-mentioned component (A) and the metal particles (B) (preferably a composite formed by the above-mentioned components) and the desired components (D), (E) and other components. For example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2- Alcohols such as butanol, n-hexanol, n-octanol, 2-octanol, 2-ethylhexanol, etc.; solvents such as methyl solvent, ethyl solvent, butyl solvent, phenyl solvent, 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 dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, Glycol ethers such as diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether; glycol esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate (PGMEA); ethers such as tetrahydrofuran (THF), methyl tetrahydrofuran, 1,4-dioxane, diethyl ether; acetic acid Esters such as ethyl ester and butyl acetate; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone; aliphatic hydrocarbons such as n-heptane, n-hexane, cyclohexane; halogenated aliphatic hydrocarbons such as 1,2-dichloroethane and chloroform; amides such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide; dimethyl sulfoxide, etc. These solvents can be used alone or in combination of two or more solvents. Furthermore, diols such as ethylene glycol, propylene glycol, and butylene glycol can be added to adjust the viscosity of the varnish. The concentration of the components dissolved or dispersed in the above-mentioned solvent is arbitrary, but the concentration of the non-solvent components in the varnish [the concentration of all components except the solvent contained in the base agent ((A) the polymer component and (B) metal particles (preferably a complex formed therefrom), (D) base resin as desired, (E) crosslinking agent and other components, etc.)] is 0.05 to 90% by mass, preferably 0.1 to 80% by mass.

The method for drying the solvent is not particularly limited, and for example, a heating plate or oven can be used to evaporate the solvent in a suitable environment, i.e., air, an inert gas such as nitrogen, or a vacuum. In this way, a base layer with a uniform film-forming surface can be obtained. The calcination temperature is not particularly limited as long as it can evaporate the solvent, but it is preferably carried out at 40 to 250°C.

[Electroless plating treatment, metal-plated film, metal-coated substrate] A metal-coated film is formed on the base layer obtained as described above by electroless plating. The metal-coated film obtained in this way and the metal-coated substrate having the electroless metal-plated base layer and the metal-coated film in this order on the substrate are also the objects of the present invention. The electroless plating treatment (step) is not particularly limited and can be carried out by any generally known electroless plating treatment, such as a method of generally using a generally known electroless plating solution and immersing the electroless metal-plated base layer formed on the substrate in the plating solution (bath).

The aforementioned electroless plating solution mainly contains metal ions (metal salts), a cathaydrant, and a reducing agent. It may contain a pH adjuster, a pH buffer, a reaction accelerator (a second cathaydrant), a stabilizer, a surfactant (for imparting gloss to the plated film, improving the wettability of the treated surface, etc.) and the like in combination with other purposes. Here, as metals used in the metal plating film formed by electroless plating, there can be cited iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, which can be appropriately selected according to the purpose. Furthermore, the above-mentioned chelating agent and reducing agent can be appropriately selected according to the metal ions.

In addition, the electroless plating solution may be a commercially available plating solution, for example, electroless nickel plating chemicals (Melplate (registered trademark) NI series) and electroless copper plating chemicals (Melplate (registered trademark) CU series) manufactured by MELTEX Co., Ltd.; electroless nickel plating solution (ICP Nicoron (registered trademark) series, Topiena 650), electroless copper plating solution (OPC-700 electroless copper M-K, ATS Adcopper IW, CT, OPC copper (registered trademark) AF series, HFS, NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (Flashgold 330, Selfgold OTK-IT), electroless silver plating solution (Mudensilver); electroless brine plating solution (Pallet II), electroless gold plating solution (Dip G series, NC Gold series) produced by Kojima Chemicals; electroless silver plating solution (S-DIA AG-40) produced by Sasaki Chemicals; electroless nickel plating solution (Kanigen (registered trademark) series, Sumer (registered trademark) series, Sumer (registered trademark), Kaniblack) produced by KANIGEN Co., Ltd. (Registered Trademark) Series), electroless palladium plating solution (S-KPD); electroless copper plating solution (Cuposit (Registered Trademark) Coppermix Series, Circuposit (Registered Trademark) Series), electroless bahedral plating solution (Paramasu (Registered Trademark) Series), electroless nickel plating solution (Duraposit (Registered Trademark) Series), electroless gold plating solution (Aurolect roless (registered trademark) series), electroless tin plating solution (Denposit (registered trademark) series); electroless copper plating solution manufactured by Uemura Industries (Thrucup (registered trademark) ELC-SP, PSY, PCY, PGT, PSR, PEA, PMK), electroless copper plating solution manufactured by ADTEC Japan (Printgant (registered trademark) PV, PVE), etc.

The electroless plating step can control the formation speed or thickness of the metal film by adjusting the temperature, pH, immersion time, metal ion concentration, stirring or stirring speed, air and oxygen supply or supply speed of the plating bath. [Example]

The present invention is described in more detail below by way of examples, but the present invention is not limited to the examples. In addition, the number average molecular weight and the weight average molecular weight are measured as follows. [Measurement of number average molecular weight and weight average molecular weight] The number average molecular weight and the weight average molecular weight of the copolymer obtained according to the following synthesis example are measured using a GPC apparatus (Shodex column KD800 and TOSOH column TSK-GEL) manufactured by TOSOH Co., Ltd., with N,N-dimethylformamide (mixed with 10 mmol/L (liter) of lithium bromide monohydrate (LiBr・H ₂ O) as an additive) as an elution solvent flowing into the column at a flow rate of 1 mL/min (column temperature 40°C). In addition, the number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) are expressed as polystyrene-converted values.

The abbreviations used in the following embodiments have the following meanings. HEA: 2-Hydroxyethyl acrylate NVA: N-vinyl acetamide GMA: Glycidyl methacrylate CYCLOMER M100: 3,4-Epoxycyclohexylmethyl methacrylate (manufactured by DAICEL) BISCOAT 3F: 2,2,2-Trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Industry) HFIP-M: Hexafluoro-2-propyl methacrylate (manufactured by CENTRAL Glass) FAMAC-6: 2-(Perfluorohexyl)ethyl methacrylate (manufactured by UNIMATEC) AMBN: 2,2'-Azo-2-methylbutyronitrile PGME: Propylene glycol monomethyl ether IPE: Diisopropyl ether BL-10: Polyvinyl acetal resin (manufactured by Sekisui Chemical Industry Co., Ltd.) 8KX-127: Acrylic resin (manufactured by Taisei Fine Chemicals Co., Ltd.) [Synthesis of polymers]

<Synthesis Example 1> 2.00 g of styrene, 1.63 g of NVA, 2.23 g of HEA, and 0.29 g of AMBN were dissolved in 14.37 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P1). The Mn of the obtained copolymer was 6,806 and the Mw was 11,797.

<Synthesis Example 2> 2.00g of styrene, 1.63g of NVA, 2.73g of GMA, and 0.32g of AMBN were dissolved in 15.59g of PGME, and the resulting copolymer solution (solid content 30% by mass) was stirred at 80°C for 20 hours and then added to 500mL of diethyl ether to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P2). The Mn of the obtained copolymer was 6,057 and the Mw was 8,884.

<Synthesis Example 3> 2.00 g of styrene, 1.63 g of NVA, 3.76 g of CYCLOMER M100, and 0.37 g of AMBN were dissolved in 18.14 g of PGME, and the resulting copolymer solution (solid content concentration 30% by mass) was stirred at 80°C for 20 hours and then added to 500 mL of diethyl ether to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P3). The Mn of the obtained copolymer was 5,336 and the Mw was 8,669.

<Synthesis Example 4> 2.00 g of styrene, 1.63 g of NVA, 1.56 g of HEA, 0.89 g of BISCOAT 3F, and 0.30 g of AMBN were dissolved in 14.90 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P4). The Mn of the obtained copolymer was 7,669 and the Mw was 16,610.

<Synthesis Example 5> 2.00 g of styrene, 1.63 g of NVA, 1.56 g of HEA, 2.49 g of FAMAC-6, and 0.38 g of AMBN were dissolved in 18.83 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P5). The Mn of the obtained copolymer was 6,146 and the Mw was 13,143.

<Synthesis Example 6> 2.00 g of styrene, 1.63 g of NVA, 1.91 g of GMA, 0.89 g of BISCOAT 3F, and 0.32 g of AMBN were dissolved in 15.76 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P6). The Mn of the obtained copolymer was 6,170 and the Mw was 10,023.

<Synthesis Example 7> 2.00 g of styrene, 1.63 g of NVA, 1.91 g of GMA, 1.36 g of HFIP-M, and 0.34 g of AMBN were dissolved in 16.92 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P7). The Mn of the obtained copolymer was 5,257 and the Mw was 9,324.

<Synthesis Example 8> 2.00 g of styrene, 1.63 g of NVA, 1.91 g of GMA, 2.49 g of FAMAC-6, and 0.40 g of AMBN were dissolved in 19.69 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P8). The Mn of the obtained copolymer was 4,718 and the Mw was 8,940.

<Synthesis Example 9> 2.00 g of styrene, 1.63 g of NVA, 2.64 g of CYCLOMER M100, 0.89 g of BISCOAT 3F, and 0.36 g of AMBN were dissolved in 17.54 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P9). The Mn of the obtained copolymer was 6,558 and the Mw was 10,706.

<Synthesis Example 10> 2.00 g of styrene, 1.63 g of NVA, 2.64 g of CYCLOMER M100, 1.36 g of HFIP-M, and 0.38 g of AMBN were dissolved in 18.70 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P10). The Mn of the obtained copolymer was 5,021 and the Mw was 8,277.

<Synthesis Example 11> 2.00 g of styrene, 1.63 g of NVA, 2.64 g of CYCLOMER M100, 2.49 g of FAMAC-6, and 0.44 g of AMBN were dissolved in 21.47 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P11). The Mn of the obtained copolymer was 4,842 and the Mw was 7,853.

<Synthesis Example 12> 2.00 g of styrene, 1.63 g of NVA, 1.88 g of CYCLOMER M100, 1.48 g of BISCOAT 3F, and 0.35 g of AMBN were dissolved in 17.14 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P12). The Mn of the obtained copolymer was 6,592 and the Mw was 10,717.

<Synthesis Example 13> 2.00 g of styrene, 1.63 g of NVA, 1.88 g of CYCLOMER M100, 4.15 g of FAMAC-6, and 0.48 g of AMBN were dissolved in 23.69 g of PGME and reacted at 80°C for 20 hours. The resulting copolymer solution (solid content concentration 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P13). The Mn of the obtained copolymer was 5,814 and the Mw was 8,518.

[Synthesis of Pd particle composite] <Synthesis Example 14> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Junyaku Co., Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P1 polymerized in Synthesis Example 1 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M1).

<Synthesis Example 15> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution prepared by dissolving 1.0 g of P2 polymerized in Synthesis Example 2 in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen atmosphere. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of an IPE/hexane solution (mass ratio 10:1) while stirring, and a polymer/Pd particle composite is precipitated. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M2).

<Synthesis Example 16> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Jun Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P3 polymerized in Synthesis Example 3 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and dried in vacuo at 50°C to obtain 0.9 g of a black powder Pd particle composite (M3).

<Synthesis Example 17> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Junyaku Co., Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P4 polymerized in Synthesis Example 4 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M4).

<Synthesis Example 18> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Jun Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P5 polymerized in Synthesis Example 5 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M5).

<Synthesis Example 19> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P6 polymerized in Synthesis Example 6 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M6).

<Synthesis Example 20> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution prepared by dissolving 1.0 g of P7 polymerized in Synthesis Example 7 in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen atmosphere. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of an IPE/hexane solution (mass ratio 10:1) while stirring, and a polymer/Pd particle composite is precipitated. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M7).

<Synthesis Example 21> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Jun Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P8 polymerized in Synthesis Example 8 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M8).

<Synthesis Example 22> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P9 polymerized in Synthesis Example 9 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen atmosphere. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M9).

<Synthesis Example 23> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Jun Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution prepared by dissolving 1.0 g of P10 polymerized in Synthesis Example 10 in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen atmosphere. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M10).

<Synthesis Example 24> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Jun Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P11 polymerized in Synthesis Example 11 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M11).

<Synthesis Example 25> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Jun Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P12 polymerized in Synthesis Example 12 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M12).

<Synthesis Example 26> In a 100 mL reaction flask equipped with a cooler, add 0.90 g of palladium acetate [produced by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stir until uniform. To the solution, add a solution of 1.0 g of P13 polymerized in Synthesis Example 13 dissolved in 16.40 g of chloroform and 6.40 g of ethanol using a dropping funnel. The mixture is stirred at 60°C for 8 hours under a nitrogen environment. After cooling to a liquid temperature of 30°C, the solution is added to 341 g of IPE/hexane solution (mass ratio 10:1) while stirring to precipitate a polymer/Pd particle composite. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of a black powder Pd particle composite (M13).

The components (C) and (D) are added to the above-mentioned Pd particle composites M1 to M13 at the ratio shown in Table 1 below to prepare an electroless plating primer. The electroless plating primers comprising M1 to M3 are comparative examples. The electroless plating primers comprising M4 to M13 are examples.

[Preparation of plating solution] <Preparation Example 1> In a 200 mL beaker, add 100 mL of pure water, 17 mL of BASIC PRINT GANTT V (Atotech), 9 mL of copper solution PRINT GANTT V (Atotech), 1.6 mL of initiator PRINT GANTT PV (Atotech), 0.24 mL of stabilizer PRINT GANTT PV (Atotech), 3.2 mL of reducing agent Cu (Atotech), 4 mL of 18.5 mass % NaOH aqueous solution, and then add pure water to make the total volume of the solution 200 mL. Stir the solution to prepare an electroless copper plating solution.

[Evaluation of plating precipitation] The electroless plating primers of Examples 1 to 10 and Comparative Examples 1 to 6 were applied to a polyimide substrate (KAPTON 100EN (registered trademark) manufactured by Dongli DuPont Co., Ltd.) with a film thickness of 6 μm using a rod, and then heated at 80°C for 5 minutes to form a coating. The coating was further heated at 250°C for 30 minutes and dried. The obtained film was immersed in the electroless copper plating solution prepared in Preparation Example 1 for 10 minutes. Subsequently, the obtained plated substrate was washed with water, and the state of the metal plating film was visually evaluated. The evaluation results are summarized in Table 2.

<Evaluation criteria for coating precipitation> ○: The coating is uniformly precipitated on the entire coating. ×: The coating is not uniformly precipitated on the entire coating.

As shown in Table 2, the electroless plating primers of Examples 1 to 13 and the electroless plating primers of Comparative Examples 1 to 3 have good plating deposition properties. On the other hand, no plating deposition was observed in the electroless plating primers of Comparative Examples 4 to 7.

Claims (18)

A primer is an electroless plating primer for forming a metal-plated film on a substrate by electroless plating treatment, and comprises (A) a copolymer, which comprises a constituent unit derived from a monomer a having at least one trifluoromethyl group and one free radical polymerizable double bond in the molecule and a constituent unit derived from a monomer b having a metal dispersing group and one free radical polymerizable double bond in the molecule, wherein the free radical polymerizable double bond is a vinyl group or a (meth)acryloyl group, (B) metal particles, and (C) a solvent. The base agent of claim 1, wherein the metal dispersing group in the aforementioned (A) copolymer comprises a complex to which the aforementioned (B) metal particles are attached or coordinated. The base agent of claim 1, wherein the monomer a is a compound represented by the following formula (1): (In formula (1), M represents a single bond, a carbonyloxy group, an amide group or a phenylene group, J represents a linear or branched alkyl group having 1 to 10 carbon atoms and having at least one trifluoromethyl group, and ^R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The base agent of claim 1, wherein the monomer b is a compound represented by the following formula (2) or (3), (In formula (2), _R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents O or N, _R2 exists only when L represents N, and represents that the hydrogen atom or _R1 and _R2 together with the atoms to which they are bonded form a 4- to 6-membered cyclic amide. In formula (3), _R3 represents a hydrogen atom or a methyl group, _R4 represents a hydrogen atom or a branched alkyl group having 1 to 10 carbon atoms, a branched alkoxy group having 1 to 10 carbon atoms, or a branched alkoxyalkyl group having 1 to 10 carbon atoms, L represents O or N, _R5 exists only when L represents N, and represents that the hydrogen atom or _R4 and _R5 together with the atoms to which they are bonded form a 4- to 6-membered cyclic amide or a 4- to 6-membered cyclic imide). The base agent of claim 4, wherein the monomer b is N-vinylpyrrolidone, N-vinylacetamide or N-vinylformamide. The base agent of claim 1 or 2, wherein the monomer mixture for obtaining the copolymer (A) comprises the monomer a in an amount of 5 to 500% by mole relative to the mole of the monomer b. The base agent of claim 1 or 2, wherein the aforementioned (A) copolymer further comprises a constituent unit derived from a monomer c having a crosslinking group and a free radical polymerizable double bond in the molecule, and the free radical polymerizable double bond is a vinyl group or a (meth)acryl group. The base agent of claim 7, wherein the monomer c is a compound represented by the following formula (4): (In formula (4), X represents a single bond, a carbonyloxy group, an amide group or a phenylene group, Y represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, an alkyl ether group having 1 to 6 carbon atoms which may have a branch, an alkyl sulfide group having 1 to 6 carbon atoms or a sulfanyl ether group having 1 to 6 carbon atoms, Z represents a crosslinking group, and ^R7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The base agent of claim 7, wherein the monomer mixture for obtaining the copolymer (A) comprises the monomer c in an amount of 5 to 300% by mole relative to the mole of the monomer b. The substrate of claim 1 or 2, wherein the aforementioned (B) metal particles are particles of at least one metal selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold (Au). The substrate of claim 10, wherein the aforementioned (B) metal particles are palladium particles. The base agent of claim 1 or 2, wherein the aforementioned (B) metal particles are particles having an average primary particle size of 1-100 nm. The base agent of claim 1 or 2, wherein the base resin further comprises (D) a non-free radical polymerizable cross-linking group. The base agent of claim 1 or 2, further comprising (E) a crosslinking agent. An electroless metal-plated base layer is formed by a film containing an electroless metal-plated base agent as described in any one of claims 1 to 14. A metal-plated film formed on an electroless metal-plated base layer as claimed in claim 15. A metal-coated substrate comprises a substrate, an electroless metal-plated base layer as claimed in claim 15 formed on the substrate, and a metal-plated film formed on the electroless metal-plated base layer. A method for manufacturing a metal-coated substrate, comprising the following steps (1) and (2), (1) step: applying an electroless plating primer as described in any one of claims 1 to 14 on a substrate to form an electroless metal-plated base layer on the substrate, (2) step: immersing the substrate on which the base layer is formed in an electroless plating bath to form a metal-plated film on the base layer.