WO2021166726A1

WO2021166726A1 - Electroless plating primer including polymer and metal fine particles

Info

Publication number: WO2021166726A1
Application number: PCT/JP2021/004682
Authority: WO
Inventors: 有輝星野; 雄大森元
Original assignee: 日産化学株式会社
Priority date: 2020-02-19
Filing date: 2021-02-08
Publication date: 2021-08-26
Also published as: CN115135803A; KR20220143007A; JPWO2021166726A1; TW202200840A

Abstract

[Problem] To provide an electroless plating primer that includes a polymer and metal fine particles. [Solution] An electroless plating primer for forming a metal plating film on a base material by electroless plating treatment, wherein the primer includes (A) a copolymer that includes a structural unit derived from a monomer a having at least one trifluoromethyl group and one radical polymerizable double bond in the molecule and a structural unit derived from a monomer b having a metal dispersive group and one radical polymerizable double bond in the molecule, (B) metal fine particles, and (C) a solvent.

Description

Electroless plating base material containing polymer and metal fine particles

The present invention relates to an electroless plating base material containing polymers and metal fine particles.

In non-electrolytic plating, a uniform thickness film can be obtained regardless of the type and shape of the substrate simply by immersing the substrate in the plating solution, and the metal plating film can be applied to non-conductor materials such as plastics, ceramics, and glass. It is widely used in various fields such as decorative applications such as giving a sense of quality and aesthetics to resin molded bodies such as automobile parts, and wiring technology for electromagnetic shielding, printed circuit boards, large-scale integrated circuits, etc. ing.
Usually, when a metal plating film is formed on a base material (object to be plated) by electroless plating, a pretreatment for improving the adhesion between the base material and the metal plating film is performed. Specifically, the surface to be treated is first roughened and / or made hydrophilic by various etching means, and then an adsorbent that promotes adsorption of the plating catalyst on the surface to be treated is supplied onto the surface to be treated for sensitization. A treatment (sensitization) and an activation treatment (activation) in which the plating catalyst is adsorbed on the surface to be treated are performed. Typically, the sensitization treatment immerses the object to be treated in an acidic solution of stannous chloride, which causes a metal (Sn ²⁺ ) that can act as a reducing agent to adhere to the surface to be treated. Then, the sensitized surface to be treated is immersed in an acidic solution of palladium chloride as an activation treatment. As a result, the palladium ions in the solution are reduced by the metal (tin ion: Sn ²⁺ ) which is a reducing agent and adhere to the surface to be treated as an active palladium catalyst nucleus. After such pretreatment, it is immersed in an electroless plating solution to form a metal plating film on the surface to be treated.

On the other hand, an example in which a composition containing a highly branched polymer having an ammonium group and metal fine particles is used as a base material (plating catalyst) for electroless plating has been reported, and a pretreatment step (coarse) of the conventional electroless plating treatment has been reported. Various improvements such as environmental aspects, cost aspects, and complicated operability have been achieved, such as avoiding the use of chromium compounds (chromic acid), which has been a problem in surface treatment), and reducing the number of pretreatment steps. A proposal for an electroless plating base material has been made (Patent Document 1).

International Patent Application Publication No. 2012/141215 Pamphlet

In the composition containing various highly branched polymers and metal fine particles proposed as a base material for electroless plating described above, other functions on the substrate (for example, adhesion, heat resistance, photosensitivity, dielectric property, etc.) ) Is required to be added to other base resins having their respective functions, but the above-mentioned base resin is contained because it contains other base resins that do not exhibit the function as a plating base agent. The agent may significantly impair the precipitation property of the plating.
That is, the electroless plating base material containing the highly branched polymer and metal fine particles proposed so far has a problem that the plating precipitation property may decrease when another base resin having no function of the plating base material is added. was there.
The present invention has been made to solve this conventional problem, and even if a plating base material having a composition containing a base resin that imparts adhesion is used, a plating base that exhibits excellent plating precipitation property is exhibited. An object of the present invention is to provide a base material capable of forming a stratum. Furthermore, an object of the present invention is to provide a new base material used as a pretreatment step of electroless plating, which can realize cost reduction in its production.

As a result of diligent studies to achieve the above object, the present inventors have found that a polymer containing a fluorine atom, specifically, a polymer having a trifluoromethyl group and a metal dispersibility group in the molecule has excellent metal dispersibility. The present invention was completed by finding that a layer obtained by combining the polymer and metal fine particles and applying the polymer onto a base material has excellent plating properties as an underlayer for electroless metal plating.

That is, the present invention is, as a first aspect, an electroless plating base material for forming a metal plating film on a base material by an electroless plating treatment.
(A) A structural unit derived from a monomer a having at least one trifluoromethyl group and one radically polymerizable double bond in the molecule, and a metal dispersible group and one radically polymerizable double bond in the molecule. A copolymer containing a structural unit derived from a monomer b having a double bond,
The present invention relates to (B) metal fine particles and (C) a base material containing a solvent.
A second aspect of the present invention relates to the base material according to the first aspect, which comprises a complex in which the (B) metal fine particles are adhered or coordinated to the metal dispersible group in the (A) copolymer.
As a third aspect, the base material according 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 base material according to the third aspect, wherein the monomer a is a compound represented by the following formula (1).

(In the formula (1), M represents a single bond, a carbonyloxy group, an amide group or a phenylene group, and J is a linear or branched group having 1 to 10 carbon atoms having at least one trifluoromethyl group. Represents an alkyl group of structure, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) As a fifth aspect, the monomer b has either a vinyl group or a (meth) acryloyl group. The base material according to the first aspect or the second aspect, which is a compound.
As a sixth aspect, the base material according to the fifth aspect, wherein the monomer b is a compound represented by the following formula (2) or (3).

(In the formula (2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents O or N, and R ₂ exists only when L represents N. Representing a hydrogen atom, or R ₁ and R ₂ may be combined with the atom to which they are attached to form a 4- to 6-membered cyclic amide.
In formula (3), R ₃ represents a hydrogen atom or a methyl group.
R ₄ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an alkoxyl having 1 to 10 carbon atoms. Representing an alkyl group, L represents O or N, R ₅ is present only if L represents N and represents a hydrogen atom, or R ₄ and R ₅ are with the atom to which they are attached. Together, they may form a 4- to 6-membered cyclic amide or a 4- to 6-membered cyclic imide. )
As a seventh aspect, the base material according to the sixth aspect, wherein the monomer b is N-vinylpyrrolidone, N-vinylacetamide or N-vinylformamide.
As an eighth aspect, the monomer mixture giving the (A) copolymer contains the monomer a in an amount that is 5 to 500% of the number of moles of the monomer b, from the first aspect to the seventh aspect. The base material according to any one of the viewpoints.
As a ninth aspect, the first to eighth aspects, wherein the copolymer (A) further contains a structural unit derived from a monomer c having a crosslinkable group and one radically polymerizable double bond in the molecule. Regarding the base material described in any one of the items.
As a tenth aspect, the base material according 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 material according to the tenth aspect, wherein the monomer c is a compound represented by the following formula (4).

(In the formula (4), X represents a single bond, a carbonyloxy group, an amide group or a phenylene group, and Y is an alkylene group having 1 to 6 carbon atoms and an oxyalkylene group having 1 to 6 carbon atoms, which are branched. May represent an alkyl ether group having 1 to 6 carbon atoms, a thioalkylene group having 1 to 6 carbon atoms or a thioalkyl ether group having 1 to 6 carbon atoms, where Z represents a crosslinkable group and R ⁷ Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
As a twelfth aspect, the monomer mixture giving the (A) copolymer contains the monomer c in an amount which is 5 to 300% of the number of moles of the monomer b, and the ninth aspect to the eleventh aspect. The base material according to any one of the viewpoints.
From the thirteenth viewpoint, the metal fine particles (B) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum ( The base material according to any one of the first to twelfth viewpoints, which is a fine particle of at least one kind of metal selected from the group consisting of Pt) and gold (Au).
As a fourteenth aspect, the base material according to the thirteenth aspect, wherein the metal fine particles (B) are palladium fine particles.
As a fifteenth viewpoint, the base material according to any one of the first to fourteenth viewpoints, wherein the metal fine particles (B) are fine particles having a primary particle average particle size of 1 to 100 nm.
As a sixteenth aspect, the base material according to any one of the first to fifteenth aspects, which contains (D) a base resin further having a non-radical polymerizable crosslinkable group.
As a 17th viewpoint, it relates to the base material according to any one of the 1st to 16th viewpoints, which further contains (E) a cross-linking agent.
As the eighteenth viewpoint, the present invention relates to an electroless metal plating base layer composed of a film containing the electroless plating base agent according to any one of the first to seventeenth viewpoints.
The nineteenth aspect relates to the metal plating film formed on the base layer of the electroless metal plating according to the eighteenth aspect.
As a twentieth viewpoint, a base material, an electroless metal plating base layer formed on the base material according to the eighteenth viewpoint, and a metal plating film formed on the electroless metal plating base layer. The present invention relates to a metal coating substrate.
As a 21st viewpoint, the present invention relates to a method for producing a metal coating base material, which comprises the following steps (1) and (2).
(1) Step: The electroless plating base material according to any one of the first to 17th viewpoints is applied onto a base material, and an electroless metal plating base layer is formed on the base material. Process,
(2) Step: A step of immersing the base material on which the base layer is formed in an electroless plating bath to form a metal plating film on the base layer.

The base material of the present invention can easily form a base layer for non-electrostatic plating simply by applying it on a base material. Further, according to the present invention, it is possible to form a base layer for plating which is excellent in adhesion to a substrate and does not affect the precipitation property of plating. Moreover, the base material of the present invention can be easily varnished with various compositions, and can have high metal fine particle dispersion stability.
Further, since the polymer used for the base material of the present invention can be easily prepared with a small number of processes, it is possible to simplify the manufacturing process of the plating base material and reduce the manufacturing cost.
Further, the electroless metal plating base layer formed from the electroless plating base agent of the present invention can easily form a metal plating film simply by immersing it in an electroless plating bath, and can easily form a base material, a base layer, and a metal. A metal film base material provided with a plating film can be easily obtained.
That is, even if a plating base agent containing a base resin that imparts adhesion of the present invention is used, a base layer that exhibits excellent plating precipitation can be formed on the base material.

Hereinafter, the present invention will be described in detail.
The base material of the present invention is a base material containing (A) a copolymer having the above-mentioned specific structural unit, (B) metal fine particles, and (C) a solvent, and if necessary, containing other components.
The base material of the present invention is suitably used as a catalyst for forming a metal plating film on a substrate by electroless plating. Hereinafter, each component will be described.
<(A) Copolymer>

The component (A) has a structural unit derived from a monomer a having a crosslinkable group and one radically polymerizable double bond in the molecule, and a metal dispersible group and one radically polymerizable double bond in the molecule. It is a copolymer containing a structural unit derived from the monomer b having.

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

Specific examples of the monomer a include a compound represented by the following formula (1).

(In the formula (1), M represents a single bond, a carbonyloxy group, an amide group or a phenylene group, and J is a linear or branched group having 1 to 10 carbon atoms having at least one trifluoromethyl group. Represents an alkyl group of structure, and R ⁶ represents an alkyl group having a hydrogen atom or 1 to 4 carbon atoms.)
　When M represents a carbonyloxy group or an amide group, it can take the structures of the following formulas (1-1) to (1-3), but the structure of the formula (1-1) is preferable.

J is a perfluoromethyl group (that is, a trifluoromethyl group), a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, 2,2. 2-Trifluoro-1- (trifluoromethyl) ethyl group, perfluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1, 2,2,3,3,3-heptafluoropropyl group, hexafluoroisopropyl group, perfluorobutyl group, 4,4,4-trifluorobutyl group, 3,3,4,5,4-pentafluorobutyl group , 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group or 2- (perfluorohexyl) Ethyl group and the like can be mentioned.
Among these, J is preferably a 2,2,2-trifluoroethyl group, a hexafluoroisopropyl group or a 2- (perfluorohexyl) ethyl group.

Specific examples of such a monomer a are not limited, but include the following. For example, 2,2,2-trifluoroethyl acrylate, hexafluoro-2-propyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate and the like can be mentioned.

[Monomer b]
In the present invention, the monomer b is a compound having a metal dispersible group and one radically polymerizable double bond in the molecule.
The metal dispersible group improves the dispersibility in the composition of the metal fine particles by interacting with the metal fine particles of the component (B) such as adhesion and / or coordination, thereby forming the metal fine particles in the composition. It is a basis for stable existence. As such a metal dispersible group, a substituent having a carbonyl and a nitrogen atom covalently bonded to the carbonyl, that is, a substituent having an -C (= O) -N-site is preferable, and more specifically, a substituent having a -C (= O) -N-site is preferable. A group selected from the group consisting of a group having an amide bond and a group having an imide bond is preferable.
The radically polymerizable double bond is preferably a compound having one of either a vinyl group or a (meth) acryloyl group. When the monomer b is a compound having a (meth) acryloyl group as a radically polymerizable double bond, the carbonyl group [-C (= O)-] contained in the (meth) acryloyl group is a metal dispersible group. It may have a structure that overlaps with the carbonyl group in the amide group as.

Specific examples of the monomer b include compounds represented by the following formula (2) or formula (3).

(In the formula (2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents O or N, and R ₂ exists only when L represents N. Representing a hydrogen atom, or R ₁ and R ₂ may be combined with the atom to which they are attached to form a 4- to 6-membered cyclic amide.
In the formula (3), R ₃ represents a hydrogen atom or a methyl group, and R ₄ may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or a branch having 1 to 10 carbon atoms. alkoxyl group or represents an alkoxyl alkyl group branched having 1 to 10 carbon atoms, L represents an O or N, R ₅ is present only when L represents N, tables hydrogen atom Alternatively, R ₄ and R ₅ may be combined with the atoms to which they are attached to form a 4- to 6-membered cyclic amide, or a 4- to 6-membered cyclic imide. )

Examples of such a monomer b include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-propyl (meth). Acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (meth) Acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-vinylphthalimide, N-vinylsuccinimide And so on.

Among them, as the monomer b, the monomer represented by the formula (2) is preferable from the viewpoint of the coordinating ability of the monomer to the metal, the monomer having an N-vinylamide group is more preferable, and N- Vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide are more preferable.
One of these monomers b may be used alone, or two or more thereof may be used in combination.

[Monomer c]
The component (A) is also a copolymer containing, in addition to the monomer a and the monomer b, a structural unit derived from the monomer c having a crosslinkable group and one radically polymerizable double bond in the molecule.
Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an epoxy group which may have a substituent Q, an alicyclic epoxy group which may have a substituent Q, and a substituent Q. Examples thereof include an oxetane group which may be used. Examples of the substituent Q include an alkyl group having 1 to 4 carbon atoms and a phenyl group which may be substituted with a halogen.

Specific examples of the monomer c include a compound represented by the following formula (4).

(In the formula (4), X represents a single bond, a carbonyloxy group, an amide group or a phenylene group, and Y is an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, and a carbon atom. Represents an alkyl ether group of number 1 to 6, a thioalkylene group having 1 to 6 carbon atoms, or a thioalkyl ether group having 1 to 6 carbon atoms, and Z is the number of carbon atoms having at least one trifluoromethyl group. 1 to 10 represents an alkyl group having a linear or branched structure, and R ⁷ represents an alkyl group having a hydrogen atom or 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 limited, but are methylene group and ethane-1,1-diyl. Group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, pentane-1 , 5-Diyl group, hexane-1,6-Diyl group and the like.

Oxyalkylene group having from 1 to 6 carbon atoms is, on linear, may be either branched, -O-R 8 ^- and an alkylene group having 1 described above as specific examples of a group which satisfies the R ⁸ 6 It is the same.

Alkyl ether group having from 1 to 6 carbon atoms is, on linear, may be either branched, -R 9 ^-O-R 9 ^- is a group satisfying, the invention is not limited to specific examples of R ⁹ Not, but independently of each other, methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2, Examples thereof include 2-diyl group, butane-1,4-diyl group and pentane-1,5-diyl group. However the total number of carbon atoms of the two R ⁹ is a 6.

Thioalkylene groups having from 1 to 6 carbon atoms is, on linear, may be either branched, -S-R 8 ^- a group that satisfies R ⁸ are as described above.

The thioalkyl ether group having 1 to 6 carbon atoms may be linear or branched, and is a group satisfying ^{—R 9} −SR ⁹ ^{−, and R 9} is as described above.

Specific examples of such a monomer c are not limited, but include the following.

Examples of the monomer having one radically polymerizable double bond and further having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, and N-methoxymethylmethacrylamide. , N-methylol acrylamide and the like.

Examples of the monomer having one radically polymerizable double bond and further having an N-hydroxymethyl group include, but are not limited to, N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide. Be done.

The monomer having one radically polymerizable double bond and further having an epoxy group is not limited, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethylacrylate, α-n-propyl. Glycidyl acrylate, α-n-butyl glycidyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7- Epoxide heptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like can be mentioned. .. Among these, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like. It is preferably used. These may be used alone or in combination.

The monomer having one radically polymerizable double bond and further having an oxetane group is not limited, and examples thereof include (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetan, 3- (acryloyloxymethyl) -3- Ethyl-oxetan, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetan, 3- (Acryloyloxymethyl) -2-phenyl-oxetan, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) Methyl) -4-trifluoromethyloxetane is preferable, and 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane and the like are preferably used.
Among these, X is preferably a carbonyloxy group or a methylene group, and Z is preferably an epoxy group from the viewpoint of adhesion to the substrate.

In the present invention, other monomers can be used together with the above-mentioned monomer a, the above-mentioned monomer b, and the above-mentioned monomer c when producing the copolymer of the component (A). Such other monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, and 2 -Ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl Methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydro Flufuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinyl naphthalene , Vinyl anthracene, vinyl biphenyl and the like.

In the present invention, when the copolymer of the component (A) is produced, the resistance of the obtained copolymer of the component (A) to a plating solution or the like can be imparted by using the above-mentioned other monomers. ..

The method for obtaining the specific copolymer used in the present invention is not particularly limited, but for example, in a solvent in which the above-mentioned monomer a, the above-mentioned monomer b, the above-mentioned monomer c, and if desired, another monomer and a polymerization initiator or the like coexist, 50 It is obtained by carrying out a polymerization reaction at a temperature of about 110 ° C. At that time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having no specific functional group used if desired, a polymerization initiator and the like. Specific examples will be described in <(C) Solvent> described later.
The specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained by the above method is put into diethyl ether or water under stirring to precipitate, and the generated precipitate is filtered and washed, and then at room temperature under normal pressure or reduced pressure. It can be dried or heat-dried to obtain a powder of a specific copolymer. By the above operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

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

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

In the present invention, the ratio of copolymerizing the monomer a and the monomer b is preferably 0.05 mol to 5 mol of the monomer a with respect to 1 mol of the monomer b, particularly from the viewpoint of reactivity and plating property. It is preferably 0.1 mol to 3 mol.
In the present invention, the ratio of copolymerizing the monomer b and the monomer c is preferably 0.05 mol to 3 mol, particularly, 0.05 mol to 3 mol of the monomer c with respect to 1 mol of the monomer b from the viewpoint of reactivity and plating property. It is preferably 0.1 mol to 1 mol.

In the present invention, when the other monomer is used in producing the copolymer as the component (A), the total number of moles of the monomer a and the monomer b, or the monomer a, the monomer b and the monomer are used. The amount of moles is 1 to 200%, more preferably 10 to 100% of the total number of moles of c.

<(B) Metal fine particles>
The (B) metal fine particles used in the base material of the present invention are not particularly limited, and the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), and silver. Examples thereof include (Ag), tin (Sn), platinum (Pt) and gold (Au), and alloys thereof, and one kind of these metals may be used, or two or more kinds of alloys may be used. Among them, palladium fine particles are mentioned as preferable metal fine particles. The metal oxide may be used as the metal fine particles.

The metal fine particles are obtained by reducing metal ions by, for example, a method of irradiating a solution of a metal salt with light with a high-pressure mercury lamp, a method of adding a compound having a reducing action (so-called reducing agent) to the solution, or the like. For example, a metal salt solution is added to a solution in which the component polymer (A) is dissolved and irradiated with ultraviolet rays, or a metal salt solution and a reducing agent are added to the solution to obtain metal ions. By reducing the above, a base material containing the component polymer (A) and the metal fine particles can be prepared while forming a complex of the component polymer (A) and the metal fine particles.

Examples of the metal salt include gold chloride acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, first platinum chloride, platinum chloride acid, Pt (dba) ₂ [dba = dibenzylidene acetone], 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 ensemble, ruthenium acetate, Ru (cod) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni (cod) _2, etc. Can be mentioned.
The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species and the like contained in the obtained base material. Examples of the reducing agent that can be used include boron hydride metal salts such as sodium boron hydride and potassium boron hydride; aluminum lithium hydride, potassium aluminum hydride, aluminum cesium hydride, aluminum berylium hydride, and hydrogenation. Aluminum hydride salts such as aluminum magnesium and aluminum hydride calcium; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary such as methanol, ethanol, isopropanol and polyols. Class alcohols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; tri-n-propylphosphine, tri-n- Butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane [DPPE], 1,3-bis (diphenylphosphino) propane [DPPP], 1 , 1'-bis (diphenylphosphino) ferrocene [DPPF], 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl [BINAP] and the like.

The average particle size of the primary particles of the metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the primary particles of the metal fine particles to 100 nm or less, the surface area is not reduced and sufficient catalytic activity can be obtained. The average particle size of the primary particles is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.
The average particle size of the primary particles can be measured by the following method.
[Measurement of average particle size of primary particles]
After dispersing the metal fine particles in ethanol, they are dropped onto a carbon support membrane and dried to prepare a sample, and then the obtained sample is microscopically subjected to a TEM device (Hitachi, Ltd .: H-8000 acceleration voltage 200 kV). The average particle size can be determined.

The amount of the copolymer, which is the component (A), added to the base material of the present invention is preferably 20 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the metal fine particles (B). When the amount of the (A) copolymer added to 100 parts by mass of the (B) metal fine particles is 20 parts by mass or more, the metal fine particles can be sufficiently dispersed, and when it is 20 parts by mass or less, the metal fine particles can be sufficiently dispersed. The dispersibility of the metal fine particles is insufficient, and precipitates and agglomerates are likely to be formed. More preferably, it is 30 parts by mass or more. Further, when 10,000 parts by mass or more of the (A) copolymer is added to 100 parts by mass of (B) metal fine particles, the amount of Pd per unit area after coating becomes insufficient, so that the precipitation property of plating becomes poor. It may decrease.

<Base material>
The electroless plating base material of the present invention contains the above-mentioned (A) copolymer, (B) metal fine particles, and (C) solvent, and further contains other components if necessary. In the electroless plating base material of the present invention, it is preferable that the copolymer which is the component (A) and the metal fine particles (B) form a composite, that is, the base material is the component (A). It is preferable to contain a composite formed by a certain copolymer and the metal fine particles (B).

Here, the composite is a composite in which both of them coexist in contact with or in close contact with the metal fine particles due to the action of the metal dispersible group of the side chain of the copolymer which is the component (A), and form a particulate form. In other words, it is expressed as a composite having a structure in which metal fine particles are attached or coordinated to the metal dispersible group of the copolymer which is the component (A).
Here, the "adhered or coordinated structure" refers to a state in which a part or all of the metal dispersible groups of the copolymer which is the component (A) interacts with the metal fine particles, thereby forming a complex-like structure. Is considered to form. Therefore, when palladium fine particles are used as the metal fine particles, it is considered that the Pd atom on the surface layer interacts with the metal dispersible group to form a structure in which the component polymer (A) surrounds the metal fine particles.

Therefore, the "complex" in the present invention includes not only those in which the metal fine particles and the copolymer (A) are bonded to form one complex as described above, but also the metal fine particles ( A) Copolymers as components may be included in which they exist independently without forming a bonding portion (those that appear to form one particle). ..

The formation of the composite of the copolymer (A) component and the (B) metal fine particles is carried out at the same time as the preparation of the base material containing the copolymer (A) component and the metal fine particles, and the method is as follows. , A method of exchanging a ligand with a polymer which is a component (A) after synthesizing metal fine particles stabilized to some extent by a metal dispersible group, or a metal ion in a solution of a polymer which is a component (A). There is a method of forming a complex by directly reducing. Further, as described above, a metal salt solution is added to a solution in which the copolymer which is the component (A) is dissolved and irradiated with ultraviolet rays, or a metal salt solution and a reducing agent are added to the solution. A complex can also be formed by reducing metal ions, such as by adding them.

As a direct reduction method, the metal ion and the copolymer (A) component are dissolved in a solvent and reduced with primary or secondary alcohols such as methanol, ethanol, 2-propanol and polyol. The desired metal fine particle composite can be obtained.
As the metal ion source used here, the above-mentioned metal salt can be used.
The solvent to be used is not particularly limited as long as it can dissolve a polymer having a metal ion and a metal dispersible group in a required concentration or more, but specifically, methanol, ethanol, n-propanol, 2-propanol and the like. Alcohols; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide (DMF) ), N-methyl-2-pyrrolidone (NMP) and the like; sulfoxides such as dimethyl sulfoxide and the like and a mixed solution of these solvents are mentioned, and alcohols, halogenated hydrocarbons, cyclic ethers and the like are preferable. , And more preferably, ethanol, 2-propanol, chloroform, tetrahydrofuran and the like can be mentioned.
The temperature of the reduction reaction (mixing the metal ion and the copolymer which is the component (A)) can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably room temperature (about 25 ° C.) to 100 ° C. Is the range of.

As another direct reduction method, the desired metal fine particle composite can be obtained by dissolving the metal ion and the copolymer (A) component in a solvent and reacting them in a hydrogen gas atmosphere.
Examples of the metal ion source used here include the above-mentioned metal salts, hexacarbonyl chrome [Cr (CO) ₆ ], pentacarbonyl iron [Fe (Co) ₅ ], and octacarbonyl dicobalt [Co ₂ (CO) ₈ ]. , Tetracarbonyl nickel [Ni (CO) ₄ ] and other metal carbonyl complexes can be used. Further, 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 metal ion and the copolymer (A) component in a required concentration or more, but specifically, alcohols such as ethanol and propanol; methylene chloride. , Halogenated hydrocarbons such as chloroform; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile and a mixture of these solvents are mentioned, preferably tetrahydrofuran. ..
The temperature at which the metal ion and the copolymer as the component (A) are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent.

Further, as a direct reduction method, the desired metal fine particle composite can be obtained by dissolving the metal ion and the copolymer (A) component in a solvent and causing a thermal decomposition reaction.
As the metal ion source used here, the above-mentioned metal salt, metal carbonyl complex, other zero-valent metal complex, and metal oxide such as silver oxide can be used.
The solvent used is not particularly limited as long as it can dissolve the metal ion and the copolymer (A) component in a required concentration or more, but specifically, methanol, ethanol, n-propanol, isopropanol, etc. Alcohols such as ethylene glycol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; benzene, toluene and the like Examples thereof include aromatic hydrocarbons and a mixed solution of these solvents, and toluene is preferable.
The temperature at which the metal ion and the copolymer which is the component (A) having a metal dispersible group are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably near the boiling point of the solvent, for example, toluene. In the case, it is 110 ° C. (heating reflux).

The composite of the copolymer and the metal fine particles, which is the component (A) thus obtained, can be in the form of a solid substance such as powder through a purification treatment such as reprecipitation.

The base material of the present invention contains the copolymer (A) component, (B) metal fine particles (preferably a composite composed of these), and (C) solvent, and further, if necessary. The base material contains other components, and the base material may be in the form of a varnish used when forming the [base layer of electroless metal plating] described later.

The electroless plating base material of the present invention can contain the base resin which is the component (D), if desired. As the component (D), a component having a non-radical polymerizable crosslinkable group, which is a group that undergoes a crosslink reaction with the crosslinkable group in the component (A) by heat, is preferable. The one described as is preferable. By adding such a component (D), it may be possible to further improve other functions (for example, adhesion, heat resistance, photosensitivity, dielectric property, etc.) of the obtained base layer.

When the plating base material of the present invention contains the component (D), the content is 0 parts by mass based on a total of 100 parts by mass of the copolymer of the component (A) and the metal fine particles of the component (B). It is preferably from 0 part by mass to 200 parts by mass, and more preferably from 0 part by mass to 150 parts by mass. If the content of the component (D) is excessive, the plating precipitation property may decrease.

The electroless plating base material of the present invention can contain a cross-linking agent which is the component (E), if desired.

Examples of the cross-linking agent as the component (E) include an epoxy compound, a methylol compound, a blocked isocyanate compound, a phenoplast compound, a compound having two or more trialkoxysilyl groups, a compound such as an alkoxysilane compound having an amino group, an alkoxy group, and the like. / Or an organic metal compound having a chelate ligand, a polymer of N-alkoxymethylacrylamide, a polymer of a compound having an epoxy group, a polymer of a compound having an alkoxysilyl group, a polymer of a compound having an isocyanate group, and Examples thereof include compounds such as melamine formaldehyde resin.

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, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N', -tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, and N, N, N', N'-tetraglycidyl-4, 4'-diaminodiphenylmethane And so on.

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

Specific examples of alkoxymethylated glycol uryl include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrax (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Co., Ltd. (high condensation type, trade name: Beccamin () Registered trademarks) J-300S, P-955, N) and the like.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)). ) 506, 508), Sanwa Chemical's methoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, the same MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MX-45, MX-410, MX-302) and the like.

Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.

The above-mentioned blocked isocyanate compound has two or more isocyanate groups in one molecule in which the isocyanate group is blocked by an appropriate protective group, and when exposed to a high temperature during thermosetting, the protective group (block portion) becomes hot. It dissociates and comes off, and the generated isocyanate group causes a cross-linking reaction with the resin.

Such a polyfunctional blocked isocyanate compound can be obtained, for example, by 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, and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate. 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-cyclohexyldiisocyanate, 2,6-bis ( Isocyanatemethyl) tetrahydrodicyclopentadiene, bis (isocyanatemethyl) dicyclopentadiene, bis (isocyanatemethyl) adamantan, 2,5-diisocyanatemethylnorbornene, norbornandiisocyanate, dicycloheptanetriisocyanate, 4,4'-diphenylmethanediisocyanate, 2 , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalenedisocyanate, p-phenylenedi isocyanate, 1,3-bis (isocyanatemethyl) benzene, dianisidine Diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,6-bis (isocyanate methyl) decahydronaphthalene, bis (diisocyanate trill) phenylmethane, 1,1'-methylenebis (3-) Methyl-4-isocyanate benzene), 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 4,4'-biphenylenediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, bis (isocyanatemethyl) thiophene, bis (isocyanatemethyl) tetrahydrothiophene, and modified compounds thereof. (For example, isocyanurate body, biuret body, ethylene glycol adduct body, propylene glycol adduct body, trimethylpropane adduct body, ethanolamine adduct body, polyester polyol adduct body, polyether polyol adduct body, polyamide adduct body, polyami (Adduct body) can be mentioned.

Examples of the blocking agent include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, and the like. 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), tri Alcohols such as ethylene glycol monoethyl ether, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dibutylaminoethanol, phenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, Phenols such as chlorophenol, o-cresol, m-cresol, p-cresol, xylenol, lactams such as α-pyrrolidone, β-butyrolactam, β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam Oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, diethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3, Pyrazoles such as 5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, benzene Mercaptans such as thiols, malonic acid diesters, acetoacetate, dinitrile malonate, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivaloylmethane, active methylene compounds such as acetone dicarboxylic acid diester, dibutylamine, diisopropylamine , Di-tert-butylamine, di (2-ethylhexyl) amine, dicyclohexylamine, benzylamine, diphenyl Amines such as nylamine, aniline and carbazole, imidazoles such as imidazole and 2-ethylimidazole, imines such as methyleneimine, ethyleneimine, polyethyleneimine and propyleneimine, acids such as acetanilide, acrylamide, acetate amide and dimer acid amide. Examples thereof include acidimides such as amides, succinateimide, maleateimide and phthalateimide, and urea compounds such as urea, thiourea and ethyleneurea. Further, it may be an internal block type due to a uretdione bond (dimerization of isocyanate groups).

Examples of commercially available products of the polyfunctional blocked isocyanate compound include the following products.
Takenate [registered trademark] B-815N, B-830, B-842N, B-846N, B-870, B-870N, B-874, B-874N, B-882, same B-882N, B-5010, B-7005, B-7030, B-7075 (all manufactured by Mitsui Chemicals, Inc.).

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

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

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

TRIXENE BI-7461, BI-7642, BI-7986, BI-7987, BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7981, BI-7982, BI-7984, BI-7986, BI-7990, BI-7991, BI-7992, BI-7770, BI-7772, BI-7779, DP9C / 214 ( Above, manufactured by Baksenden Chemicals Co., Ltd.).

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

Further, examples of the polyfunctional blocked isocyanate compound include homopolymers or copolymers obtained by radical polymerization of (meth) acrylate having a blocked isocyanate group. Here, the copolymer means a polymer obtained by polymerizing two or more kinds of monomers. The copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having a blocked isocyanate group, or polymerizing a (meth) acrylate having a blocked isocyanate group and another (meth) acrylate. It may be the obtained copolymer. Commercially available products of (meth) acrylates having such a blocked isocyanate group include, for example, Showa Denko KK Karens [registered trademark] MOI-BM, AOI-BM, MOI-BP, AOI-BP, and the like. Examples thereof include the MOI-DEM, the MOI-CP, the MOI-MP, the MOI-OEt, the MOI-OBu, and the MOI-OiPr.

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

Specific examples of the above-mentioned phenoplast compound include the following compounds, but the phenoplast 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, and 4,4'-bis (tri). Methoxysilyl) biphenyl, 4,4'-bis (triethoxysilyl) biphenyl, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, Bis (trimethoxysilyl) ethylene, bis (triethoxysilyl) ethylene, 1,3-bis (trimethoxysilylethyl) tetramethyldisiloxane, 1,3-bis (triethoxysilylethyl) tetramethyldisiloxane, bis ( Triethoxysilylmethyl) amine, bis (trimethoxysilylmethyl) amine, bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) carbonate, bis (3-tri) Ethoxysilylpropyl) carbonate, bis [(3-trimethoxysilyl) propyl] disulfide, bis [(3-triethoxysilyl) propyl] disulfide, bis [(3-trimethoxysilyl) propyl] thiourea, bis [(3-trimethoxysilyl) propyl] Triethoxysilyl) propyl] thiourea, bis [(3-trimethoxysilyl) propyl] urea, bis [(3-triethoxysilyl) propyl] urea, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4 -Bis (triethoxysilylmethyl) benzene, tris (trimethoxysilylpropyl) amine, tris (triethoxysilylpropyl) amine, 1,1,2-tris (trimethoxysilyl) ethane, 1,1,2-tris ( Examples thereof include compounds such as triethoxysilyl) ethane, tris (3-trimethoxysilylpropyl) isocyanurate, and tris (3-triethoxysilylpropyl) isocyanurate.

Specific examples of the alkoxysilane compound having an amino group include, for example, N, N'-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N, N'-bis [3- (tri). Ethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2- Ethandiamine, bis- {3- (trimethoxysilyl) propyl} amine, bis- {3- (triethoxysilyl) propyl} amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, trimethoxy {3 -(Methylamino) propylsilane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-allylamino) propyltriethoxysilane, 3- (diethylamino) propyltrimethoxysilane, 3- (diethylamino) propyltriethoxysilane Examples thereof include compounds such as silane, 3- (phenylamino) propyltrimethoxysilane, and 3- (phenylamino) propyltriethoxysilane.

Specific examples of the organic metal compound having an alkoxy group and / or a chelating ligand include, for example, diisopropoxyethylacetoneacetate aluminum, diisopropoxyacetylacetonealuminum, triacetylacetonealuminum, tetrakisisopropoxytitanium, and tetrakis. Compounds such as normal butoxytitanium, tetraoctyl titanate, diisopropoxybis (acetylacetoneate) titanium, titanium tetraacetylacetone, tetrakis (normalpropoxy) zirconium, tetrakis (normalbutoxy) zirconium, tetrakis (acetylacetoneate) zirconium Can be mentioned.

Further, examples of the above-mentioned N-alkoxymethylacrylamide polymer include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth). ) Examples thereof include polymers produced by using an acrylamide compound or a methacrylicamide compound substituted with a hydroxymethyl group such as acrylamide or an alkoxymethyl group.

Specific examples of such polymers include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N. Examples thereof include a copolymer of -ethoxymethylmethacrylamide and benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide, benzylmethacrylate and 2-hydroxypropylmethacrylate. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

Examples of the polymer of the compound having an epoxy group include a polymer produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate. Be done.

Specific examples of such polymers include poly (3,4-epoxycyclohexylmethylmethacrylate), poly (glycidylmethacrylate), copolymers of glycidylmethacrylate and methylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate. Examples thereof include a copolymer with methyl methacrylate and a copolymer with glycidyl methacrylate and styrene. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

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

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

These cross-linking agents can be used alone or in combination of two or more.

When the plating base material of the present invention contains the component (E), the content is 0 parts by mass based on a total of 100 parts by mass of the copolymer of the component (A) and the metal fine particles of the component (B). It is preferably from 0 parts by mass to 100 parts by mass, and more preferably from 0 parts by mass to 50 parts by mass.

<Other additives>
As the base material of the present invention, additives such as a surfactant, various surface conditioners, and thickeners may be appropriately added 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 octylphenyl ether and polyoxy. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, Solbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate. EF Top (registered trademark) EF-301, EF-303, EF-352 [above, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.], Megafuck (registered trademark) F-171, F-173, R -08, R-30 [above, manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430, FC-431 [above, manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) AG-710 Fluorine-based surfactants such as [manufactured by Asahi Glass Co., Ltd.] and Surflon (registered trademark) S-382 [manufactured by AGC Seimi Chemical Co., Ltd.] can be mentioned.

Further, as the surface conditioner, a silicone-based leveling agent such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; BYK (registered trademark) -302, 307, 322, 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.

Examples of the thickener include polyacrylic acids (including crosslinked ones) such as carboxyvinyl polymer (carbomer); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and polystyrene (PS). ) And other vinyl polymers; polyethylene oxides; polyester; polycarbonate; polyamide; polyurethane; dextrin, agar, caraginan, alginic acid, Arabic gum, guar gum, tragant gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose Polysaccharides such as, and proteins such as gelatin and casein. In addition, each of the above polymers includes not only homopolymers but also copolymers. These thickeners may be used alone or in combination of two or more.
In the base material of the present invention, the viscosity and rheological characteristics of the base material can be adjusted by adding a thickener as necessary, and the base material can be appropriately applied according to the application method, application location, and the like. Can be adopted / selected.

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

[Base layer of electroless metal plating]
The electroless plating base material of the present invention described above can be applied onto a base material to form an electroless metal plating base layer. The base layer of this electroless metal plating is also an object of the present invention.

The base material is not particularly limited, but a non-conductive base material or a conductive base material can be preferably used.
Examples of the non-conductive base material include glass, ceramic, etc .; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene). Examples thereof include terephthalate) resin, PEEK (polyether ether ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, LCP (liquid crystal polymer) resin, and the like. These are preferably used in the form of a sheet, a film, or the like, and the thickness in this case is not particularly limited.
Examples of the conductive substrate include ITO (tin-doped indium oxide), ATO (antimon-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide), and the like. Various stainless steels, aluminum alloys such as aluminum and duralmin, iron and iron alloys, copper and brass, copper alloys such as phosphor bronze, white copper and beryllium copper, nickel and nickel alloys, and metals such as silver alloys such as silver and western silver. And so on.
Further, a base material in which a thin film is formed of these conductive base materials on the non-conductive base material can also be used.
Further, the base material may be a three-dimensional molded product.

It contains the copolymer (A) component, (B) metal fine particles (preferably a composite composed of these), and (C) solvent, and further contains (D) base resin and (E) cross-linking as required. As a specific method for forming a base layer for electroless metal plating from an electroless plating base material containing an agent and other components, first, the component polymer (A) and fine metal particles (B) (preferably a composite composed of these) are used. ) (And, if necessary, (D) base resin, (E) cross-linking agent and other components) are dissolved or dispersed in (C) solvent to form a varnish, and the varnish is used as a group to form a metal plating film. Spin coating method; blade coating method; dip coating method; roll coating method; bar coating method; die coating method; spray coating method; inkjet method; fountain pen nanolithography (FPN), dip pen nanolithography (DPN), etc. Pen lithography; typographic printing, flexo printing, resin letterpress printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), nanotransfer printing (nTP) and other letterpress printing methods; gravure printing, engraving, etc. The concave printing method; the flat printing method; the stencil printing method such as screen printing and copying plate; the offset printing method and the like are applied, and then the solvent is evaporated and dried to form a thin layer.
Among these coating methods, bar coating method, flexographic printing, gravure printing, spin coating method, spray coating method, inkjet method, pen lithography, contact printing, μCP, NIL and nTP are preferable. When the spin coating method is used, since it can be applied in a single time, there is an advantage that even a highly volatile solution can be used and a highly uniform application can be performed. When the spray coating method is used, a highly uniform coating can be performed with a very small amount of varnish, which is industrially very advantageous. When the inkjet method, pen lithography, contact printing, μCP, NIL, or nTP is used, fine patterns such as wiring can be efficiently formed (drawn), which is industrially very advantageous.

<(C) Solvent>
Further, as the solvent used here, the polymer which is the component (A), (B) fine metal particles (preferably a composite composed of these), and optionally the component (D), the component (E) and other components are dissolved. Alternatively, it is not particularly limited as long as it disperses, but for example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, and the like. Alcohols such as 2-butanol, n-hexanol, n-octanol, 2-octanol, 2-ethylhexanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve; propylene glycol monomethyl ether (PGME), propylene glycol Monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Glycol ethers such as 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; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Glycol esters such as (PGMEA); ethers such as tetrahydrofuran (THF), methyl tetrahydrofuran, 1,4-dioxane, diethyl ether; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone Ketones such as (MIBK), cyclopentanone, cyclohexanone; aliphatic hydrocarbons such as n-heptane, n-hexane, cyclohexane; halogenated aliphatic hydrocarbons such as 1,2-dichloroethane, chloroform; N- Methyl-2-pyrrolidone (NMP), N, N-dime Amides such as tylformamide (DMF), N, N-dimethylacetamide; dimethyl sulfoxide and the like can be used. These solvents may be used alone or may be a mixture of two or more kinds of solvents. Further, glycols such as ethylene glycol, propylene glycol and butylene glycol may be added for the purpose of adjusting the viscosity of the varnish.
The concentration to be dissolved or dispersed in the solvent is arbitrary, but the concentration of the non-solvent component in the varnish [the polymer which is the component ((A)) and the metal fine particles (B) (preferably) of all the components except the solvent contained in the base material. Concentration of (complex composed of these), optionally (D) base polymer, (E) cross-linking agent, other components, etc.)] is 0.05 to 90% by mass, preferably 0.1 to 80% by mass. be.

The method for drying the solvent is not particularly limited, and for example, it may be evaporated in an appropriate atmosphere, that is, in an atmosphere, an inert gas such as nitrogen, or in a vacuum, using a hot plate or an oven. This makes it possible to obtain a base layer having a uniform film-forming surface. The firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably performed at 40 to 250 ° C.

[Electroless plating, metal plating film, metal film base material]
By electroless plating the base layer of the electroless metal plating formed on the base material obtained as described above, a metal plating film is formed on the base layer. The metal plating film thus obtained, and the metal coating base material provided on the base material in the order of the electroless metal plating base layer and the metal plating film are also the objects of the present invention.
The electroless plating treatment (process) is not particularly limited and can be performed by any generally known electroless plating treatment. For example, the plating is performed using a conventionally known electroless plating solution. A general method is to immerse the base layer of electroless metal plating formed on the base material in a liquid (bath).

The electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and is a pH adjuster, a pH buffer, and a reaction accelerator (second complexing agent) according to other uses. , Stabilizers, surfactants (for imparting gloss to the plating film, for improving the wettability of the surface to be treated, etc.) and the like are appropriately included.
Examples of the metal used for the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and alloys thereof, which are appropriately selected according to the purpose. Will be done.
Further, the complexing agent and the reducing agent may be appropriately selected according to the metal ions.

A commercially available electroless plating solution may be used as the electroless plating solution. For example, an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd. and an electroless copper plating chemical (Melplate (Melplate)) may be used. (Registered trademark) CU series); Electroless nickel plating solution (ICP Nicolon (registered trademark) series, Top Piena 650) manufactured by Okuno Pharmaceutical Co., Ltd., electroless copper plating solution (OPC-700 electroless copper MK, ATS Ad Copper IW, CT, OPC Copper (registered trademark) AF series, HFS, NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (flash gold 330, self gold OTK) -IT), electroless silver plating solution (Muden Silver); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd., electroless gold plating solution (Dip G series, NC gold series); Sasaki Chemical Electroless silver plating solution manufactured by Yakuhin Co., Ltd. (Sdia AG-40); Electroless nickel plating solution manufactured by Nippon Kanizen Co., Ltd. Kani Black (registered trademark) series), electroless palladium plating solution (S-KPD); electroless copper plating solution manufactured by Dow Chemical Co., Ltd. Electroless palladium plating solution (Palamers (registered trademark) series), electroless nickel plating solution (Duraposit (registered trademark) series), electroless gold plating solution (Aurorectores (registered trademark) series), electroless tin plating solution (Tinposit (registered trademark) series); Electroless copper plating solution manufactured by Uemura Kogyo Co., Ltd. (Sulcup (registered trademark) ELC-SP, PSY, PCY, PGT, PSR, PEA, PMK) , Electroless copper plating solution (Print Gant (registered trademark) PV, PVE) manufactured by Atotech Japan Co., Ltd. can be preferably used.

In the electroless plating step, the formation speed of the metal film is adjusted by adjusting the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring and stirring speed, presence / absence of supply of air / oxygen, supply speed, and the like. And the film thickness can be controlled.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measurement of the number average molecular weight and the weight average molecular weight is as follows.
[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the copolymers obtained according to the following synthesis examples were determined by using a GPC apparatus (Shodex column KD800 and TOSOH column TSK-GEL) manufactured by Toso Co., Ltd., and the elution solvent N, N-dimethylformamide was used. (as an additive, lithium bromide - hydrate _{(LiBr · H 2 O) 10mmol} / L ( liter) mixing) on the condition that is eluted by flowing through the column at a flow rate of 1 mL / min (column temperature 40 ° C.) It was measured. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.

The meanings of the abbreviations used in the following examples are as follows.
HEA: 2-Hydroxyethyl acrylate NVA: N-Vinylacetamide GMA: Glycidyl methacrylate cyclomer M100: 3,4-Epoxycyclohexylmethylmethacrylate (manufactured by Daicel)
Viscoat 3F: 2,2,2-trifluoroethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HFIP-M: Hexafluoro-2-propyl methacrylate (manufactured by Central Glass)
FAMAC-6: 2- (Perfluorohexyl) Ethyl Methacrylate (manufactured by Unimatec)
AMBN: 2,2'-azobis-2-methylbutyronitrile PGME: propylene glycol monomethyl ether IPE: diisopropyl ether BL-10: polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd.)
8KX-127: Acrylic resin (manufactured by Taisei Fine Chemicals Co., Ltd.)
[Polymer synthesis]

<Synthesis example 1>
A polymer solution (solid content concentration: 30 mass) obtained by dissolving 2.03 g of styrene, 1.63 g of NVA, 2.23 g of HEA, and 0.29 g of AMBN in 14.37 g of PGME and reacting at 80 ° C. for 20 hours. %) Was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P1). The obtained polymer had Mn of 6,806 and Mw of 11,797.

<Synthesis example 2>
A copolymer solution (solid content concentration 30) obtained by dissolving 2.03 g of styrene, 1.63 g of NVA, 2.73 g of GMA, and 0.32 g of AMBN in 15.59 g of PGME and reacting at 80 ° C. for 20 hours. Mass%) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P2). The obtained copolymer had Mn of 6,057 and Mw of 8,884.

<Synthesis example 3>
Copolymer solution (solid content) obtained by dissolving 2.03 g of styrene, 1.63 g of NVA, 3.76 g of cyclomer M100, and 0.37 g of AMBN in 18.14 g of PGME and reacting at 80 ° C. for 20 hours. A concentration of 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P3). The obtained copolymer had Mn of 5,336 and Mw of 8,669.

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

<Synthesis example 5>
Coweight obtained by dissolving 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 in 18.83 g of PGME and reacting at 80 ° C. for 20 hours. The coalesced solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P5). The obtained copolymer had Mn of 6,146 and Mw of 13,143.

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

<Synthesis example 7>
Coweight obtained by dissolving 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 in 16.92 g of PGME and reacting at 80 ° C. for 20 hours. The coalesced solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P7). The obtained copolymer had Mn of 5,257 and Mw of 9,324.

<Synthesis Example 8>
Coweight obtained by dissolving 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 in 19.69 g of PGME and reacting at 80 ° C. for 20 hours. The coalesced solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P8). The obtained copolymer had Mn of 4,718 and Mw of 8,940.

<Synthesis example 9>
The copolymer obtained by dissolving 2.00 g of styrene, 1.63 g of NVA, 2.64 g of Cyclomer M100, 0.89 g of Viscoat 3F, and 0.36 g of AMBN in 17.54 g of PGME and reacting at 80 ° C. for 20 hours. A polymer solution (solid content concentration: 30% by mass) was added to 500 mL of diethyl ether with stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain a copolymer powder (P9). The obtained copolymer had Mn of 6,558 and Mw of 10,706.

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

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

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

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

[Synthesis of Pd particle complex]
<Synthesis Example 14>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P1 l. Polymerized in this solution in Synthesis Example 1. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M1) as a black powder.

<Synthesis Example 15>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P2 l. Polymerized in this solution in Synthesis Example 2. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M2) as a black powder.

<Synthesis Example 16>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P3 l. Polymerized in this solution in Synthesis Example 3. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M3) as a black powder.

<Synthesis example 17>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P4 l. Polymerized in this solution in Synthesis Example 4. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M4) as a black powder.

<Synthesis Example 18>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P5 l. Polymerized in this solution in Synthesis Example 5. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M5) as a black powder.

<Synthesis Example 19>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P6 l. Polymerized in this solution in Synthesis Example 6. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M6) as a black powder.

<Synthesis Example 20>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P7 l. Polymerized in this solution in Synthesis Example 7. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M7) as a black powder.

<Synthesis example 21>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P8 l. Polymerized in this solution in Synthesis Example 8. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M8) as a black powder.

<Synthesis Example 22>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P9 l. Polymerized in this solution in Synthesis Example 9. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M9) as a black powder.

<Synthesis Example 23>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P10 l. Polymerized in this solution in Synthesis Example 10. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M10) as a black powder.

<Synthesis Example 24>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P11 l. Polymerized in this solution in Synthesis Example 11. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M11) as a black powder.

<Synthesis Example 25>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P12 l. Polymerized in this solution in Synthesis Example 12. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M12) as a black powder.

<Synthesis Example 26>
0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform were placed in a 100 mL reaction flask equipped with a cooler, and the mixture was stirred until uniform. P13 l. Polymerized in this solution in Synthesis Example 13. A solution prepared by dissolving 0 g in 16.40 g of chloroform and 6.40 g of ethanol was added using a dropping funnel. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 341 g of an IPE / hexane solution (mass ratio 10: 1) with stirring to precipitate a polymer / Pd particle composite. The precipitated polymer / Pd particle complex was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 0.9 g of the Pd particle complex (M13) as a black powder.

The components (C) and (D) were added to the complexes M1 to M13 of the Pd particles at the ratios shown in Table 1 below to prepare an electroless plating base material. The electroless plating base material containing M1 to M3 is used as a comparative example. Examples include electroless plating base materials containing M4 to M13, respectively.

[Preparation of plating solution]
<Preparation Example 1>
200 mL Beaker with 100 mL of pure water, Basic Print Gantt V (Atotech) 17 mL, Copper Solution Print Gantt V (Atotech) 9 mL, Starter Print Gantt PV (Atotech) 1.6 mL, Stabilizer Print Gantt PV (Atotech) 0. 24 mL, reducer Cu (manufactured by Atotech) 3.2 mL, 18.5 mass% NaOH aqueous solution 4 mL were charged, and pure water was further added to bring the total volume of the solution to 200 mL. This solution was stirred to obtain an electroless copper plating solution.

[Evaluation of plating precipitation]
The electroless plating base materials of Examples 1 to 10 and Comparative Examples 1 to 6 are coated with a bar coat having a film thickness of 6 μm on a polyimide (Kapton 100EN (registered trademark) manufactured by Toray DuPont Co., Ltd.) substrate. Then, a coating film was formed by heating at 80 ° C. for 5 minutes. The coating film was further dried by heating at 250 ° C. for 30 minutes. The obtained film was immersed in the electroless copper plating solution prepared in Preparation Example 1 for 10 minutes. Then, after washing the obtained plating base material with water, the state of the metal plating film was visually evaluated. The evaluation results are summarized in Table 2 later.

<Evaluation criteria for plating precipitation>
◯: Plating is uniformly deposited on the entire surface of the coating film.
X: Plating is not uniformly deposited on the entire surface of the coating film.

As shown in Table 2, the electroless plating base materials of Examples 1 to 13 and the electroless plating base materials of Comparative Examples 1 to 3 had good plating precipitation properties. On the other hand, the deposition of plating could not be confirmed in the electroless plating base materials of Comparative Examples 4 to 7.

Claims

An electroless plating base material for forming a metal plating film on a substrate by electroless plating.
(A) A structural unit derived from a monomer a having at least one trifluoromethyl group and one radically polymerizable double bond in the molecule, and a metal dispersible group and one radically polymerizable double bond in the molecule. A copolymer containing a structural unit derived from a monomer b having a double bond,
A base material containing (B) fine metal particles and (C) a solvent.
The base material according to claim 1, which comprises a complex in which the (B) metal fine particles are adhered or coordinated to the metal dispersible group in the (A) copolymer.
The base material according to claim 1 or 2, wherein the monomer a is a compound having either a vinyl group or a (meth) acryloyl group.
The base material according to claim 3, wherein the monomer a is a compound represented by the following formula (1).

(In the formula (1), M represents a single bond, a carbonyloxy group, an amide group or a phenylene group, and J is a linear or branched group having 1 to 10 carbon atoms having at least one trifluoromethyl group. Represents an alkyl group of structure, and R 6 represents an alkyl group having a hydrogen atom or 1 to 4 carbon atoms.)
The base material according to claim 1 or 2, wherein the monomer b is a compound having either a vinyl group or a (meth) acryloyl group.
The base material according to claim 5, wherein the monomer b is a compound represented by the following formula (2) or (3).

(In the formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L represents O or N, and R 2 exists only when L represents N. Representing a hydrogen atom, or R 1 and R 2 may be combined with the atom to which they are attached to form a 4- to 6-membered cyclic amide.
In the formula (3), R 3 represents a hydrogen atom or a methyl group, and R 4 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or a branch having 1 to 10 carbon atoms. alkoxyl group or represents an alkoxyl alkyl group branched having 1 to 10 carbon atoms, L represents an O or N, R 5 is present only when L represents N, tables hydrogen atom Alternatively, R 4 and R 5 may be combined with the atoms to which they are attached to form a 4- to 6-membered cyclic amide, or a 4- to 6-membered cyclic imide. )
The base material according to claim 6, wherein the monomer b is N-vinylpyrrolidone, N-vinylacetamide or N-vinylformamide.
Any one of claims 1 to 7, wherein the monomer mixture that gives the copolymer (A) contains the monomer a in an amount that is 5 to 500% of the number of moles of the monomer b. The base material described in item 1.
Any one of claims 1 to 8, wherein the copolymer (A) further contains a structural unit derived from a monomer c having a crosslinkable group and one radically polymerizable double bond in the molecule. The base material described in the section.
The base material according to claim 9, wherein the monomer c is a compound having either a vinyl group or a (meth) acryloyl group.
The base material according to claim 10, wherein the monomer c is a compound represented by the following formula (4).

(In the formula (4), X represents a single bond, a carbonyloxy group, an amide group or a phenylene group, and Y is an alkylene group having 1 to 6 carbon atoms and an oxyalkylene group having 1 to 6 carbon atoms, which are branched. May represent an alkyl ether group having 1 to 6 carbon atoms, a thioalkylene group having 1 to 6 carbon atoms or a thioalkyl ether group having 1 to 6 carbon atoms, where Z represents a crosslinkable group and R 7 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
Any one of claims 9 to 11, wherein the monomer mixture that gives the copolymer (A) contains the monomer c in an amount that is 5 to 300% of the number of moles of the monomer b. The base material described in item 1.
The metal fine particles (B) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold ( The base material according to any one of claims 1 to 12, which is a fine particle of at least one kind of metal selected from the group consisting of Au).
The base material according to claim 13, wherein the metal fine particles (B) are palladium fine particles.
The base material according to any one of claims 1 to 14, wherein the metal fine particles (B) are fine particles having an average primary particle particle size of 1 to 100 nm.
(D) The base material according to any one of claims 1 to 15, which contains a base resin further having a non-radical polymerizable crosslinkable group.
(E) The base material according to any one of claims 1 to 16, further containing a cross-linking agent.
An electroless metal plating base layer comprising a film containing the electroless plating base agent according to any one of claims 1 to 17.
The metal plating film formed on the base layer of the electroless metal plating according to claim 18.
A metal comprising a base material, an electroless metal plating base layer formed on the base material, and a metal plating film formed on the electroless metal plating base layer. Coating substrate.
A method for producing a metal film base material, which comprises the following steps (1) and (2).
(1) Step: The electroless plating base material according to any one of claims 1 to 17 is applied onto a base material, and an electroless metal plating base layer is formed on the base material. Process,
(2) Step: A step of immersing the base material on which the base layer is formed in an electroless plating bath to form a metal plating film on the base layer.