TW202035787A - Electroless plating base material containing polymer and metal fine particles - Google Patents

Abstract

To provide an electroless plating undercoat agent containing a polymer and metallic microparticles. Provided is an electroless plating undercoat agent for forming a metal plating film on a substrate by electroless plating, said agent containing: (A)a copolymer containing a structural unit derived from a monomer a, which has, in a molecule, a metal dispersive group and one radical-polymerizable double bond, and a structural unit derived from a monomer b which has, in a molecule, a crosslinkable group and one radical-polymerizable double bond; (B) metallic microparticles; and (c) a solvent.

Description

Electroless plating base agent containing polymer and metal particles

The present invention relates to an electroless plating base containing a polymer and metal fine particles.

Electroless plating involves only immersing the substrate in the plating solution, and regardless of the type or shape of the substrate, a uniform thickness can be obtained. For plastic, ceramic, glass and other non-conducting materials, a metal plating film can also be formed. Therefore, it can be widely used in various fields such as high-grade sense of resin moldings such as automobile parts, or decorative applications that impart beautiful appearance, or wiring technology such as electromagnetic shielding, printed circuit boards and large-scale integrated circuits. Generally, when a metal plating film is formed on a substrate (object to be plated) by electroless plating, a pretreatment to improve the adhesion between the substrate and the metal plating film is performed. Specifically, the surface to be treated is roughened and/or hydrophilized by various etching methods first, and then an adsorbent that promotes the adsorption of the plating catalyst on the surface to be treated is supplied to the treated surface The above-mentioned sensitization process (sensitization), and activation process (activation) in which the plating catalyst is adsorbed on the treated surface. In a typical method, the susceptibility treatment involves immersing the object to be treated in an acidic solution of first tin chloride, whereby the metal (Sn ²⁺ ) acting as a reducing agent adheres to the surface to be treated. Then, the susceptible surface is immersed in an acidic solution of palladium chloride as an activation treatment. Thereby, the palladium ions in the solution are reduced by the metal (tin ion: Sn ²⁺ ) of the reducing agent, and are attached to the treated surface as an active palladium catalyst nucleus. After performing the pretreatment in this way, it is immersed in an electroless plating solution to form a metal plating film on the surface to be processed.

On the other hand, an example of using a composition containing a hyperbranched polymer having an ammonium group and metal fine particles as a base agent (plating catalyst) for electroless plating has been reported, avoiding the use of electroless plating in the past Chromium compound (chromic acid) that has become a problem in the pre-treatment step (roughening treatment), and the number of pre-treatment steps is to be reduced, so as to achieve various improvements in environmental, cost, and troublesome operability. The agent has been proposed (Patent Document 1). [Prior Technical Literature] [Patent Literature]

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

[Problem Solved by Invention]

A composition containing a hyperbranched polymer having an ammonium group and fine metal particles proposed as a base for the above-mentioned electroless plating. When this is applied to wiring technology in semiconductor manufacturing, etc., the hyperbranched polymer contained therein The heat-resistant temperature of the material is low. For solder reflow or high temperature processing, the high branch polymer may be decomposed. In addition, there is also a problem that it is difficult to provide adhesion to LCP (liquid crystal polymer) substrates that are excellent in electrical characteristics for use in 5G and other next-generation communication devices. In this way, the electroless plating base proposed so far does not contain corrosive atoms such as halogen atoms or sulfur atoms in addition to plating performance as a plating base, and can provide plating with high heat resistance. The composition can be easily painted, and it has various properties such as high metal particle dispersion stability, adhesion to LCP substrates, and operability that can be easily manufactured with a small number of processes, and these characteristics can be fully realized. There has not yet been a proposal for an electroless plating base agent. The present invention focuses on this subject, and aims to provide the following novel base, which has high heat resistance and can form a plating base layer with excellent adhesion to LCP substrates, and can further achieve low Cost-effective use in the pre-treatment steps of electroless plating. [Means to solve the problem]

The inventors of the present invention conducted a detailed review to achieve the above-mentioned object. They reviewed a polymer containing a metal dispersing group but no corrosive atoms, and found that the polymer was combined with metal microparticles and coated on a substrate. The layer not only has the plating properties as a base layer of electroless metal plating, but also has high heat resistance, and has excellent adhesion to the LCP substrate, and the present invention has been completed.

(式(1)中，R₁ 表示氫原子或碳原子數1至6的烷基，L表示O或N，R₂ 僅存在於當L表示N時，其表示氫原子，或R₁ 及R₂ 與此等所鍵結的原子共同可形成4至6員之環狀醯胺。 式(2)中，R₃ 表示氫原子或甲基， R₄ 表示氫原子或碳原子數1至10的可為分支之烷基、碳原子數1至10的可為分支之烷氧基，或碳原子數1至10的可為分支之烷氧基烷基，L表示O或N，R₅ 僅存在於當L表示N時，其表示氫原子，或R₄ 及R₅ 與此等鍵結的原子共同可形成4至6員之環狀醯胺，或4至6員之環狀醯亞胺。) 作為第5觀點，其係關於前述單體a為N-乙烯基吡咯啶酮、N-乙烯基乙醯胺或N-乙烯基甲醯胺之第4觀點所記載的基劑。 作為第6觀點，其係關於前述單體b為，具有乙烯基及(甲基)丙烯醯基中任一方之化合物的第1觀點或第2觀點所記載的基劑。 作為第7觀點，其係關於前述單體b為下式(3)所示化合物之第6觀點所記載的基劑。

(式(3)中，X表示單鍵、羰氧基、醯胺基或伸苯基，Y表示碳數1至6的伸烷基、碳數1至6的氧基伸烷基、可為分支的碳數1至6的烷基醚基、碳數1至6的硫代伸烷基或碳數1至6的硫烷基醚基，Z表示交聯性基，R⁶ 表示氫原子或碳數1至4的烷基。) 作為第8觀點，其係關於賦予前述(A)共聚物的單體中，對於前述單體a的莫耳數，含有成為5~500%的莫耳數之量的前述單體b的第1觀點至第7觀點中任一所記載的基劑。 作為第9觀點，其係關於前述(B)金屬微粒子為選自由鐵(Fe)、鈷(Co)、鎳(Ni)、銅(Cu)、鈀(Pd)、銀(Ag)、錫(Sn)、鉑(Pt)及金(Au)所成群的至少一種金屬微粒子之第1觀點至第8觀點中任一所記載的基劑。 作為第10觀點，其係關於前述(B)金屬微粒子為鈀微粒子之第9觀點所記載的基劑。 作為第11觀點，其係關於前述(B)金屬微粒子為具有1~100nm的一次粒子平均粒徑之微粒子的第1觀點至第10觀點中任一所記載的基劑。 作為第12觀點，其係關於進一步含有具有(D)非自由基聚合性交聯性基之基礎樹脂的第1觀點至第11觀點中任一所記載的基劑。 作為第13觀點，其係關於進一步含有(E)交聯劑之第1觀點至第12觀點中任一所記載的基劑。 作為第14觀點，其係關於使用如第1觀點至第13觀點中任一所記載的無電解鍍敷基劑而得之無電解金屬鍍敷的基層。 作為第15觀點，其係關於形成在第14觀點所記載的無電解金屬鍍敷之基層上的金屬鍍敷膜。 作為第16觀點，其係關於具備：基材、形成於該基材上的如第14觀點所記載的無電解金屬鍍敷之基層，與形成於該無電解金屬鍍敷的基層上之金屬鍍敷膜的金屬被膜基材。 作為第17觀點，其係關於含有下述(1)步驟及(2)步驟之金屬被膜基材的製造方法。 (1)步驟：將如第1觀點至第13觀點中任一所記載的無電解鍍敷基劑塗布於基材上，使無電解金屬鍍敷的基層具備於該基材上之步驟、 (2)步驟：將具備該基層之基材浸漬於無電解鍍敷浴中，使金屬鍍敷膜形成於該基層上之步驟。 [發明之效果]That is, as the first viewpoint in the present invention, it relates to an electroless plating base used when forming a metal plating film on a substrate by electroless plating, and the base contains: (A) The constitutional unit of monomer a having a metal dispersible group and one radical polymerizable double bond in the molecule, and the constitution of monomer b having a crosslinkable group and one radical polymerizable double bond in the molecule Unit copolymer, (B) metal particles, and (C) solvent. As a second point of view, it relates to the base agent described in the first point of view, which contains the aforementioned (B) complex of metal particles attached or coordinated in the metal dispersible group in the copolymer (A). As a third viewpoint, it is a base described in the first viewpoint or the second viewpoint regarding the compound in which the monomer a has either a vinyl group or a (meth)acryloyl group. As a fourth viewpoint, it is a base described in the third viewpoint regarding the monomer a being a compound represented by the following formula (1) or (2).

(In formula (1), 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, which represents a hydrogen atom, or R ₁ and R ₂ and these bonded atoms can form a 4- to 6-membered cyclic amide. In formula (2), R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a carbon atom with 1 to 10 It can be a branched alkyl group, a branched alkoxy group with 1 to 10 carbon atoms, or a branched alkoxyalkyl group with 1 to 10 carbon atoms, L represents O or N, R ₅ only exists When L represents N, it represents a hydrogen atom, or R ₄ and R ₅ together with these bonded atoms can form a 4 to 6 membered cyclic amide or a 4 to 6 membered cyclic amide. ) As a fifth viewpoint, it is the base described in the fourth viewpoint regarding the monomer a being N-vinylpyrrolidone, N-vinylacetamide, or N-vinylformamide. As a sixth viewpoint, it is the base described in the first viewpoint or the second viewpoint in which the monomer b is a compound having any one of a vinyl group and a (meth)acryloyl group. As a seventh viewpoint, it is the base described in the sixth viewpoint regarding the monomer b being a compound represented by the following formula (3).

(In formula (3), X represents a single bond, a carbonyloxy group, an amido group or a phenylene group, and Y represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, which may be branched Alkyl ether group with 1 to 6 carbons, thioalkylene group with 1 to 6 carbons or sulfanyl ether group with 1 to 6 carbons, Z represents a crosslinkable group, R ⁶ represents a hydrogen atom or carbon An alkyl group having a number of 1 to 4.) As an eighth point of view, it relates to the number of moles of the monomer a that is 5 to 500% of the number of moles of the monomer given to the (A) copolymer. The amount of the base described in any one of the first to seventh aspects of the monomer b. As a ninth viewpoint, it relates to the aforementioned (B) metal fine particles being selected from iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn) ), a base described in any one of the first to eighth viewpoints of at least one metal fine particle composed of platinum (Pt) and gold (Au). As a tenth viewpoint, it is the base described in the ninth viewpoint regarding the aforementioned (B) metal fine particles being palladium fine particles. As an eleventh viewpoint, it is a base agent described in any one of the first to tenth viewpoints regarding the aforementioned (B) metal fine particles being fine particles having an average primary particle diameter of 1 to 100 nm. As a twelfth viewpoint, it is a base agent described in any one of the first viewpoint to the eleventh viewpoint which further contains a base resin having (D) a non-radical polymerizable crosslinkable group. As a 13th viewpoint, it is the base agent described in any one of the 1st viewpoint to the 12th viewpoint which further contains (E) a crosslinking agent. As a 14th viewpoint, it is about the base layer of electroless metal plating obtained using the electroless plating base agent described in any one of the 1st viewpoint thru|or 13th viewpoint. As a fifteenth aspect, it relates to the metal plating film formed on the base layer of the electroless metal plating described in the fourteenth aspect. As a 16th viewpoint, it relates to a base layer formed on the base material, the electroless metal plating as described in the 14th viewpoint, and the metal plating formed on the base layer of the electroless metal plating. The coated metal coating substrate. As a 17th viewpoint, it relates to the manufacturing method of the metal coating base material which contains the following (1) process and (2) process. (1) Step: A step of applying the electroless plating base as described in any one of the first to the 13th viewpoint on a substrate, and providing a base layer of electroless metal plating on the substrate, ( 2) Step: the step of immersing the substrate with the base layer in an electroless plating bath to form a metal plating film on the base layer. [Effects of Invention]

The base of the present invention can easily form the base layer of electroless plating only by coating on the substrate. According to the present invention, it is possible to form a plating base layer with excellent plating performance and high heat resistance, and excellent adhesion to LCP substrates. In addition, the base of the present invention can be easily painted on various compositions, and can be one with high metal particle dispersion stability. In addition, the polymer used in the base of the present invention can be easily prepared with fewer processes, so that the manufacturing steps of the plating base can be simplified, and the manufacturing cost can also be reduced. In addition, the base layer of electroless metal plating formed by the electroless plating base of the present invention is simply immersed in an electroless plating bath, and a metal plating film can be easily formed, and a base layer with a base and a base layer can be easily obtained. , And the metal coating substrate of the metal plating film. That is, by using the electroless plating base of the present invention to form a base layer on a base material, a metal plating film having excellent adhesion to the base material, especially the LCP substrate, and heat resistance can be formed.

[Type of Implementation of Invention]

The present invention will be described in detail below. The base of the present invention is a base containing (A) a copolymer having the above-mentioned specific structural unit, (B) metal fine particles, and (C) a solvent, and optionally contains other components. The base of the present invention is a catalyst suitable for forming a metal plating film on a substrate by electroless plating. The ingredients are explained below. ＜(A)Copolymer＞

The component (A) contains a structural unit derived from a monomer a having a metal dispersible group and a radical polymerizable double bond in the molecule, and a component derived from a crosslinkable group and a radical polymerizable group in the molecule. A copolymer of the constituent unit of the monomer b of the double bond.

[Monomer a] In the present invention, the monomer a is a compound having a metal dispersible group and one radical polymerizable double bond in the molecule. The metal dispersibility group is to increase the dispersibility in the composition of the metal microparticles by interacting with the metal microparticles of the component (B) by adhesion and/or coordination, thereby making the metal microparticles stable in the composition The basis of existence. As such a metal-dispersing group, a substituent having a site where a carbonyl group is bonded to a nitrogen atom by a covalent bond, that is, a substituent having a -C(=O)-N- site, is preferred, and more specifically selected from A group having an amide bond and a group having an amide bond are preferred. As the radically polymerizable double bond, a compound having any one of a vinyl group and a (meth)acryloyl group is preferred. In addition, when monomer a 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 may also be A structure repeated with the carbonyl group in the amide group as the metal dispersible group.

(式(1)中，R₁ 表示氫原子或碳原子數1至6的烷基，L表示O或N，R₂ 僅存在於當L表示N時，其表示氫原子，或R₁ 及R₂ 與此等所鍵結的原子共同可形成4至6員之環狀醯胺。 式(2)中，R₃ 表示氫原子或甲基， R₄ 表示氫原子或碳原子數1至10的可為分支之烷基、碳原子數1至10的可為分支之烷氧基，或碳原子數1至10的可為分支之烷氧基烷基，L表示O或N，R₅ 僅存在於當L表示N時，其表示氫原子，或R₄ 及R₅ 與此等鍵結的原子共同可形成4至6員之環狀醯胺，或4至6員之環狀醯亞胺。)As a specific monomer a, the compound represented by following formula (1) or formula (2) is mentioned, for example.

(In formula (1), 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, which represents a hydrogen atom, or R ₁ and R ₂ and these bonded atoms can form a 4- to 6-membered cyclic amide. In formula (2), R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a carbon atom with 1 to 10 It can be a branched alkyl group, a branched alkoxy group with 1 to 10 carbon atoms, or a branched alkoxyalkyl group with 1 to 10 carbon atoms, L represents O or N, R ₅ only exists When L represents N, it represents a hydrogen atom, or R ₄ and R ₅ together with these bonded atoms can form a 4 to 6 membered cyclic amide or a 4 to 6 membered cyclic amide. )

As such a monomer a, for example, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl(meth)propylene Amide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide Amine, N-hexyl(meth)acrylamide, N-octyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-methoxybutyl (methyl) )Acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide , N-isobutoxyethyl (meth)acrylamide, N-vinyl phthalimide, N-vinyl succinate amide, etc.

Among them, as the monomer a, from the viewpoint of coordination energy to the metal of the monomer, the monomer represented by formula (1) is preferred, and the monomer having an N-vinylamino group is preferred. In consideration of availability, etc., N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide are more preferable. These monomer a may be used individually by 1 type, and may use 2 or more types together.

[Monomer b] Monomer b is a monomer having a crosslinkable group and one radical polymerizable double bond in the molecule. Examples of the crosslinkable group include N-alkoxymethyl, N-hydroxymethyl, epoxy group which may have substituent Q, alicyclic epoxy group which may have substituent Q, and which may have substituent The oxetanyl of Q and so on. As the substituent Q, an alkyl group having 1 to 4 carbons, a phenyl group, etc., which may be substituted with halogen, can be mentioned.

(式(3)中，X表示單鍵、羰氧基、醯胺基或伸苯基，Y表示碳數1至6的伸烷基、碳數1至6的氧基伸烷基、碳數1至6的烷基醚基、碳數1至6的硫代伸烷基或碳數1至6的硫烷基醚基，Z表示交聯性基，R⁶ 表示氫原子或碳數1至4的烷基。)As a specific monomer b, the compound represented by following formula (3) is mentioned, for example.

(In formula (3), X represents a single bond, a carbonyloxy group, an amide group or a phenylene group, Y represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, and a carbon number of 1 Alkyl ether group up to 6, thioalkylene group having 1 to 6 carbons or sulfanyl ether group having 1 to 6 carbons, Z represents a crosslinkable group, and R ⁶ represents a hydrogen atom or a carbon number of 1 to 4的alkyl.)

The alkylene having 1 to 6 carbon atoms represented by Y may be either linear or branched. Although the specific example is not particularly limited, it may include methylene, ethane-1,1- Diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,4-diyl, Pentane-1,5-diyl, hexane-1,6-diyl, etc.

The oxyalkylene group having 1 to 6 carbon atoms may be either linear or branched, and specific examples of R ⁷ as a group that satisfies -OR ⁷ -are the same as the above-mentioned 1 to 6 alkylene groups.

The alkyl ether group having 1 to 6 carbon atoms may be either linear or branched. Examples of groups satisfying -R ⁸ -OR ⁸ -and R ⁸ are not particularly limited, but each independently can Methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl Base, butane-1,4-diyl, pentane-1,5-diyl, etc. However, the total carbon number of the two R ⁸ is only 6.

The thioalkylene group having 1 to 6 carbon atoms may be either linear or branched, and satisfies -SR ⁷ -and R ^{7 is} as shown above.

The alkyl ether group having 1 to 6 carbon atoms may be either linear or branched, and -R ⁸ -OR ⁸ -is as shown above.

Although it does not specifically limit as a specific example of such a monomer, the following can be mentioned.

Examples of monomers having one radically polymerizable double bond and N-alkoxymethyl group include N-butoxymethacrylamide, N-isobutoxymethacrylamide, N-methoxymethacrylamide, N-methoxymethylmethacrylamide, N-methylolmethacrylamide, etc.

Although there are no particular limitations on the monomer having one radically polymerizable double bond and N-hydroxymethyl group, for example, N-hydroxymethacrylamide and N-hydroxymethylmethacrylamide can be mentioned. Amine etc.

The monomer having one radical polymerizable double bond and an epoxy group is not particularly limited, but examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl α-ethyl acrylate. , Α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6 ,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m- Vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p -Vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. are preferred. These can be used alone or in combination.

Although it does not specifically limit as a monomer which has one radically polymerizable double bond and has an oxetanyl group, (meth)acrylate etc. which have an oxetanyl group are mentioned, for example. Among such monomers, 3-(methacryloxymethyl)oxetane, 3-(acryloxymethyl)oxetane, 3-(methacryloxymethyl) )-3-Ethyl-oxetane, 3-(acryloxymethyl)-3-ethyl-oxetane, 3-(methacryloxymethyl)-2-tri Fluoromethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyl-oxy Etidine, 3-(acryloxymethyl)-2-phenyl-oxetane, 2-(methacryloxymethyl)oxetane, 2-(acryloxymethyl) Methyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, 2-(acryloxymethyl)-4-trifluoromethyl Oxetane is preferably 3-(methacryloxymethyl)-3-ethyl-oxetane, 3-(acryloxymethyl)-3-ethyl- Oxetane etc. are preferred. Among these, from the viewpoint of adhesion to the substrate, X is preferably a carbonyloxy group or a methylene group, and Z is preferably an epoxy group.

In the present invention, when manufacturing the copolymer of the component (A), the above-mentioned monomer a and the above-mentioned monomer b are used, and other monomers may also be used. Examples of such other monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methyl benzyl methacrylate, naphthalene methacrylate, and anthracenyl methacrylate. Esters, anthracenyl methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl Methyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methacrylate, ethyl acrylate, isopropyl acrylate, benzyl Acrylate, naphthalene acrylate, anthracenyl acrylate, anthracenyl methacrylate, phenyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxy Ethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8 -Tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, etc.

In the present invention, when the copolymer of the component (A) is produced, by using the above-mentioned other monomers, the resulting copolymer of the component (A) can be imparted with resistance to plating liquids and the like.

The method for obtaining a specific copolymer used in the present invention is not particularly limited. For example, the above-mentioned monomer a, the above-mentioned monomer b, and other monomers as required may be combined in a solvent coexisting with a polymerization initiator, etc. It is obtained by polymerization reaction at a temperature of 50 to 110°C. In this case, the solvent used can only dissolve monomers having a specific functional group, monomers that do not have a specific functional group, polymerization initiators, and the like used as needed, and is not particularly limited. As a specific example, it is described in the below-mentioned <(C) solvent>. The specific copolymer obtained by the aforementioned method is usually in a solution state dissolved in a solvent.

In addition, the solution of the specific copolymer obtained by the above method is poured into diethyl ether or water under stirring to precipitate it, and the resulting precipitate is filtered and washed, and then placed under normal pressure or reduced pressure , Drying at room temperature or heating to obtain a powder of specific copolymer. Through the foregoing operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If it is not possible to purify sufficiently in one operation, the obtained powder is re-dissolved in the solvent, and the above operation can be repeated.

For the present invention, the specific copolymer can be used in the form of a powder or in the form of a solution in which the purified powder is re-dissolved in the solvent described below.

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

In the present invention, the ratio of copolymerizing the aforementioned monomer a and the aforementioned monomer b is preferably from the standpoint of reactivity or plating property to the aforementioned monomer a 1 mole being the aforementioned monomer b 0.05 mole Ear to 5 mol, particularly preferably 0.1 mol to 3 mol.

In the present invention, when the copolymer of component (A) is produced, when the above-mentioned other monomers are used, the total molar number of the aforementioned monomer a and monomer b is 1 to 200% of the molar number. , Preferably 10 to 100% of the molar amount.

＜(B) Metal fine particles＞ The (B) metal fine particles used in the base of the present invention are not particularly limited. Examples of metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and palladium (Pd). ), silver (Ag), tin (Sn), platinum (Pt), gold (Au), and these alloys may be one type of these metals, or two or more types of alloys. Among them, the metal fine particles preferably include palladium fine particles. In addition, oxides of the aforementioned metals can also be used as metal fine particles.

The aforementioned metal fine particles are, for example, a method in which a metal salt solution is irradiated with light by a high-pressure mercury lamp, or a method in which a compound having a reducing effect (a so-called reducing agent) is added to the solution, etc., which can be reduced by metal ions And gotta. For example, by adding a metal salt solution to the solution in which the polymer of component (A) is dissolved and irradiating it with ultraviolet rays, or adding a metal salt solution and a reducing agent to the solution, the metal ions can be reduced. (A) A composite of the component polymer and the metal fine particles, while preparing a base containing the (A) component polymer and the metal fine particles.

Examples of the aforementioned metal salt include chloroauric acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, first platinum chloride, chloroplatinic acid, Pt(dba) ₂ [dba=diphenylene Methyl 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 chloride, ruthenium acetate, Ru(cod)(cot)[cot=cyclooctatriene ], iridium chloride, iridium acetate, Ni(cod) ₂ etc. Although there are no particular limitations on the aforementioned reducing agent, various reducing agents can be used, and it is preferable to select the reducing agent based on the metal species contained in the resulting base, etc. Examples of usable reducing agents include metal salts of boron hydride such as sodium borohydride and potassium borohydride; aluminum hydrides such as lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum hydride, magnesium aluminum hydride, and calcium aluminum hydride. Salts; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; methanol, ethanol, isopropanol, polyols and other primary or secondary alcohols; trimethylamine, triethyl Tertiary amines such as methylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA], etc.; hydroxylamine; tri-n- Propylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tritylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis(diphenylphosphine)ethane [DPPE] , 1,3-bis(diphenylphosphine)propane [DPPP], 1,1'-bis(diphenylphosphine)ferrocene [DPPF], 2,2'-bis(diphenylphosphine)-1 , 1'-Binaphthalene [BINAP] and other phosphines.

The average particle size of the primary particles of the aforementioned metal fine particles is preferably 1-100 nm. When the average particle diameter of the primary particles of the metal fine particles is set to 100 nm or less, sufficient catalyst activity can be obtained with a small reduction in surface area. The average particle diameter of the primary particles is preferably 75 nm or less, and particularly preferably 1 to 30 nm. The average particle diameter 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, dropping them on the carbon support film, and drying the sample to make the sample, the sample obtained can be obtained by the microscope method with a TEM device (manufactured by Hitachi, Ltd.: H-8000 acceleration voltage 200kV) Obtain the average particle size of the primary particles.

The addition amount of the copolymer of the component (A) in the base 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 (B) metal fine particles. For 100 parts by mass of (B) metal fine particles, when the addition amount of (A) copolymer is set to 20 parts by mass or more, the metal fine particles can be sufficiently dispersed, and when it is set to 20 parts by mass or less, the metal fine particles The dispersibility will become insufficient, and it is easy to produce precipitates or aggregates. Preferably it is 30 parts by mass or more. In addition, with respect to 100 parts by mass of the (B) metal fine particles, when 10,000 parts by mass or more of the (A) copolymer is added, the amount of Pd per unit area after coating becomes insufficient, so there is a concern that the precipitation property of the plating is reduced.

＜Base agent＞ The electroless plating base of the present invention contains the aforementioned (A) copolymer, (B) metal fine particles, and (C) solvent, and may contain other components as necessary. For the electroless plating base of the present invention, it is preferable that the copolymer of the aforementioned (A) component and the aforementioned (B) metal fine particles form a complex, that is, it contains a copolymer containing the aforementioned base as the aforementioned (A) component. It is preferably a complex formed by the aforementioned (B) metal fine particles.

The so-called complex is one in which the metal dispersible group of the side chain of the copolymer of the aforementioned component (A) allows the two to coexist in contact with or close to the metal fine particles to form a particulate form, in other words, it It is a composite having a structure in which metal fine particles are attached or coordinated to the metal dispersible group of the copolymer of the aforementioned component (A). The so-called "adhesion or coordination structure" is considered to mean a state in which a part or all of the metal dispersible group of the copolymer of the component (A) interacts with metal fine particles, thereby forming a structure like a complex. Therefore, when palladium microparticles are used as the metal microparticles, it is considered that the Pd atoms in the surface layer interact with the metal dispersible group to form a structure in which the (A) component polymer is surrounded by the metal microparticles.

Therefore, the "composite body" in the present invention is not only a composite body formed by bonding the above-mentioned metal microparticles and the copolymer of (A) component, but also a copolymer containing metal microparticles and (A) component. Form a bonding part and exist independently of each other (obviously form a particle).

The formation of the aforementioned composite of the copolymer of the component (A) and the metal microparticles (B) is carried out at the same time as the preparation of the base agent of the copolymer containing the component (A) and the metal microparticles. As this method, there are After synthesizing metal particles with a certain degree of stabilization of the metal dispersible group, the method of exchanging ligands by the polymer of component (A) or in the solution of the copolymer of component (A) by making metal ions Direct reduction to form a complex method. Also, as described above, in the solution in which the copolymer of component (A) is dissolved, the metal salt solution is added and then irradiated with ultraviolet rays, or the metal salt solution and reducing agent are added to the solution to reduce the metal ions. Can form a complex.

As a direct reduction method, a copolymer of metal ions and component (A) is dissolved in a solvent and reduced by a primary or secondary alcohol such as methanol, ethanol, 2-propanol, and polyol. Obtain the target metal particle composite. As the metal ion source used here, the above-mentioned metal salt can be used. As the solvent used, it is not particularly limited as long as the metal ion and the polymer having a metal dispersible group can be dissolved in a solvent above the necessary concentration. Specific examples include methanol, ethanol, n-propanol, 2- Alcohols such as propanol; halogenated hydrocarbons such as dichloromethane 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 other amines; dimethyl sulfide and other sulfides, etc., and mixtures of these solvents, including alcohols , Halogenated hydrocarbons and cyclic ethers are preferred, and ethanol, 2-propanol, chloroform, tetrahydrofuran and the like are preferred. The temperature of the reduction reaction (copolymer of mixed metal ion and component (A)) can be generally used in the range of 0°C to the boiling point of the solvent, preferably in the range of room temperature (about 25°C) to 100°C.

As another direct reduction method, the copolymer of metal ions and component (A) is dissolved in a solvent and reacted in a hydrogen environment to obtain the target metal microparticle composite. As the metal ion source used here, in addition to the above metal salts, chromium hexacarbonyl [Cr(CO) ₆ ], iron pentacarbonyl [Fe(Co) ₅ ], dicobalt octacarbonyl [Co ₂ (CO) ₈ ], tetracarbonyl nickel [Ni(CO) ₄ ] and other metal carbonyl complexes. In addition, zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used. The solvent used is a solvent that can dissolve the copolymer of metal ions and component (A) to a concentration higher than the necessary concentration, and is not particularly limited. Specific examples include alcohols such as ethanol and propanol; dichloromethane, chloroform Halogenated hydrocarbons such as; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran; nitriles such as acetonitrile and butyronitrile, etc., and mixtures of these solvents, preferably tetrahydrofuran. The temperature of the copolymer of the mixed metal ion and the component (A) is usually in the range of 0°C to the boiling point of the solvent.

In addition, as a direct reduction method, the copolymer of the metal ion and the component (A) is dissolved in a solvent and subjected to a thermal decomposition reaction to obtain the target metal microparticle composite. As the metal ion source used here, metal oxides such as the aforementioned metal salts, metal carbonyl complexes, other zero-valent metal complexes, and silver oxide can be used. The solvent used is a solvent that can dissolve the copolymer of the metal ion and the component (A) to a necessary concentration or higher, and is not particularly limited. Specific examples include methanol, ethanol, n-propanol, isopropanol, Alcohols such as ethylene glycol; halogenated hydrocarbons such as dichloromethane and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; benzene, toluene A mixture of aromatic hydrocarbons, etc., and these solvents, preferably toluene. The temperature at which the metal ion and the copolymer of component (A) having a metal dispersible group are mixed can usually be used in the range of 0°C to the boiling point of the solvent, preferably near the boiling point of the solvent, for example, 110°C in the case of toluene ( Heat to reflux).

The composite of the copolymer of the component (A) and the metal microparticles thus obtained can be subjected to purification treatments such as reprecipitation, etc., into the form of solid components such as powder.

The base of the present invention is a copolymer containing the aforementioned (A) component, (B) metal microparticles (preferably a composite of this type), and (C) a solvent, and further contains other components as necessary. The agent may also be in the form of lacquer used in the formation of the [base layer of electroless metal plating] described later.

The electroless plating base of the present invention can contain the base resin of the component (D) as required. As the component (D), it is preferable to have a group that undergoes a crosslinking reaction with the crosslinkable group in the component (A) by heat, that is, one having a non-radical polymerizable crosslinkable group, for example, as described in WO2014/171376 (B) It is better to record the ingredients. By adding such a component (D), it may be possible to further improve the adhesion of the base layer.

When the plating base of the present invention contains the component (D), the content is based on the total of 100 parts by mass of the copolymer of the component (A) and the metal fine particles of the component (B), which is 0 to 200 parts by mass Preferably, it is preferably 0 parts by mass to 150 parts by mass. (D) If the content of the component is too large, the plating depositability will decrease.

The electroless plating base of the present invention may contain the crosslinking agent of component (E) as required.

As the crosslinking agent of the component (E), epoxy compounds, methylol compounds, blocked isocyanate compounds, phenolic resin compounds, compounds having two or more trialkoxysilyl groups, and alkylene compounds having amino groups can be mentioned. Compounds such as oxysilane compounds, organometallic compounds with alkoxy groups and/or chelating ligands, polymers of N-alkoxymethacrylamide, polymers of compounds with epoxy groups, polymers with alkyl groups Polymers of oxysilyl compounds, polymers of compounds with isocyanate groups, and polymers such as melamine formaldehyde resins.

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

As specific examples of the above-mentioned methylol compound, compounds such as alkoxymethylated glycol urea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine can be cited.

As a specific example of the alkoxymethylated glycol urea, for example, 1,3,4,6-four (methoxymethyl) glycol urea, 1,3,4,6-four ( Butoxymethyl) glycol urea, 1,3,4,6-tetra-(hydroxymethyl) glycol urea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3- Four (butoxymethyl) urea, 1,1,3,3-four (methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazoline Ketones, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc. Examples of commercially available products include compounds such as ethylene glycol urea compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: Cymel (registered trademark) 1170, Powder link (registered trademark) 1174), and methylated urea resins (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (shares) urea/formaldehyde resin (high condensation Model, trade name: Becamine (registered trademark) J-300S, same as P-955, same as N), etc.

As a specific example of alkoxymethylated benzoguanamine, tetramethoxymethyl benzoguanamine etc. are mentioned, for example. Examples of sales products include Mitsui Cytec (trade name: Cymel (registered trademark) 1123), and Sanwa Chemical (trade name: NIKALACK (registered trademark) BX-4000, the same as BX-37). , Same as BL-60, same as BX-55H) etc.

As a specific example of alkoxymethylated melamine, hexamethoxymethyl melamine etc. are mentioned, for example. Examples of sold products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: Cymel (registered trademark) 300, same 301, same 303, same 350), butoxymethyl type melamine Compound (trade name: Mycoat (registered trademark) 506, same as 508), Sanwa Chemical's methoxymethyl type melamine compound (trade name: NIKALACK (registered trademark) MW-30, same as MW-22, same as MW-11 , Same MS-001, Same MX-002, Same MX-730, Same MX-750, Same MX-035), Butoxymethyl type melamine compound (trade name: NIKALACK (registered trademark) MX-45, Same MX -410, same as MX-302) etc.

In addition, it may also be a melamine compound, a urea compound, a glycol urea compound, and a compound obtained by condensing a benzoguanamine compound in which the hydrogen atom of the amino group is replaced by a methylol group or an alkoxymethyl group. For example, high-molecular-weight compounds produced from the melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6,323,310 can be mentioned. As a commercial product of the aforementioned melamine compound, trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), etc., and as a commercial product of the aforementioned benzoguanamine compound, trade name: Cymel (Registered trademark) 1123 (Mitsui Cytec (stock) system), etc.

The above-mentioned blocked isocyanate compound refers to an isocyanate group that has two or more isocyanate groups in one molecule and is blocked by a suitable protective group. When exposed to high temperatures during thermal curing, the protective group (blocked part) will be heated Dissociation and separation, the generated isocyanate group will cause a crosslinking reaction with the resin.

Such a multifunctional blocked isocyanate compound, for example, a multifunctional isocyanate compound having two or more isocyanate groups in one molecule can be reacted with an appropriate blocking agent.

Examples of the polyfunctional isocyanate compound include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- Trimethyl-1,6-hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane Diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6-bis(isocyanate methyl)tetrahydrodicyclopentadiene, bis(isocyanate methyl) Dicyclopentadiene, bis(isocyanate methyl)adamantane, 2,5-diisocyanate methyl norbornene, norbornane diisocyanate, dicycloheptane triisocyanate, 4,4'-diphenylmethane Isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 1 ,3-bis(isocyanate methyl)benzene, dianisidine diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,6-bis( Isocyanate methyl) decahydronaphthalene, bis(diisocyanate toluene) phenylmethane, 1,1'-methylene bis(3-methyl-4-isocyanate benzene), 1,3-bis(1-isocyanate-1 -Methylethyl)benzene, 1,4-bis(1-isocyanate-1-methylethyl)benzene, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4 '-Biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, bis(isocyanatemethyl)thiophene, bis(isocyanatemethyl)tetrahydrothiophene, and these modifications Compounds (e.g. isocyanurate, biuret, ethylene glycol adduct, propylene glycol adduct, trimethylolpropane adduct, ethanolamine adduct, polyester polyol adduct, poly Ether polyol adduct, polyamide adduct, polyamine adduct).

Examples of the aforementioned blocking agent include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, and stearyl alcohol. Base alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, ethyl lactate, pentyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), triethylene glycol monoethyl ether, N, N -Dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol and other alcohols, phenol, ethylphenol, propylphenol, butylphenol, octylphenol , Nonylphenol, nitrophenol, chlorophenol, o-cresol, m-cresol, p-cresol, xylenol and other phenols, α-pyrrolidone, β-butyrolamide, β-propanol Endoamides, γ-butyrolactamide, δ-valerolactamide, ε-caprolactamide, etc., acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, diethyl Ketoxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and other oximes, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3 ,5-Dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, etc. Pyrazoles, butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, benzene mercaptan and other mercaptans, malonate diester, acetyl acetate, malonate dinitrile, acetone , Methylene bismuth, dibenzylidene methane, dineopentyl methane, acetone dicarboxylic acid diester and other active methylene compounds, dibutylamine, diisopropylamine, di-tert -Butylamine, bis(2-ethylhexyl)amine, dicyclohexylamine, benzylamine, diphenylamine, aniline, carbazole and other amines, imidazole, 2-ethylimidazole and other imidazoles, sub Imines such as methylimine, ethyleneimine, polyethyleneimine, and propyleneimine, acid amides such as acetaniline, acrylamide, amide acetate, dimer amide, Acid imines such as succinic acid imines, maleic acid imines, and phthalic acid imines, and urea compounds such as urea, thiourea, and ethylene urea. In addition, it may also be an internal block type by uretdione bond (2 quantification of isocyanate group).

As a commercial product of the said polyfunctional block isocyanate compound, the following products are mentioned, for example. Takenate [registered trademark] B-815N, same as B-830, same as B-842N, same as B-846N, same as B-870, same as B-870N, same as B-874, same as B-874N, same as B-882, same B-882N, same as B-5010, same as B-7005, same as B-7030, same as B-7075 (above, manufactured by Mitsui Chemicals Co., Ltd.).

Duranate [registered trademark] ME20-B80S, same MF-B60B, same MF-B60X, same MF-B90B, same MF-K60B, same MF-K60X, same SBN-70D, same 17B-60P, same 17B-60PX, same TPA-B80E, same as TPA-B80X, same as E402-B80B, same as E402-B80T, same as K6000 (above, manufactured by Asahi Kasei Chemical Co., Ltd.), Corona[registered trademark] 2503, same as 2507, same as 2512, same as 2513, same as 2515 , Same as 2520, same as 2554, same as BI-301, same as AP-M, Millionate MS-50 (above, Tosoh Corporation (share) system).

Burnock [registered trademark] D-500, same as D-550, same as DB-980K (above, DIC (share) system).

Sumidure[registered trademark]BL-3175, same as BL-4165, same as BL-4265, same as BL-1100, same as BL-1265, Desmodur[registered trademark]TPLS-2957, same as TPLS-2062, same as TPLS-2078, same as TPLS -2117, same as BL-3475, Desmosam [registered trademark] 2170, same as 2265 (above, Sumika Bayer Carbamate (stock) system).

TRIXENE BI-7641, same BI-7642, same BI-7986, same BI-7987, same BI-7950, same BI-7951, same BI-7960, same BI-7961, same BI-7963, same BI-7981 Same as BI-7982, same BI-7984, same BI-7986, same BI-7990, same BI-7991, same BI-7992, same BI-7770, same BI-7772, same BI-7779, same DP9C/214 ( Above, made by Baxenden Chemicals).

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

Moreover, as the said polyfunctional blocked isocyanate compound, the homopolymer or copolymer obtained by radically polymerizing the (meth)acrylate which has a blocked isocyanate group is mentioned. Here, the "copolymer" means a polymer obtained by polymerizing two or more monomers. The copolymer may also be a copolymer obtained by polymerizing two or more (meth)acrylates having a blocked isocyanate group, or a (meth)acrylate having a blocked isocyanate group and other (meth)acrylates ) Copolymer obtained by polymerization of acrylate. As a sales product of (meth)acrylate having such a blocked isocyanate group, for example, Karenz [registered trademark] MOI-BM, the same as AOI-BM, the same as MOI-BP, and the same as AOI manufactured by Showa Denko Corporation -BP, same MOI-DEM, same MOI-CP, same MOI-MP, same MOI-OEt, same MOI-OBu, same MOI-OiPr.

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

As specific examples of the above-mentioned phenol resin compound, the following compounds can be cited, but the phenol resin compound is not limited to the following compound examples.

As specific examples of compounds having two or more trialkoxysilyl groups, for example, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 4,4'-bis(trimethoxysilyl)biphenyl, 4,4'-bis(triethoxysilyl)biphenyl, bis(trimethoxysilyl)ethane, bis(triethyl) (Oxysilyl)ethane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(trimethoxysilyl)ethylene, bis(triethoxysilyl) Ethylene, 1,3-bis(trimethoxysilylethyl) tetramethyldisiloxane, 1,3-bis(triethoxysilylethyl) tetramethyldisiloxane, double (Triethoxysilylmethyl)amine, bis(trimethoxysilylmethyl)amine, bis(triethoxysilylpropyl)amine, bis(trimethoxysilylpropyl)amine, double (3-Trimethoxysilylpropyl) carbonate, bis(3-triethoxysilylpropyl)carbonate, bis[(3-trimethoxysilyl)propyl]disulfide, bis[ (3-Triethoxysilyl)propyl]disulfide, bis[(3-trimethoxysilyl)propyl]thiourea, bis[(3-triethoxysilyl)propyl]sulfur Urea, bis[(3-trimethoxysilyl)propyl]urea, bis[(3-triethoxysilyl)propyl]urea, 1,4-bis(trimethoxysilylmethyl)benzene , 1,4-bis(triethoxysilylmethyl)benzene, ginseng(trimethoxysilylpropyl)amine, ginseng(triethoxysilylpropyl)amine, 1,1,2-gin (Trimethoxysilyl)ethane, 1,1,2-ginseng (triethoxysilyl)ethane, ginseng (3-trimethoxysilylpropyl) isocyanurate, and ginseng (3 -Triethoxysilylpropyl) isocyanurate and other compounds.

As a specific example of the alkoxysilane compound having an amino group, for example, N,N'-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N,N '‐Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine, N-[3-(trimethoxysilyl)propyl]-1,2-ethanedi Amine, N-[3-(triethoxysilyl)propyl]-1,2-ethanediamine, bis-{3-(trimethoxysilyl)propyl}amine, bis-{3- (Triethoxysilyl)propyl)amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, trimethoxy{3-(methylamino)propyl Silane, 3-(N-allylamino)propyltrimethoxysilane, 3-(N-allylamino)propyltriethoxysilane, 3-(diethylamino)propyl Trimethoxysilane, 3-(diethylamino)propyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane and 3-(phenylamino)propyltriethoxy Base silane and other compounds.

As specific examples of organometallic compounds having alkoxy groups and/or chelating ligands, for example, aluminum diisopropoxy ethyl acetate acetate, aluminum diisopropoxy acetone pyruvate , Aluminum triacetate pyruvate, titanium isopropoxide, titanium n-butoxide, tetraoctyl titanate, diisopropoxy bis(acetylpyruvate) titanium, titanium tetraacetone acetone Compounds such as acid salt, Si (n-propoxy) zirconium, Si (n-butoxy) zirconium, Si (acetylpyruvate) zirconium and other compounds.

Furthermore, as the polymer of the above-mentioned N-alkoxymethacrylamide, for example, the use of N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide and other hydroxymethyl or alkoxymethyl substituted acrylamide compounds or methacrylic acid It is a polymer produced from an amide compound.

As specific examples of such polymers, for example, poly(N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, N-hydroxymethylmethyl Copolymer of acrylamide and methyl methacrylate, copolymer of N-ethoxymethyl methacrylamide and methyl benzyl methacrylate, and N-butoxy methacrylamide and benzyl Copolymer of methyl acrylate and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of such a polymer is 1,000 to 200,000, preferably 3,000 to 150,000, more preferably 3,000 to 50,000.

As the polymer of the compound having an epoxy group, for example, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl ethyl methyl Polymers made from compounds having epoxy groups such as acrylates.

As specific examples of such polymers, for example, poly(3,4-epoxycyclohexyl methyl methacrylate), poly(glycidyl methacrylate), glycidyl methacrylate and methyl Copolymer of methyl acrylate, copolymer of 3,4-epoxycyclohexyl methyl methacrylate and methyl methacrylate, copolymer of glycidyl methacrylate and styrene, etc. The weight average molecular weight of such a polymer is 1,000 to 200,000, preferably 3,000 to 150,000, more preferably 3,000 to 50,000.

As the polymer of the compound having the above-mentioned alkoxysilyl group, for example, a polymer produced by a compound having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane can be mentioned.

As specific examples of such polymers, for example, poly(3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane and styrene , 3-Methacryloxypropyltrimethoxysilane and methyl methacrylate copolymer, etc. The weight average molecular weight of such a polymer is 1,000 to 200,000, preferably 3,000 to 150,000, more preferably 3,000 to 50,000. In this specification, the above-mentioned "poly((meth)acryloxypropyltrimethoxysilane)" means poly(meth)acrylate having an alkoxysilyl group.

These crosslinking agents can be used individually or in combination of 2 or more types.

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

＜Other additives＞ The base of the present invention only does not impair the effects of the present invention, and additives such as surfactants, various surface modifiers, tackifiers, etc. can be further suitably added.

Examples of the aforementioned surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl aryl ethers such as oxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene and polyoxypropylene block copolymers; sorbitol monolaurate, Sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol tristearate, sorbitol trioleate and other sorbitol fatty acid esters; poly Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate and other polyoxyethylene non-ionic systems Surfactant; EFTOP (registered trademark) EF-301, same as EF-303, same as EF-352 [above, manufactured by Mitsubishi Materials Electronics Chemical (stock)], Megafac (registered trademark) F-171, same as F-173, same R-08, same as R-30 [above, DIC (share) system], Novec (registered trademark) FC-430, same as FC-431 [above, Sumitomo 3M (share) system], Asahi Guard (registered trademark) AG- 710 [manufactured by Asahi Glass Co., Ltd.], Surflon (registered trademark) S-382 [manufactured by AGCSeimi Chemical Co., Ltd.] and other fluorine-based surfactants.

In addition, as the above-mentioned surface conditioning agent, there can be mentioned Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.] and other silicone-based leveling agents; BYK (registered trademark)-302, the same as 307, The same as 322, the same 323, the same 330, the same 333, the same 370, the same 375, the same 378 [above, manufactured by BYK･Japan (stock)] and other silicone-based surface modifiers.

As the above-mentioned thickener, for example, polyacrylic acid such as carboxyvinyl polymer (Carbomer) (including crosslinked ones); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate Polyester (PVAc), polystyrene (PS) and other vinyl polymers; polyethylene oxides; polyester; polycarbonate; polyamide; polyurethane; dextrin, cold weather, carrageenan Gum, alginic acid, gum arabic, guar gum, tragacanth, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other polysaccharides; gelatin, phenol Protein and other proteins. In addition, each of the above-mentioned polymers may contain not only a homopolymer but also a copolymer. These tackifiers may be used alone or in combination of two or more. In the base of the present invention, by adding a tackifier as necessary, the viscosity or rheological properties of the base can be adjusted, and the applicable method or application of the base can be appropriately adopted and selected according to the application.

These additives may be used individually by 1 type, and may use 2 or more types together. The amount of additives used is preferably 0.001-50 parts by mass, preferably 0.005-10 parts by mass, for 100 parts by mass of the composite formed by the polymer of component (A) and metal microparticles of component (B) Preferably, it is more preferably 0.01 to 5 parts by mass.

[Base layer of electroless metal plating] The above-mentioned electroless plating base of the present invention can form a base layer of electroless metal plating by coating on a substrate. The base layer of the electroless metal plating is also the object of the present invention.

Although it does not specifically limit as said base material, it is preferable to use a non-conductive base material or a conductive base material. Examples of non-conductive substrates include glass, ceramics, etc.; polyethylene resin, polypropylene resin, chlorinated vinyl resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic Resin, PEN (ethylene naphthalate) resin, PET (ethylene terephthalate) resin, PEEK (polyether ether ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, Epoxy resin, polyacetal resin, LCP (liquid crystal polymer) resin, etc.; paper, etc. These can be suitably used in the form of a sheet, film, etc., and the thickness at this time is not specifically limited. Also, as a conductive substrate, for example, ITO (tin-doped indium oxide), or ATO (antimony-doped tin oxide), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (Gallium doped zinc oxide), various stainless steel, aluminum and duralumin and other aluminum alloys, iron and iron alloys, copper and brass, phosphor bronze, cupronickel and beryllium copper and other copper alloys, nickel and nickel alloys, and Metals such as silver alloys such as silver and foreign silver can be cited. Furthermore, it can also be used for the base material which forms a film with these conductive base materials on the said non-conductive base material. In addition, the above-mentioned base material may be a three-dimensional molded body.

As a copolymer containing the above-mentioned (A) component, (B) metal microparticles (preferably a composite formed therefrom), and (C) a solvent, (D) a base polymer, (E) ) Crosslinking agent and other components of the electroless plating base agent, the specific method of forming the base layer of electroless metal plating, firstly combine the aforementioned (A) component polymer and (B) metal particles (preferably by this) The resulting composite) (if necessary with (D) base polymer, (E) crosslinking agent and other components) is dissolved or dispersed in (C) solvent to form a form of painting, and the painting is used to form a metal plating On the substrate of the film, spin coating method; knife coating method; dip coating method; roll coating method; bar coating method; die coating method; spray coating method; inkjet method; pen nanolithography (FPN), dip Pen nanolithography (DPN) and other pen lithography; letterpress printing, flexographic printing, resin relief printing, contact printing, micro contact printing (μCP), nano imprint lithography (NIL), nano Relief printing methods such as transfer printing (nTP); gravure printing methods such as gravure printing and engraving; offset printing methods; stencil printing methods such as screen printing and mimeograph; offset printing methods, etc. After the solvent is evaporated and dried, a thin layer is formed. Among these coating methods, bar coating, flexographic printing, gravure printing, spin coating, spray coating, inkjet, pen photolithography, contact printing, μCP, NIL, and nTP are also preferred. When the spin coating method is used, coating can be performed in a short time, so even a highly volatile solution can be used, and it has the advantage of being able to perform coating with high uniformity. When the spray coating method is used, a very uniform coating can be carried out with a very small amount of paint, which is very advantageous for the industry. When inkjet, pen lithography, contact printing, μCP, NIL, nTP are used, for example, wiring and other fine patterns can be efficiently formed (painted), which is very advantageous industrially.

＜(C) Solvent＞ In addition, as the solvent used here, the polymer of the above-mentioned (A) component and (B) metal fine particles (preferably a composite of these) can be used, and the (D) component, (E) Components and other components can be dissolved or dispersed, and are not particularly limited. For example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, and dichlorobenzene; methanol, Ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n-hexanol, n-octanol, 2-octanol, 2-ethylhexanol and other alcohols; methyl cellosolve Cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve and other cellosolves; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether Base 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, two Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl Glycol ethers such as methyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether ethyl Glycol esters such as PGMEA; ethers such as tetrahydrofuran (THF), methyltetrahydrofuran, 1,4-dioxane, and diethyl ether; esters such as ethyl acetate and butyl acetate; acetone, methyl Ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone; aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; 1, Halogenated aliphatic hydrocarbons such as 2-dichloroethane and chloroform; N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethyl Dimethyl acetamide and other amides; dimethyl sulfide etc. These solvents may be used alone, or a mixture of two or more kinds of solvents may be used. And for the purpose of adjusting the viscosity of the paint, glycols such as ethylene glycol, propylene glycol and butylene glycol can also be added. In addition, although the concentration to be dissolved or dispersed in the above-mentioned solvent is arbitrary, the concentration of the non-solvent component in the paint [excluding all components of the solvent contained in the base (the polymer of component (A) and the metal fine particles (B)) Preferably, the concentration of (D) base polymer, (E) cross-linking agent and other components, etc.) of the composite formed by the above) is 0.05 to 90% by mass, preferably 0.1 to 80 quality%.

Although there is no particular limitation on the drying method of the solvent, for example, a hot plate or an oven may be used, and evaporation may be carried out in an appropriate environment, that is, in the atmosphere, an inert gas such as nitrogen, and a vacuum. Thereby, a base layer with a uniform film-forming surface can be obtained. The firing temperature is not particularly limited as long as the solvent can evaporate, but it is preferably carried out at 40 to 250°C.

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

The aforementioned electroless plating solution mainly contains metal ions (metal salt), complexing agent, and reducing agent, and for other purposes, it contains pH adjuster, pH buffering agent, reaction accelerator (second complexing agent), stabilizer , Surfactant (for the purpose of imparting gloss to the plating film, improving the wettability of the treated surface, etc.), etc. Among them, as the metal used for the metal plating film formed by electroless plating, iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and these alloys can be mentioned. select. In addition, the above-mentioned complexing agent and reducing agent may be blended with metal ions and selected appropriately.

In addition, as the electroless plating solution, commercially available plating solutions can be used. For example, an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex, and an electroless copper plating chemical (Melplate ( Registered trademark) CU series); electroless nickel plating solution (ICPNicolon (registered trademark) series, Top piena650) manufactured by Okuno Pharmaceutical Industry Co., Ltd., electroless copper plating solution (OPC-700 electroless copper MK, ATSAd CopperIW) , Same as CT, OPCCopper (registered trademark) AF series, same as HFS, same as NCA), electroless tin plating solution (SubstarSN-5), electroless gold plating solution (Flash gold330, Self goldOTK-IT), electroless silver Plating solution (Muden Silver); electroless palladium plating solution (paletteII), electroless gold plating solution (DipG series, NCgold series) manufactured by Kojima Chemical Co., Ltd.; electroless manufactured by Sasaki Chemical Co., Ltd. Silver plating solution (Esudaiya AG-40); Electroless nickel plating solution (Kanigen (registered trademark) series, Schumer (registered trademark) series, Schumer (registered trademark) Crab black (registered trademark) series manufactured by Japan Kanigen (Stock) ), electroless palladium plating solution (S-KPD); electroless copper plating solution (Cueposit (registered trademark) Coppermix series, Circuposit (registered trademark) series) manufactured by The Dow Chemical Company, electroless palladium plating solution ( Paramarth (registered trademark) series), electroless nickel plating solution (Duraposit (registered trademark) series), electroless gold plating solution (Aurolectrores (registered trademark) series), electroless tin plating solution (Timposit (registered trademark) Series); Uemura Industry Co., Ltd.'s electroless copper plating solution (Sur Cup (registered trademark) ELC-SP, same PSY, same PCY, same PGT, same PSR, same PEA, same PMK), Atotech Japan (share) Electroless copper plating solution (Print gantt (registered trademark) PV, same as PVE) etc.

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

The following examples are given to further illustrate the present invention in more detail, but the present invention is not limited to these examples. In addition, the measurement of number average molecular weight and weight average molecular weight are as follows. [Determination of number average molecular weight and weight average molecular weight] The number average molecular weight and weight average molecular weight of the copolymer obtained according to the following synthesis examples will be determined using Tosoh (stock) GPC equipment (Shodex column KD800 and TOSOH column TSK-GEL), The dissolving solvent N,N-dimethylformamide (as an additive, mixed lithium bromide-hydrate (LiBr･H ₂ O) 10mmol/L (liter)) flows into the column at a flow rate of 1mL/min (column temperature 40 ℃) and make the measurement under the conditions of dissociation. In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

The meanings of the abbreviations used in the following examples are as follows. MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate NVA: N-vinyl acetamide GMA: Glycidyl methacrylate Cyclomer M100: 3,4-epoxycyclohexyl methacrylate (made by Daicel) AMBN: 2,2’-azobis-2-methylbutyronitrile PGME: Propylene glycol monomethyl ether IPE: Diisopropyl ether DAA: Diacetone alcohol BL-10: Polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd.)

＜Synthesis example 1＞ Styrene 2.00g, NVA 1.63g, GMA 2.73g, AMBN 0.32g were dissolved in PGME 15.59g, and the copolymer solution (solid content concentration 30% by mass) obtained by reacting at 80°C for 20 hours was stirred while diethyl 500 mL of base ether was poured into the bottom, and a polymer was deposited. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P1). The Mn of the obtained copolymer was 6,057 and the Mw was 8,884.

＜Synthesis example 2＞ Styrene 2.00 g, NVA 1.63 g, Cyclomer M100 3.76 g, and AMBN 0.37 g were dissolved in 18.14 g of PGME, and the copolymer solution (solid content concentration 30% by mass) obtained by reacting at 80°C for 20 hours was stirred while diethyl 500 mL of base ether was poured into the bottom, and a polymer was deposited. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P2). The Mn of the obtained copolymer was 5,336 and the Mw was 8,669.

＜Synthesis example 3＞ Dissolve 2.00 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 put the polymer solution (solid content 30% by mass) obtained by reacting at 80°C for 20 hours in diethyl 500ml of base ether was purified by reprecipitation. The precipitated polymer was filtered under reduced pressure, and vacuum dried at 50°C to obtain polymer powder (P3). The Mn of the obtained polymer was 6,806 and the Mw was 11,797.

＜Synthesis example 4＞ Dissolve 2.00 g of MMA, 1.11 g of HEMA, and 0.16 g of AMBN in 7.63 g of PGME. The copolymer solution (solid content 30% by mass) obtained by the reaction at 80°C for 20 hours while stirring 500 mL of diethyl ether Put in, and precipitate the polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50°C to obtain a copolymer powder (P4). The Mn of the obtained copolymer was 13,186 and the Mw was 24,452.

＜Synthesis example 5＞ A 100 mL reaction flask equipped with a cooler was charged with 0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stirred until uniform. For this solution, a solution of 1.0 g of P1 polymerized in Synthesis Example 1 dissolved in 16.40 g of chloroform and 6.40 g of ethanol 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 poured into 341 g of an IPE/hexane solution (mass ratio 10:1) while stirring, and a polymer/Pd particle composite was deposited. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of black powder of the Pd particle composite (M1).

＜Synthesis example 6＞ A 100 mL reaction flask equipped with a cooler was charged with 0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stirred until uniform. For this solution, a solution of 1.0 g of P2 polymerized in Synthesis Example 2 dissolved 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 poured into 341 g of an IPE/hexane solution (mass ratio 10:1) while stirring, and a polymer/Pd particle composite was deposited. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of black powder of the Pd particle composite (M2).

＜Synthesis example 7＞ A 100 mL reaction flask equipped with a cooler was charged with 0.90 g of palladium acetate [manufactured by Wako Pure Chemical Industries, Ltd.] and 9.10 g of chloroform, and stirred until uniform. For this solution, a solution of 1.0 g of P3 polymerized in Synthesis Example 3 dissolved in 16.40 g of chloroform and 6.40 g of ethanol 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 poured into 341 g of an IPE/hexane solution (mass ratio 10:1) while stirring, and a polymer/Pd particle composite was deposited. The precipitated polymer/Pd particle composite was filtered under reduced pressure and vacuum dried at 50°C to obtain 0.9 g of black powder of the Pd particle composite (M3).

[Preparation of plating solution] <Preparation example 1> In a 300 mL beaker, 20 mL of TopNicolon SA-98-MLF (manufactured by Okuno Pharmaceutical Co., Ltd.) and 11 mL of TopNicolon SA-98-1LF (manufactured by Okuno Pharmaceutical Co., Ltd.) were placed, and pure water was further added to bring the total amount of the solution to 200 mL. After stirring this solution, an electroless nickel plating solution was obtained.

[Assessment of dispersion] The obtained Pd particle composite was thrown in as shown in Table 1, and after stirring for 1 hour, the state of the static solution was visually evaluated. The evaluation results are summarized in Table 2 below.

＜Assessment criteria for dispersion＞ ○: A homogeneous solution is obtained. ×: A precipitate is seen, and a uniform solution is not obtained.

[Evaluation of plating precipitation] The LCP (Baeliqueur (registered trademark) LCP manufactured by Chiyoda Integre Co., Ltd.) substrate was subjected to surface treatment for 30 seconds using a UV ozone cleaning device (UV-208 manufactured by Techno Vision Co., Ltd.). After the electroless plating base was applied to the surface-treated LCP by bar coating to a film thickness of 6 μm, it was heated at 80° C. for 5 minutes to form a coating film. The coating film was further heated at 200°C for 10 minutes and then cured. The obtained cured film was immersed in the electroless nickel plating solution prepared in Preparation Example 1 for 2 minutes. After that, the obtained plating substrate was washed with water, and the state of the metal plating film was visually evaluated. The evaluation results are summarized in Table 2 below.

＜Evaluation criteria of plating precipitation＞ ○: The precipitation coating film is uniformly plated throughout. -: Not implemented because a homogeneous solution was not obtained

＜Assessment of adhesion＞ The part of the metal plating film on the plating substrate obtained above was cut into 10×10 units with a 1mm interval in vertical and horizontal directions with a cutter. Paste the plastic tape (registered trademark) made by Nichiban (stock) on the cut, and wipe it strongly to make it fully adhered, then peel off the adhered adhesive tape at one time, and the state of the metal plating film is based on the following criteria Perform a visual assessment. The evaluation results are summarized in Table 2 below.

＜Assessment criteria for adhesion＞ ○: None of the 100 pieces remained without peeling. ×: Even if it is 1 unit, it is peeled off. -: It was not implemented because a uniform solution could not be obtained.

As shown in Table 2, the dispersibility and plating precipitation properties of Examples 1 to 5 and Comparative Examples 1 and 2 are all good. In addition, Examples 1 to 5 have good adhesion. On the other hand, in Comparative Examples 1 and 2, sufficient adhesion was not confirmed.

Claims (17)

An electroless plating base agent, which is an electroless plating base agent used when forming a metal plating film on a substrate by electroless plating treatment, and is characterized in that it contains: (A) A structural unit derived from a monomer a having a metal dispersible group and a radical polymerizable double bond in the molecule, and a structural unit derived from a monomer having a crosslinkable group and a radical polymerizable double bond in the molecule The copolymer of the constituent unit of monomer b, (B) Metal particles, and (C) Solvent. The base of claim 1, wherein the metal dispersible base in the (A) copolymer contains a complex in which (B) metal fine particles are attached or coordinated. Such as the base of claim 1 or claim 2, wherein the aforementioned monomer a has a compound of either a vinyl group or a (meth)acryloyl group. The base agent of claim 3, wherein the aforementioned monomer a is a compound represented by the following formula (1) or (2);

(In formula (1), 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, which represents a hydrogen atom, or R ₁ and R ₂ and these bonded atoms can form a 4- to 6-membered cyclic amide; In formula (2), R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a carbon atom of 1 to 10 It can be a branched alkyl group, a branched alkoxy group with 1 to 10 carbon atoms, or a branched alkoxyalkyl group with 1 to 10 carbon atoms, L represents O or N, R ₅ only exists When L represents N, it represents a hydrogen atom, or R ₄ and R ₅ together with these bonded atoms can form a 4- to 6-membered cyclic amide or a 4- to 6-membered cyclic amide) . The base agent of claim 4, wherein the aforementioned monomer a is N-vinylpyrrolidone, N-vinylacetamide or N-vinylformamide. Such as the base of claim 1 or claim 2, wherein the aforementioned monomer b is a compound having any one of a vinyl group and a (meth)acrylic group. The base agent of claim 6, wherein the aforementioned monomer b is a compound represented by the following formula (3);

(In formula (3), X represents a single bond, a carbonyloxy group, an amido group or a phenylene group, and Y represents an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, which may be branched Alkyl ether group with 1 to 6 carbons, thioalkylene group with 1 to 6 carbons or sulfanyl ether group with 1 to 6 carbons, Z represents a crosslinkable group, R ⁶ represents a hydrogen atom or carbon Number of 1 to 4 alkyl). Such as the base of any one of claims 1 to 7, wherein among the monomers imparted to the aforementioned (A) copolymer, the number of moles of the aforementioned monomer a contains 5 to 500% of the number of moles The amount of the aforementioned monomer b. Such as the base agent of any one of claim 1 to claim 8, the aforementioned (B) metal fine particles are selected from iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), At least one kind of metal particles composed of silver (Ag), tin (Sn), platinum (Pt), and gold (Au). The base agent of claim 9, wherein the aforementioned (B) metal fine particles are palladium fine particles. The base agent of any one of claim 1 to claim 10, wherein the aforementioned (B) metal fine particles are fine particles having an average primary particle diameter of 1-100 nm. The base of any one of claims 1 to 11, which further contains a base resin having (D) a non-radical polymerizable crosslinkable group. The base agent of any one of claims 1 to 12, which further contains (E) a crosslinking agent. A base layer for electroless metal plating, which is characterized by using an electroless plating base as defined in any one of Claims 1 to 13. A metal plating film characterized by being formed on a base layer of electroless metal plating as in claim 14. A metal coating substrate, characterized by comprising: a substrate, a base layer of electroless metal plating according to claim 14 formed on the substrate, and a metal plating formed on the base layer of electroless metal plating membrane. A method for manufacturing a metal coating substrate, which is characterized by the following steps (1) and (2); (1) Step: the step of coating the electroless plating base agent as described in any one of claim 1 to claim 13 on a substrate, so that the base layer of electroless metal plating is provided on the substrate; (2) Step: the step of immersing the substrate with the base layer in an electroless plating bath to form a metal plating film on the base layer.