WO2006095590A1

WO2006095590A1 - Filler for resin, resin base material containing same and electronic component substrate material

Info

Publication number: WO2006095590A1
Application number: PCT/JP2006/303599
Authority: WO
Inventors: Toshifumi Kawamura; Toru Imori
Original assignee: Nippon Mining & Metals Co., Ltd.
Priority date: 2005-03-10
Filing date: 2006-02-27
Publication date: 2006-09-14
Also published as: JPWO2006095590A1; JP5072094B2

Abstract

Disclosed is a technique which can be applied to a resin base material commonly used as substrate material and enables to improve the adhesion strength between the base material and a plated metal layer, namely a general resin base material improved in adhesion to a plated metal layer. Specifically disclosed is a filler for resins composed of a silica which is surface-treated with both a solution containing a silane coupling agent such as one obtained by a reaction between an azole compound or amine compound and an epoxysilane compound and a solution containing a noble metal compound, or alternatively surface-treated with a mixture of these solutions. Also specifically disclosed are a resin base material containing such a filler and an electronic component substrate material obtained by electroless plating such a resin base material.

Description

Specification

Resin filler, resin base material containing the same, and electronic component base material

Technical field

The present invention relates to a resin filler, a resin base material containing the same, and an electronic component base material.

Background art

[0002] In recent years, the wiring density of printed circuit boards has been increasing due to demands for smaller and higher performance devices. Along with this, the surface of a board, such as a build-up board, is rope-filed in order to make the wiring finer, and due to the low roughness of this surface, the adhesion between the board and the metal plating film formed on the board is increased. It has become difficult to take sufficient sex. However, in order to satisfy the above requirements, this improvement in adhesion strength is also required.

[0003] Various proposals have already been made to meet such demands. Among them, what is proposed in Patent Document 2 or 2 is that a polyimide resin precursor solution containing a palladium compound is applied and dried on a polyimide resin substrate to form a polyimide resin precursor layer. After forming a plating base nucleus by irradiating ultraviolet rays in the presence of a hydrogen donor, a polyimide base metal layer is formed by an electroless plating process, and a surface plating layer is further formed or before the polyimide is formed. When the resin precursor layer is heated and imidized to form a polyimide resin layer. This is because the adhesive base nucleus is formed in the polyimide resin layer, and the anchoring effect improves the adhesion strength between the polyimide resin layer and the plating base metal layer.

Patent Document 1: Japanese Patent Laid-Open No. 2002-30216

Patent Document 2: Japanese Patent Laid-Open No. 2002-374055

Disclosure of the invention

Problems to be solved by the invention

However, in the above proposal, the substrate material is limited to polyimide resin, and cannot be applied to a substrate for electronic parts in general. Further, the ultraviolet ray treatment is required for activating noradium, and further, high temperature heating is required for imido, so that the treatment process is complicated. [0005] The present invention provides a technique that can be applied to a general resin base material as a substrate material and can more easily improve the adhesion strength between the base material and the metal layer. That is, an object of the present invention is to provide a general resin substrate useful as an electronic component substrate having improved adhesion strength with a plated metal layer.

Means for solving the problem

[0006] As a result of diligent investigations, the present inventor has found that the filler is a solution containing a noble metal compound that is an electroless plating catalyst and a solution containing a silane coupling agent that traps the noble metal, or a mixed solution thereof. By surface-treating and blending the resin filler with the resin base material, the surface of the resin base material can be made to appear on the surface of the resin base material, and the surface can be activated. It is possible to give an anchor effect to the deposited metal by attaching via the silane coupling agent, and to improve the adhesion strength between the metal layer and the resin substrate by electroless plating. As a result, the present invention has been achieved.

That is, the present invention provides:

[1] A resin filler that is surface-treated with a solution containing a silane coupling agent and a solution containing a noble metal compound, or a mixed solution thereof.

[2] The resin filler according to [1], wherein the filler is silica.

[3] The resin filler according to [1] or [2], wherein the silane coupling agent is a silane coupling agent obtained by reacting an azole compound or an amine compound with an epoxy silane compound.

[4] The resin filler according to any one of [1] to [3], wherein the noble metal compound is a palladium compound.

[5] A resin base material containing the resin filler according to any one of [1] to [4].

[6] The resin substrate according to [5], wherein the resin of the resin substrate is an epoxy resin.

[7] An electronic component base material obtained by applying electroless plating to the resin base material according to [5] or [6].

[8] The electronic component base material according to [7], wherein the electronic component base material is a build-up substrate.

About.

The invention's effect

[0008] According to the present invention, a solution containing a silane coupling agent and a solution containing a noble metal compound, By blending the filler whose surface has been treated with each or a mixed solution thereof into the resin base material, the filler appears on the surface of the resin base material, and the resin base material is electrolessly electrolyzed. The deposited metal can obtain an anchor effect through the silane coupling agent, and as a result, the adhesion strength between the resin layer of the resin base material and the metal layer due to electroless plating is improved. Can do.

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] As the filler used in the present invention, it is possible to use a filler that is generally blended with sallow. For example, inorganic fillers such as silica, alumina, glass fiber or organic fillers can be raised.

The filler preferably has an average particle size of 0.1 to 50 μm, more preferably 1 to 10 μm.

[0010] The silane coupling agent used in the present invention is preferably an azole compound or a silane coupling agent that traps a noble metal obtained by the reaction of an amine compound and an epoxy silane compound.

As the amine compound to be reacted with the epoxysilane compound, lower dialkylamines such as dimethylamine and jetamine are preferred.

The azole compound is a compound containing an azole group, and preferred azole groups include imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, Examples include thiatriazole, bendazole, indazole, benzimidazole, and benzotriazole. Of these, an imidazole group is particularly preferable.

[0011] The silane coupling agent is a compound having a SIX X X group in addition to a noble metal ion-trapping group derived from the azole compound or an amine compound,

1 2 3 1, X

2,

X means alkyl group, halogen or alkoxy group, and can be fixed to filler

Three

Any functional group may be used. X, X, and X may be the same or different.

one two Three

[0012] Further, as an epoxy group-containing silane compound to be reacted with the above-mentioned amine compound or azole compound,

[Chemical 1] C ^ ₂ flops _{_{H- CH 2 0 (CH 2)}} 3 S i (OR 3) n R 4 (3 one ")

O

(Wherein R ³ and R ⁴ are hydrogen or an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 3).

[0013] The reaction between the azole compound and the epoxy group-containing silane compound can be performed under the conditions described in JP-A-6-256358. For example, at 80 to 200 ° C., 0.1 to 10 mol of an epoxy group-containing silane compound is added dropwise to 1 mol of an azole compound, and reacted for 5 minutes to 2 hours. In that case, an organic solvent such as chloroform, dioxane methanol, ethanol, or the like, which does not particularly require a solvent, may be used.

[0014] Other examples of the silane coupling agent having a metal scavenging ability used in the present invention include y-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-j8 (aminoethyl) _Ί — Examples include aminopropyltrimethoxysilane, N-j8 (aminoethyl) γ-aminopropyltriethoxysilane, and _Ί -mercaptopropyltrimethoxysilane.

In the present invention, the particularly preferred U ヽ silane coupling agent is imidazole silane, which is represented by the following (1), (2) and (3).

[Chemical 2]

NCH ₂ CHCH ₂ 0 (CH ₂ ) ₃ Si (〇R ³ ) _n R ⁴ ₍₃ — _nl (1)

OH

(Where R ¹ is hydrogen or an alkyl group having 120 carbon atoms, R ² is hydrogen, a beer group or an alkyl group having 15 carbon atoms, R ³ R ⁴ is an alkyl group having 13 carbon atoms, and n is 1 indicates 3.)

[0016] the above formula (1), (2), in (3), I ^ R ⁴ has a meaning of as being the defined, in particular ease force R ¹ of the synthesis is hydrogen, methyl, Echiru, Undeshiru R ² is preferably hydrogen, methyl, and ethyl. R ³ R ⁴ is preferably methyl and ethyl.

[0017] The two synthesis methods are disclosed in JP-A-5-186479.

That is, it can be synthesized by an equimolar reaction of the following imidazole compound and 3-glycidoxypropyl silane compound. The above synthesis method (1), (2

) Even when it is obtained as a mixture of imidazole silanes represented by (3), it is advantageous to use it in the form of a mixture that does not need to be separated.

[0018] [Chemical 3] S i (OR ³ ) _n R ⁴ —

(Four )

(In the above formula, R ¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ² is hydrogen, a bur group or an alkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ are carbon atoms having 1 to 3 carbon atoms. Alkyl group, n represents 1-3.)

Preferable examples of the imidazole compound represented by the general formula (4) include imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, and 4-bulimidazole. Among these, imidazole; 2-alkylimidazole is particularly preferred as 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole; and 2,4 dialkylimidazole. Can include 2-ethyl-4-methylimidazole and the like. [0020] The 3-glycidoxypropyl trisilane compound represented by the general formula (5) includes 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3 —Glycidoxypropylalkoxydialkylsilanes. Among these, particularly preferred are 3-glycidoxypropyltrialkoxysilanes: 3-glycidoxypropinoletrimethoxysilane, 3-glycidoxypro Pinoletriethoxysilane, 3-glycidoxypropyldialkoxyalkylsilane as 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylalkoxydialkylsilane as 3-glycidoxypropylethoxydimethylsilane Etc.

In the present invention, the silane coupling agent is used in the treatment agent at a concentration of 1 to 30000 mgZL, preferably 10 to 20000 mgZL.

[0021] The noble metal compound includes palladium, silver, platinum, gold and other chlorides, hydroxides, oxides, and the like that exhibit a catalytic effect when copper or nickel is deposited from an electroless plating solution. Forces including ammine complexes such as sulfates and ammonium salts Particularly preferred are palladium compounds, especially palladium soap. The precious metal compound is preferably used as an aqueous solution, and the concentration in the treating agent is preferably 1 to 30000 mg ZL. In this specification, the concentration in the treatment agent refers to the concentration in the solution when the filler is pretreated.

[0022] In the present invention, the filler treatment is performed using a force performed by a solution of each of the silane coupling agent and the noble metal compound or a mixed solution of the silane coupling agent and the noble metal compound. When the filler is treated with a solution of each of the silane coupling agent and the noble metal compound, it is preferable to treat with a solution containing the silane coupling agent first.

Examples of solvents used in this solution include water, methyl alcohol, ethyl alcohol, 2-propanol, butyl alcohol, acetone, toluene, ethylene glycol, polyethylene glycol, dimethylformamide, dimethyl sulfoxide, dioxane, and the like. It can be used in a solution dissolved in a mixed solution or the like.

When using water, it is necessary to optimize the pH of the solution, especially according to the surface of the filler and the mating conditions.

[0023] The surface-treated resin filler may be blended with a material to be a resin base material to obtain a resin base material. Thus, the filler appears on the surface of the obtained resin base material. The amount of the surface-treated resin filler is arbitrarily adjusted depending on the resin substrate used so that the filler appears on the surface of the resin substrate obtained by adding the resin filler.

[0024] The resin base material used in the present invention is not particularly limited, including those used as electronic component base materials. For example, epoxy resin, phenol resin, melamine resin, polyurethane resin, silicon resin and the like can be mentioned.

In the present invention, a particularly preferred resin is epoxy resin. This epoxy resin includes, for example, diglycidyl ethers of bisphenols such as bisphenol A and bisphenol F (bisphenol type epoxy resin), side chain, or main chain with rubber, urethane, poly Those modified with flexible resins such as ether and polyester, phenol novolaks, cresol boracs, and other glycidyl etherified products (novolac type epoxy resins), or conjugated diene polymer epoxy compounds such as polybutadiene, etc. Is raised.

[0025] Further, in order to further enhance the electroless binding activity of the filler treated with each of the solution containing the noble metal compound and the solution containing the silane coupling agent or a mixed solution thereof, Before starting, it is preferable to treat the resin base material containing the filler with a reducing agent. As this reducing agent, a known reducing agent that is usually used in electroless plating can be used. Preferably, hypophosphorous acid, alkali metal hypophosphite such as sodium hypophosphite, Dimethylamine borane can be raised.

Further, before the treatment with the reducing agent, the adhesion strength is further improved by treating the resin base material containing the filler with permanganic acid or the like and roughening the surface.

[0026] In the present invention, the resin base material containing the filler treated with each of the solution containing the noble metal compound and the solution containing the silane coupling agent or the mixed solution thereof is subjected to non-electrolysis. It includes electronic component base materials and build-up base materials.

In the present invention, the electroless plating itself is not particularly limited by a known method. Electroless plating is preferably copper plating, but nickel, cobalt, etc. may also be used. Further, after electroless plating, electric plating can be performed. A known technique with no particular limitation can be applied to this electric plating method. For example, copper, chromium, nickel, silver, etc. can be applied.

Example

[0027] Example 1

A commercially available silica-based filler (manufactured by Tatsumori Co., Ltd., maximum particle size of 35 μm, average particle size of 5 m) is mixed with imidazole silane (imidazole and 3-glycidoxypropyltrimethoxysilane). The product was immersed in a butanol solution containing lgZL and Pd soap (palladium naphthenate lgZUPd equivalent 200 mgZL), and air-dried and the solvent was removed for surface treatment. Bisphenol A-type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001) 90 parts by weight, multifunctional epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 154) 10 parts by weight, dicyandiamide cured 2 parts by weight of agent, imidazole silane curing accelerator (manufactured by Nikko Materials Co., Ltd.) 0.2 part by weight, 50 parts by weight of the filler treated as described above is added and heat molded. An insulated insulating resin was obtained. By treating this with an activator such as hypophosphorous acid (phosphinic acid) 30 g ZL, Pd was electrolessly activated. Electroless copper plating (high temperature type formalin copper plating solution, KC500 (manufactured by Nikko Metal Plating Co., Ltd., 0.3 m thickness)), followed by electric copper plating (copper sulfate plating solution, current density 1. 5 A / dm ² , 35 m thickness) The peel strength was 0.9 kgfZcm, and the peel strength was 90 ° peel strength (JIS C6481).

[0028] Example 2

A commercially available silica-based filler (manufactured by Tatsumori Co., Ltd., maximum particle size of 35 μm, average particle size of 5 m) is mixed with imidazole silane (imidazole and 3-glycidoxypropyltrimethoxysilane). The product was immersed in a butanol solution containing lgZL and Pd soap (palladium naphthenate lgZUPd equivalent 200 mgZL), and air-dried and the solvent was removed for surface treatment. 90 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001), 10 parts by weight of polyfunctional type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 154), dicyandiamide curing agent 2 parts by weight, imidazole silane curing accelerator (manufactured by Nikko Materials) 0.2 part by weight 50 parts by weight of the filler treated as described above An insulating resin containing a filler was obtained by heat molding. After roughening with permanganic acid, this was treated with an activator consisting of hypophosphorous acid (phosphinic acid) 30 g / L to make Pd electroless plating activity. Electroless copper plating (high temperature type formalin copper plating solution, KC 500 (manufactured by Nikko Metal Plating Co., Ltd., 0.3 m thickness) was applied, and then electric copper plating (copper sulfate plating solution, Current density 1.

35 m thick). The peel strength was 1.3 kgf / cm.

[0029] Example 3

A commercially available silica-based filler (manufactured by Tatsumori Co., Ltd., with a maximum particle size of 35 μm and an average particle size of 5 μm) was added to imidazole silane (equimolar amount of imidazole and 3-glycidoxypropyltrimethoxysilane). The product was treated with butanol solution containing lg / L · After drying, treated with butanol solution containing 100 mg / L of palladium chloride (Pd conversion 60mgZL) · Surface treatment was carried out by drying.Bisphenol A type Epoxy resin (Oka Shell Epoxy Co., Ltd., Epicoat 1001) 90 parts by weight, polyfunctional epoxy resin (Oka Chemical Shell Epoxy Co., Ltd., Epicoat 154) 10 parts by weight, dicyandiamide curing agent 2 parts by weight, Imidazole silane curing accelerator (manufactured by Nikko Materials Co., Ltd.) 0.2 parts by weight, 50 parts by weight of the filler treated as described above is added and heat-molded to obtain insulating resin containing filler. This was obtained with hypophosphorous acid ( Phosphinic acid) Pd was electrolessly activated by treatment with an activator consisting of 30 g ZL.Electroless copper plating (high-temperature type formalin copper plating solution, KC500 (manufactured by Nikko Metal Plating Co., Ltd., 0 3m thick), followed by electrolytic copper plating (copper sulfate plating solution, current density 1.5A 35m thick), peel strength was 0.8kgfZcm.

[0030] Example 4

Commercially available silica-based filler (manufactured by Tatsumori Co., Ltd., maximum particle size 35 μm, average particle size 5 μm) is treated with equimolar reaction of imidazole silane (imidazole and 3-glycidoxypropyltrimethoxysilane). Product) Surface treatment was performed by dipping in an aqueous solution containing 200 mg ZL, palladium chloride (60 mg ZL in terms of lOOmgZUPd) and ethylene glycol 20 g / L and drying. 90 parts by weight of bisphenol A type epoxy resin (Epicor Shell Epoxy Co., Ltd., Epicoat 1001), 10 parts by weight of polyfunctional epoxy resin (Epicoat 154, Epicoat 154), dicyandiamide curing agent 2 parts by weight, imidazole silane curing accelerator (Nikko Materia Co., Ltd.) (Luz) 0.2 parts by weight, 50 parts by weight of the filler treated as described above was added and heat-molded to obtain a filler-containing insulating resin. This was treated with an activator comprising hypophosphorous acid (phosphinic acid) 30 g / L to make Pd electroless plating activity. Electroless copper plating (high-temperature type formalin copper plating solution, KC500 (manufactured by Nikko Metal Plating Co., Ltd., 0.3 m thickness)), followed by electrolytic copper plating solution (copper sulfate plating solution, current density 1 The peel strength was 1. OkgfZcm.

[0031] Example 5

A commercially available silica-based filler (manufactured by Tatsumori Co., Ltd., maximum particle size of 35 μm, average particle size of 5 m) is mixed with imidazole silane (imidazole and 3-glycidoxypropyltrimethoxysilane). The product was immersed in a butanol solution containing lgZL and Pd soap (palladium naphthenate lgZUPd equivalent 200 mgZL), and air-dried and the solvent was removed for surface treatment. Polyaminobismaleimide (Kerimid, manufactured by Rhone Pouleic) 100 parts by weight dissolved in 50 parts by weight of N-methylpyrrolidone Add 100 parts by weight of the filler treated as described above and press-mold. Insulating polyimide resin containing a filler was obtained. By treating this with an activator that has a hypophosphorous acid (phosphinic acid) strength of 30 g / L, Pd was activated electrolessly. Electroless copper plating (high temperature type formalin copper plating solution, KC500 (manufactured by Nikko Metal Plating Co., Ltd., 0.3 / zm thickness)), followed by electrolytic copper plating (copper sulfate plating solution, current density) 1. 5AZdm ² (35 m thickness) The peel strength was 0.8 kgfZcm.

[0032] Example 6

The same treatment as in Example 1 was conducted except that the silica-based filler was changed to an alumina-based filler (Showa Denko KK, maximum particle size 30 m, average particle size 4 m). Peel strength was 0.9kgfZcm

[0033] Comparative Example 1

Using fillers that were not surface-treated in Example 1, insulating filler containing filler was prepared, and electroless copper plating (0.3 μm thick) with normal Sn—Pd colloid, followed by electrolytic copper plating ( Copper sulfate plating solution, current density 1.5AZdm ² , 35 m thickness). The peel strength was as low as O. lkgfZc m. Comparative Example 2

Using fillers that were not surface-treated in Example 2, a filler-filled insulating resin was prepared, and electroless copper plating (0.3 m thick) with ordinary Sn-Pd colloid and subsequent electrolytic copper plating (copper sulfate) Plating solution, current density 1.5 AZdm ² , 35 / zm thickness). Peel strength is 0.6kgf

Claims

The scope of the claims

[1] A resin filler that has been surface-treated with a solution containing a silane coupling agent and a solution containing a noble metal compound, or a mixed solution thereof.

[2] The resin filler according to claim 1, wherein the filler is silica.

[3] The silane coupling agent according to claim 1 or 2, wherein the silane coupling agent is a silane coupling agent obtained by a reaction of an azole compound or an amine compound and an epoxy silane compound. Fira.

[4] The resin filler according to any one of claims 1 to 3, wherein the noble metal compound is a palladium compound.

[5] A resin base material containing the resin filler according to any one of claims 1 to 4

6. The resin substrate according to claim 5, wherein the resin of the resin substrate is an epoxy resin.

[7] An electronic component base material obtained by electroless plating the resin base material according to claim 5 or 6.

8. The electronic component base material according to claim 7, wherein the electronic component base material is a build-up substrate.