JP6291742B2 - Resin composition, adhesion auxiliary layer for plating process, adhesion auxiliary layer for plating process with support, laminated board for wiring board, method for producing laminated board for wiring board, multilayer wiring board, and method for producing multilayer wiring board - Google Patents

Description

  The present invention relates to a resin composition, an adhesion auxiliary layer for plating process used in a plating process, an adhesion auxiliary layer for plating process with a support having the adhesion auxiliary layer for plating process, a laminated board for wiring board, and a laminated board for wiring board And a multilayer wiring board and a manufacturing method of the multilayer wiring board.

  In recent years, electronic devices have become increasingly smaller, lighter, and more functional, and as a result, LSIs and chip components have become more highly integrated, and their forms have rapidly changed to multi-pin and miniaturized. Yes. For this reason, in order to improve the mounting density of electronic components, multilayer wiring boards are being developed for fine wiring. As a manufacturing method of multilayer wiring boards that meet these requirements, an insulating resin (insulating resin film) that does not contain glass cloth is used as an insulating layer instead of a prepreg, and a wiring layer is formed while connecting via holes. Multilayer wiring boards have come to be widely used as methods suitable for weight reduction, miniaturization, and miniaturization.

  In such a build-up type multilayer wiring board, an insulating resin film is laminated on an inner circuit board, cured by heating, and then a via hole is formed by laser processing. And a roughening process and a smear process are performed by an alkali permanganate process etc., electroless copper plating is performed, and the via hole which enables interlayer connection with a 2nd circuit is formed (refer patent documents 1-3).

  On the other hand, when an insulating resin that does not contain glass cloth is used as the insulating layer in place of the prepreg for the multilayer wiring board, warping during mounting tends to increase and connection reliability tends to decrease. Accordingly, prepregs containing glass cloth have been reviewed again. However, via holes formed by laser processing used in the build-up method and high-density wiring by a semi-additive construction method are required even for substrates containing glass cloth.

  The resin used for the glass cloth-containing substrate is required to have a low coefficient of thermal expansion in order to suppress warping during mounting. However, such a resin system has a rigid skeleton, so that the elongation is small. Low adhesive strength with copper. Therefore, an M-SAP (Modified Semi-Additive Process) method has been proposed in which an ultrathin copper foil is used as a power feeding layer instead of the electroless plating layer, and a circuit is formed by a semi-additive method. However, in this method, since the power feeding layer is too thick as compared with the electroless copper plating in the build-up method, it is difficult to form a fine circuit with a Line / Space of 15 μm / 15 μm or less (see Patent Document 4).

  Therefore, it has been proposed to provide an adhesion auxiliary layer having high adhesion to plated copper on a prepreg including glass cloth. When laminating the adhesion auxiliary layer and the prepreg, the adhesion auxiliary layer is laminated with a prepreg in a state where an unreacted epoxy resin and an epoxy resin curing agent remain, a so-called semi-cured state (B stage state). The By carrying out like this, it is thought that an adhesion auxiliary layer and a prepreg can adhere firmly.

Japanese Patent Laid-Open No. 7-304931 JP 2002-3705 A JP-A-11-1547 JP 2003-101194 A

However, in the method of laminating the above-mentioned adhesion auxiliary layer on the prepreg, when the reactivity of the adhesion auxiliary layer in the B stage state is low, the components of the adhesion auxiliary layer are dispersed in the prepreg during lamination, and the characteristics of the adhesion auxiliary layer Will fall.
Accordingly, the present invention provides a resin composition having good reactivity in a B-stage state, having a small surface roughness and excellent adhesion to plated copper, an auxiliary adhesion layer used in a plating process, and a support. It is an object of the present invention to provide a method for manufacturing an adhesion auxiliary layer for a plating process, a laminated board for a wiring board and a laminated board for a wiring board, a multilayer wiring board formed by a plating process, and a method for producing a multilayer wiring board.

As a result of conducting research to solve the above problems, the present inventors have developed a resin composition containing a polyfunctional epoxy resin, an epoxy resin curing agent, a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin, and a phosphorus-based curing accelerator. The present inventors have found that the adhesion auxiliary layer for plating process formed by use exhibits excellent adhesiveness to the prepreg and the plated copper, and arrived at the present invention. That is, the present invention is as follows.
<1> A resin composition containing (A) a polyfunctional epoxy resin, (B) an epoxy resin curing agent, (C) a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin, and (D) a phosphorus curing accelerator.
<2> The resin composition according to <1>, wherein the (A) polyfunctional epoxy resin has a biphenyl structure.
<3> The resin composition according to the above <1> or <2>, wherein the (A) polyfunctional epoxy resin is an aralkyl novolac type epoxy resin.
<4> The resin composition according to any one of <1> to <3>, wherein the (D) phosphorus curing accelerator is an adduct of a tertiary phosphine and a quinone.
<5> An adhesion auxiliary layer for a plating process containing the resin composition according to any one of <1> to <4>.
<6> The adhesion auxiliary layer for plating process according to <5>, wherein the adhesion auxiliary layer for plating process has a thickness of 1 to 10 μm.
<7> The adhesion auxiliary layer for plating process according to <5> or <6>, wherein the surface roughness Ra after the roughening treatment of the adhesion auxiliary layer for plating process is 0.4 μm or less.
<8> An adhesion auxiliary layer for a plating process with a support, wherein the adhesion auxiliary layer for a plating process according to any one of <5> to <7> is disposed on a support.
<9> A plating process adhesion auxiliary layer according to any one of the above <5> to <7> and a wiring board prepreg, wherein the adhesion auxiliary layer and the surface of the wiring board prepreg are in contact with each other. A laminated board for a wiring board, which is laminated on.
<10> The adhesion auxiliary layer for a plating process with a support according to <8> above is overlaid so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact, and the support and the end plate are overlaid and press-molded. A method for producing a laminated board for a wiring board, wherein the end plate and the support are removed after molding.
<11> The support auxiliary layer for a plating process with a support according to <8> above is laminated so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact with each other, and is laminated by heating and pressurizing with a laminator. A method for producing a laminated board for wiring board, which is cured afterwards and the support is removed after curing.
<12> The adhesion auxiliary layer for plating process according to any one of the above <5> to <7>, a prepreg for wiring board, and a wiring board on which circuit processing has been performed are included in this order. Multilayer wiring board.
<13> The adhesion auxiliary layer for a plating process with a support according to <8> above is overlaid so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact with each other, and the back surface of the prepreg for wiring board is subjected to circuit processing. A method of manufacturing a multilayer wiring board, wherein the substrate and the end plate are stacked so as to be in contact with the surface of the printed wiring board, the end plate is overlapped and press molded, and the end plate and the support are removed after molding.
<14> The support auxiliary layer for plating process with support according to <8> above is overlaid so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact, and the back surface of the prepreg for wiring board is subjected to circuit processing. A method for producing a multilayer wiring board, wherein the multilayered wiring board is laminated so as to be in contact with the surface of the printed wiring board, laminated by heating and pressing with a laminator, cured after lamination, and the support is removed after curing.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has favorable reactivity in a B stage state, surface roughness is small, and is excellent in adhesiveness with plated copper, the adhesion auxiliary layer used for a plating process, a support body It is possible to provide a method for manufacturing an adhesion auxiliary layer for a plating process, a laminated board for a wiring board and a laminated board for a wiring board, a multilayer wiring board formed by a plating process, and a method for producing a multilayer wiring board.

Hereinafter, the present invention will be described in detail.
[Resin composition for adhesion auxiliary layer]
The resin composition according to the present invention includes (A) a polyfunctional epoxy resin (hereinafter sometimes referred to as (A) component), (B) an epoxy resin curing agent (hereinafter sometimes referred to as (B) component). , (C) a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin (hereinafter sometimes referred to as (C) component), and (D) a phosphorus-based curing accelerator (hereinafter sometimes referred to as (D) component) (Hereinafter, sometimes referred to as a resin composition for an adhesion auxiliary layer).
Hereinafter, the components (A) to (D) will be described.

<(A) component>
The polyfunctional epoxy resin as the component (A) is an epoxy resin having two or more epoxy groups in the molecule. For example, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, an aralkyl novolak type epoxy resin, and the like can be given. These polyfunctional epoxy resins may be used alone or in combination of two or more.
Especially, the polyfunctional epoxy resin which has a biphenyl structure is preferable from the point which the adhesive force with plated copper improves, and it is more preferable that it is an aralkyl novolak type epoxy resin.
Examples of the aralkyl novolac type epoxy resin include an aralkyl novolak type epoxy resin having a biphenyl structure represented by the following formula (I).

（式中、ｐは、１〜５を示す）

(Wherein p represents 1 to 5)

In addition, as a commercial item of the said resin, Nippon Kayaku Co., Ltd. NC-3000 (epoxy resin of the formula (I) whose p is 1.7), NC-3000-H (p is a formula of 2.8 ( I) epoxy resin) and the like.
(A) As a compounding quantity of a polyfunctional epoxy resin, it is preferable that it is 20-80 mass% in solid content conversion in the resin composition for adhesion auxiliary layers, for example, and it is more preferably 40-70 mass%. preferable. When the blending amount of the component (A) is 20% by mass or more, a conductor layer and good adhesive strength can be obtained, and when it is 80% by mass or less, sufficient solder heat resistance can be maintained.

<(B) component>
As the epoxy resin curing agent as component (B), for example, various phenol resins, acid anhydrides, amines, hydrazides and the like can be used. As the phenol resins, for example, novolak type phenol resins, resol type phenol resins and the like can be used. As acid anhydrides, for example, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid and the like can be used. Examples of amines that can be used include dicyandiamide, diaminodiphenylmethane, and guanylurea. In order to improve the reliability, for example, a novolac type phenol resin is preferable.
(B) As a compounding quantity of a component, it is preferable that it is 0.5-1.5 equivalent with respect to an epoxy group, for example. (B) When the compounding quantity of a component is 0.5-1.5 equivalent with respect to an epoxy group, the fall of the adhesive force with plated copper is prevented, and Tg (glass transition temperature) and insulation fall are prevented. be able to.

<(C) component>
The phenolic hydroxyl group-containing polybutadiene-modified polyamide resin as component (C) has structural units represented by the following formulas (i), (ii), and (iii).

式中、ａ、ｂ、ｃ、ｘ、ｙ及びｚは、それぞれ平均重合度であって、ａ＝２〜１０、ｂ＝０〜３、ｃ＝３〜３０、ｘ＝１に対しｙ＋ｚ＝２〜３００（（ｙ＋ｚ）／ｘ）の整数を示し、さらにｙ＝１に対しｚ≧２０（ｚ／ｙ）である。Ｒ、Ｒ’、及びＲ’’は、それぞれ独立に、芳香族ジアミン又は脂肪族ジアミンに起因する２価の基であり、複数のＲ’’’は、それぞれ独立に、芳香族ジカルボン酸、脂肪族ジカルボン酸、又は両末端にカルボキシル基を有するオリゴマーに起因する２価の基である。なお、Ｒ、Ｒ’、Ｒ’’及びＲ’’’は、具体的には、後述するジアミン原料及びジカルボン酸原料に由来するものである。また、（Ｃ）成分の重量平均分子量は、例えば、６０，０００〜２５０，０００であることが好ましく、８０，０００〜２００，０００であることがより好ましい。

In the formula, a, b, c, x, y, and z are average polymerization degrees, respectively, and a = 2 to 10, b = 0 to 3, c = 3 to 30, and x = 1, y + z = 2. An integer of ˜300 ((y + z) / x) is shown, and z ≧ 20 (z / y) with respect to y = 1. R, R ′, and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and a plurality of R ′ ″ are each independently an aromatic dicarboxylic acid, A divalent group derived from an aromatic dicarboxylic acid or an oligomer having carboxyl groups at both ends. R, R ′, R ″ and R ′ ″ are specifically derived from the diamine raw material and dicarboxylic acid raw material described later. In addition, the weight average molecular weight of the component (C) is, for example, preferably 60,000 to 250,000, and more preferably 80,000 to 200,000.

The (C) component phenolic hydroxyl group-containing polybutadiene-modified polyamide resin includes, for example, diamine, phenolic hydroxyl group-containing dicarboxylic acid, dicarboxylic acid not containing phenolic hydroxyl group, and polybutadiene having carboxyl groups at both ends. It is synthesized by polycondensation of a carboxyl group and an amino group in an organic solvent such as 2-pyrrolidone (NMP) in the presence of a phosphite ester and a pyridine derivative as a catalyst.
In the present invention, the diamine (diamine raw material) used for the production of the component (C) may be an aromatic diamine or an aliphatic diamine.

  Examples of the aromatic diamine include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylenediamine , Methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), isopropylidenedianiline, diamino Benzophenone, diaminodimethylbenzophenone, diamino Ntorakinon, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, diaminofluorene and the like.

Examples of the aliphatic diamine include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, and triazaundecadiamine. Is mentioned.
These aromatic and aliphatic diamines may be used alone or in combination of two or more.
In the present invention, the phenolic hydroxyl group-containing dicarboxylic acid used for the production of the component (C) includes, for example, hydroxyisophthalic acid, but is not limited thereto, hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, It may be dihydroxyterephthalic acid or the like.

In the present invention, the dicarboxylic acid not containing a phenolic hydroxyl group (dicarboxylic acid raw material) used for the production of the component (C) may be an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an oligomer having carboxyl groups at both ends.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, sulfonylbenzoic acid, and naphthalenedicarboxylic acid.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth) acryloyloxysuccinic acid, di (meta) ) Acryloyloxysuccinic acid, (meth) acryloyloxymalic acid, (meth) acrylamide succinic acid, (meth) acrylamide malic acid and the like.
In the present invention, the polybutadiene having carboxyl groups at both ends used for the production of the component (C) is preferably, for example, an oligomer having a number average molecular weight of 200 to 10,000, and more preferably an oligomer having a number average molecular weight of 500 to 5,000. preferable.
Commercially available products can be used as the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin as component (C). Examples of commercially available products include BPAM-155 manufactured by Nippon Kayaku Co., Ltd.

  In the resin composition for an adhesion auxiliary layer, the blending ratio of the component (C) is preferably 5 to 30 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). If it is 5 mass parts or more, the toughness of the resin composition for adhesion auxiliary layers is high, and a finer roughened shape can be obtained, and the adhesive force with the plated copper can be increased. Moreover, if the mixture ratio of (C) component is 30 mass parts or less, there will be no heat resistant fall and the fall with respect to the chemical | medical solution at the time of a roughening process can also be prevented. Moreover, sufficient adhesiveness with plated copper can be ensured.

  In addition, since the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin contains a phenolic hydroxyl group having good compatibility with the epoxy resin and polybutadiene incompatible with the epoxy resin, the blending ratio thereof is the component (A) and the component (B). In the case of 5 to 30 parts by mass with respect to 100 parts by mass in total, it is considered that a fine sea-island structure is formed. It is speculated that the formation of this sea-island structure makes it possible to form a dense shape during the roughening treatment by utilizing the fact that the amount of roughening between the sea layer and the island layer differs during the roughening treatment. Since this surface shape is fine and has little variation, it is considered that a high physical adhesive force due to the anchor effect is expressed and the adhesive force with the conductor layer is remarkably improved.

  When the blending ratio of component (C) is 5 parts by mass or more, the domain size of the sea-island structure does not become too large, and Ra after the roughening treatment can be reduced. Further, the toughness of the resin is not lowered, a dense roughened shape is obtained, and the adhesive force with the conductor layer is improved. On the other hand, when the blending ratio of the component (C) is 30 parts by mass or less, the domain size of the sea-island structure does not become too small, the adhesive force due to the anchor effect does not decrease, and good adhesive strength with the plated copper is obtained. It is done. Moreover, heat resistance suppresses a fall and the tolerance to the chemical | medical solution at the time of a roughening process also improves.

  In addition, when a phenolic hydroxyl group-containing polyamide resin or a phenolic hydroxyl group-containing acrylonitrile-butadiene modified polyamide resin is used without using the component (C), the compatibility with the epoxy resin compared with the phenolic hydroxyl group-containing polybutadiene modified polyamide resin Therefore, the sea-island structure is not formed, and it is difficult to exert an adhesive force with the conductor layer. Moreover, when a nitrile group is introduced, the moisture absorption rate is increased and the insulating properties are also lowered. In addition, the transition of the resin component in the prepreg in the B stage state to the adhesion auxiliary layer becomes remarkable, and the domain size of the sea-island structure in the adhesion auxiliary layer cannot be controlled, and the adhesion force between the adhesion auxiliary layer and the plated copper is reduced. May be exacerbated.

<(D) component>
The (D) phosphorus curing accelerator used in the resin composition for an auxiliary adhesion layer according to the present invention is particularly limited as long as it is a curing accelerator containing a phosphorus atom and accelerating the curing reaction of the epoxy resin. is not. Moreover, even if a phosphorus type hardening accelerator is used independently, you may use together 1 type (s) or 2 or more types of other hardening accelerators. Examples of phosphorus curing accelerators include triphenylphosphine, diphenyl (alkylphenyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, and tris. (Trialkylphenyl) phosphine, Tris (tetraalkylphenyl) phosphine, Tris (dialkoxyphenyl) phosphine, Tris (trialkoxyphenyl) phosphine, Tris (tetraalkoxyphenyl) phosphine, Trialkylphosphine, Dialkylarylphosphine, Alkyldiarylphosphine Organic phosphines, complexes of these organic phosphines with organic borons, and addition of tertiary phosphines with quinones. Things and the like.

The (D) phosphorus curing accelerator used in the present invention is, for example, an adduct of a tertiary phosphine and a quinone that can exhibit high adhesiveness when the curing reaction of the adhesion auxiliary layer for plating process proceeds sufficiently. Is preferred. Although it does not specifically limit as a tertiary phosphine, For example, dibutylphenyl phosphine, butyl diphenyl phosphine, ethyl diphenyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine A tertiary phosphine having an aryl group such as is preferred. Examples of quinones include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone.
Among these, in addition to adhesiveness, the adduct of triphenylphosphine and p-benzoquinone is preferable from the viewpoint of heat resistance and storage stability.

  As a method for producing an adduct of a tertiary phosphine and a quinone, for example, a method in which both are stirred and mixed in a solvent in which the tertiary phosphine and the quinone as raw materials are dissolved, followed by addition reaction, and then isolated. Etc. The production conditions in this case are from room temperature to 80 ° C. in a solvent such as methyl isobutyl ketone, methyl ethyl ketone, acetone and other ketones having a high raw material solubility and a low solubility of the resulting adduct for 1 hour to 12 hours. It is preferable to stir for a period of time for the addition reaction.

In the adhesion auxiliary layer for plating process in the present invention, the curing reaction sufficiently proceeds by using (D) a phosphorus-based curing accelerator.
The reason for this is not necessarily clear, but in conventional nitrogen-based curing accelerators typified by imidazole, the nitrogen atoms of the nitrogen-based curing accelerator are affected by the copper atoms of the copper foil, and curing acceleration is suppressed. On the other hand, since a phosphorus hardening accelerator is hard to receive this influence, it is guessed that hardening reaction fully arises.
In addition, since the curing reaction proceeds sufficiently by using a phosphorus curing accelerator, each component in the prepreg and the plating process adhesion auxiliary layer is dispersed to the other when the plating process adhesion auxiliary layer is laminated on the prepreg. Therefore, it is considered that the characteristics of the prepreg and the adhesion auxiliary layer for the plating process can be sufficiently expressed, and high adhesive strength can be obtained.

<Filler>
The adhesion auxiliary layer for plating process according to the present invention may include a filler. Examples of the filler include inorganic fillers and crosslinkable organic fillers.
Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica is particularly preferable. The inorganic filler may be used alone or in combination of two or more.
The inorganic filler need not be spherical, but preferably has a specific surface area of 20 m ² / g or more from the viewpoint of forming fine wiring on the interlayer insulating layer. When an inorganic filler having a specific surface area of 20 m ² / g or more is used, the surface roughness after the roughening treatment in the plating process becomes small. In addition, when an inorganic filler having a specific surface area of 20 m ² / g or more is used, the interface between the adhesion auxiliary layer resin composition and the inorganic filler increases. For this reason, even with a small blending amount, the thermal conductivity can be brought close to the glass cloth substrate, and good laser processability can be obtained.
The specific surface area can be obtained by the BET method in which nitrogen is adsorbed on the surface of the powder sample at the liquid nitrogen temperature and the specific surface area of the powder sample is obtained from the adsorbed amount.
A commercial item can be used for an inorganic filler. As a commercially available product, for example, as a silica filler, AEROSIL R972 (Nippon Aerosil Co., Ltd., trade name, specific surface area: 110 ± 20 m ² / g), AEROSIL R202 (Nippon Aerosil Co., Ltd., trade name, specific surface area: 100 ± 20 m ² / g), PL-1 (manufactured by Fuso Chemical Industries, trade name, specific surface area: 181 m ² / g), PL-7 (manufactured by Fuso Chemical Industries, trade name, specific surface area: 36 m ² / G) and the like. Examples of the alumina filler include NanoTek (trade name, specific surface area: 55 m ² / g, manufactured by CII Kasei Co., Ltd.).

  The inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance. Moreover, in order to improve the dispersibility of the inorganic filler in the resin composition for adhesion auxiliary layers, it may be hydrophobized.

  As a compounding quantity of an inorganic filler, it is preferable that it is 1-10 mass% in conversion of solid content in the resin composition for adhesion auxiliary layers, for example. When the blending amount is 1% by mass or more, the difference in thermal conductivity with the glass cloth-containing substrate becomes small, and good laser processability can be obtained. Further, it is preferable that the blending amount is 10% by mass or less because a good surface shape can be formed after the roughening treatment, the plating characteristics are not deteriorated, and the insulation reliability between the layers is not deteriorated.

  Furthermore, in order to improve the extensibility of the adhesion auxiliary layer for the plating process, for example, a crosslinked organic filler or the like may be added. The crosslinked organic filler is not particularly limited. For example, as a copolymer of acrylonitrile butadiene, crosslinked NBR particles obtained by copolymerizing acrylonitrile and butadiene, or acrylonitrile, butadiene, and carboxylic acid such as acrylic acid are copolymerized. So-called core-shell rubber particles having polybutadiene, NBR, or silicone rubber as the core and acrylic acid derivatives as the shell can be used.

A commercial item can be used for a crosslinked organic filler. Examples of commercially available crosslinked organic fillers include, for example, paraloid EXL2655 (trade name, manufactured by Rohm and Haas Japan Co., Ltd.), which is a core-shell particle of butadiene rubber-acrylic resin, and core-shell rubber particles of crosslinked silicone rubber-acrylic resin. GENIOPERL P52 (trade name, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and the like.
It is preferable that the compounding quantity of a bridge | crosslinking organic filler is 10 mass% or less in conversion of solid content in the resin composition for adhesion auxiliary layers, for example. When the blending amount is 10% by mass or less, chemical resistance does not decrease, and deterioration of plating characteristics such as heat resistance can be suppressed.

<Method for producing resin composition for adhesion auxiliary layer>
In addition to the components (A) to (D), the resin composition for an auxiliary adhesion layer of the present invention includes a thixotropic agent, a surfactant, and a coupling agent that are used in ordinary resin compositions as necessary. Various additives such as inorganic fillers, crosslinkable organic fillers, and the like are appropriately blended, mixed, and then allowed to stand until there are no bubbles. In addition, as a method for dispersing the inorganic filler or the like in the resin composition for the auxiliary adhesion layer, known kneading methods and dispersing methods such as a kneader, a ball mill, a bead mill, a three-roll mill, and a nanomizer can be used.

  The resin composition for an auxiliary adhesion layer in the present invention is preferably mixed with a solvent, diluted, or dispersed in a solvent to form a varnish from the viewpoint of workability. As this solvent, for example, methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. These solvents may be used alone or in combination of two or more. What is necessary is just to adjust suitably the ratio of the resin composition for adhesion auxiliary layers with respect to this solvent according to the installation of a coating film.

<Adhesion auxiliary layer for plating process>
The adhesion auxiliary layer for plating process according to the present invention includes the above-described resin composition for adhesion auxiliary layer.
The adhesion auxiliary layer for plating process of the present invention is provided on, for example, a prepreg or insulating resin layer laminated between circuit layers, and after thermosetting, the adhesion auxiliary for plating process is performed by roughening treatment and electroless plating treatment. A conductor layer is formed on the surface of the layer. At that time, the adhesion auxiliary layer for the plating process exists between the surface of the prepreg, the insulating resin layer or the like and the conductor layer. Thereafter, a circuit layer can be formed on the adhesion auxiliary layer for plating process by further performing electroplating treatment. In the present invention, “for plating process” means an application for providing a plating layer (conductor layer and circuit layer) on the surface of an adhesion auxiliary layer provided on a prepreg or an insulating resin layer laminated between circuit layers. Means.

The adhesion auxiliary layer for plating process according to the present invention is in a semi-cured state (so-called B-stage state) on a support or a prepreg before being made a part of a layer of a wiring board laminate or multilayer wiring board. Preferably it is present.
The thickness of the adhesion auxiliary layer for plating process according to the present invention is preferably 1 to 10 μm, for example, from the viewpoint of reducing the total thickness in the form of the laminated board for wiring board and the multilayer wiring board. When the thickness of the adhesion auxiliary layer for plating process is 1 μm or more and 10 μm or less, good adhesive force with a prepreg, an insulating resin layer or the like can be obtained. Moreover, the favorable adhesive force with the conductor layer formed in the surface of the adhesion auxiliary layer for plating processes is also acquired.

Moreover, it is preferable that surface roughness Ra after the roughening process of the adhesion assistance layer for plating processes which concerns on this invention is 0.4 micrometer or less. If the surface roughness Ra after the roughening treatment is 0.4 μm or less, it can contribute to fine wiring.
Examples of the roughening treatment include the following methods. First, as a swelling liquid, an aqueous solution of diethylene glycol monobutyl ether and NaOH is heated to 70 ° C., and the laminate or multilayer wiring board is immersed for 5 minutes. Next, as a roughening solution, an aqueous solution of KMnO and NaOH is heated to 80 ° C. and immersed for 10 minutes. Subsequently, it is neutralized by immersing it in a neutralizing solution, for example, an aqueous hydrochloric acid solution of stannous chloride (SnCl ₂ ) at room temperature for 5 minutes. The roughening treatment is usually performed in a state where the adhesion auxiliary layer for plating process is cured (so-called C stage state).

<Adhesion auxiliary layer for plating process with support>
The adhesion auxiliary layer for a plating process with a support according to the present invention is one in which the adhesion auxiliary layer for a plating process described above is disposed on a support.
When the resin composition for the auxiliary adhesion layer is arranged on the support, the amount of the solvent used is adjusted so that the solid content of the auxiliary auxiliary layer resin composition excluding the solvent is, for example, 8 to 40% by mass in the varnish. It is preferable to do.
The support used here is preferably, for example, an unroughened copper foil, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide film, a polyimide film, and an aluminum foil that have been subjected to a release treatment. .
Further, since the adhesion auxiliary layer for the plating process in the B stage state before lamination needs to react with the prepreg in the B stage state, it is important to control the degree of curing. The degree of cure can be measured by the reaction rate measured from a differential scanning calorimeter. Specifically, the reaction rate of the adhesion auxiliary layer for the plating process in the B-stage state is preferably 50 to 99%. If the reaction rate of the adhesion auxiliary layer for the plating process in the B stage state is 50% or more, the adhesion auxiliary layer for the plating process is not mixed with the prepreg in the B stage state during the heat curing at the time of lamination. This is preferable in that the plating characteristics of the adhesion auxiliary layer do not deteriorate. On the other hand, if it is 99% or less, the adhesive strength at the interface between the plating process adhesion auxiliary layer and the prepreg does not decrease, and this is preferable in that the adhesive strength with the conductor layer does not decrease.
Examples of a method for producing an adhesion auxiliary layer for a plating process with a support include a method in which a resin composition for an adhesion auxiliary layer is applied to a support using a comma coater, a gravure coater, a die coater, and the like, and then dried. .

<Laminated board for wiring boards>
The laminated board for wiring boards according to the present invention has a plating process adhesion auxiliary layer and a wiring board prepreg, and is laminated so that the adhesion auxiliary layer and the surface of the wiring board prepreg are in contact with each other.
The laminated board for wiring boards according to the present invention is formed by stacking the support auxiliary adhesion layer for plating process with the support so that the adhesion auxiliary layer for plating process and the surface of the prepreg for wiring board are in contact with each other. It can be manufactured by stacking a mirror plate on the support of the process adhesion auxiliary layer, press molding, and removing the mirror plate and the support after molding.
Further, as another method for producing a laminated body for a wiring board, the above-mentioned adhesion auxiliary layer for plating process with a support is stacked so that the adhesion auxiliary layer for plating process and the surface of the prepreg for wiring board are in contact with each other, Examples include a method of laminating by heating and pressurizing with a laminator using a rubber sheet or the like, curing after lamination, and removing the support after curing.
In the laminated board for wiring board of the present invention, the adhesion auxiliary layer for plating process may be formed not only on one surface of the prepreg for wiring board but also on the other surface, that is, on both surfaces of the prepreg for wiring board by the above method. .
Moreover, the prepreg for wiring boards used by this invention will not be restrict | limited especially if it is a prepreg used when manufacturing a wiring board, A commercial item can also be used. As a commercial item of the prepreg for wiring boards, Hitachi Chemical Co., Ltd. GEA-67N, GEA-679F, GEA-679GT, GEA-700G (R), GEA-705G etc. are mentioned, for example.

<Multilayer wiring board>
The multilayer wiring board which concerns on this invention is a multilayer wiring board containing the layer by which the adhesion auxiliary layer for plating processes mentioned above, the prepreg for wiring boards, and the wiring board by which circuit processing was performed are arrange | positioned in this order.
In the multilayer wiring board according to the present invention, the above-mentioned adhesion auxiliary layer for plating process with a support is stacked so that the adhesion auxiliary layer for plating process and the surface of the prepreg for wiring board are in contact with each other, and the plating process for the prepreg for wiring board The surface where the adhesion auxiliary layer for contact is not in contact (referred to as “rear surface” in the present invention) is overlapped with the surface of the circuit board that has been subjected to circuit processing (also referred to as the inner layer circuit board), and further the plating process with support A mirror plate is superimposed on the support of the adhesive auxiliary layer for use and press-molded. After molding, the mirror plate and the support are removed. Then, it can manufacture by performing a roughening process, an electroless-plating process, and an electroplating process in order, and forming a circuit layer on the adhesion auxiliary layer for plating processes.
As another method for manufacturing a multilayer wiring board, the above-mentioned adhesion auxiliary layer for plating process with a support is stacked so that the adhesion auxiliary layer for plating process and the surface of the prepreg for wiring board are in contact with each other, The back surface is stacked so as to be in contact with the surface of the circuit board on which circuit processing has been performed, and is laminated by heating and pressing with a laminator using a heat-resistant rubber sheet or the like, cured after lamination, and the support is removed after curing. A method is mentioned. Thereafter, a circuit layer can be formed on the adhesion auxiliary layer for the plating process by sequentially performing a roughening treatment, an electroless plating treatment, and an electroplating treatment.
The multilayer wiring board of the present invention may include a prepreg for wiring board in which an adhesion auxiliary layer for plating process is formed on both surfaces by the above method.

  The inner layer circuit board is, for example, an inner layer board having a first circuit layer (inner layer wiring) formed on the surface, and a known laminated board used in a normal wiring board can be used as the inner layer board. Examples of the inner layer substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, and a BT resin substrate.

  Also, there is no particular limitation on the method for forming a circuit, and a subtractive method in which an unnecessary portion of the copper foil is removed by etching using a copper-clad laminate in which a copper foil and the inner layer substrate are bonded, or the inner layer substrate is used. A well-known method for manufacturing a wiring board such as an additive method for forming a circuit by electroless plating can be used.

  Next, if necessary, the surface of the circuit layer is surface-treated in a state suitable for adhesion. This method is also not particularly limited. For example, a copper oxide needle crystal is formed on the surface of the circuit layer with an alkaline aqueous solution of sodium hypochlorite, and the formed copper oxide needle crystal is immersed in a dimethylamine borane aqueous solution. Then, a known production method such as reduction can be used.

When forming a circuit by a plating method on the adhesion auxiliary layer for the plating process of the laminated board or multilayer wiring board of the present invention, it is preferable to perform a roughening treatment. As the roughening liquid, for example, an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkali permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, or a borofluoric acid roughening liquid may be used. it can.
Examples of the roughening treatment include the above-described roughening treatment.

  After the roughening treatment, a plating catalyst applying treatment for attaching palladium is performed. The plating catalyst treatment is performed by immersing in a palladium chloride plating catalyst solution. Next, it is immersed in an electroless plating solution to deposit an electroless plating layer (conductor layer) having a thickness of 0.1 to 1.5 μm on the entire surface of the adhesion auxiliary layer. If necessary, further electroplating is performed to obtain a necessary thickness. As the electroless plating solution used for electroless plating, a known electroless plating solution can be used, and there is no particular limitation. Also, electroplating can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Further, unnecessary portions can be removed by etching to form a circuit. By repeating these steps, a multilayer wiring board having a large number of layers can be produced.

EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
[Preparation of resin composition for adhesion auxiliary layer]
(Preparation Example 1)
After blending 70.0 g of N-methyl-2-pyrrolidone (NMP) with 2.7 g of the phenolic hydroxyl group-containing polybutadiene-modified polyamide (BPAM-155, Nippon Kayaku Co., Ltd., trade name) as component (C) , (A) component biphenylaralkyl novolac type epoxy resin (NC-3000H, Nippon Kayaku Co., Ltd., trade name) 10.0 g, (B) component bisphenol A novolak type phenol resin (YLH129, Mitsubishi Chemical Corporation) 3.9 g made by company, trade name) and 0.20 g of triphenylphosphine as a phosphorus-based curing accelerator as component (D), and then diluted with a mixed solvent consisting of NMP and methyl ethyl ketone, and an inorganic filler (AEROSIL) R972, Nippon Aerosil Co., Ltd., trade name) 0.96 g was added, and the disperser (Nanomizer, The varnish (solid content concentration of about 20% by mass) of the resin composition for the adhesion auxiliary layer was obtained using a trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.
(Preparation Example 2)
Instead of the component (D) of Preparation Example 1, it was the same as Preparation Example 1 except that an adduct of triphenylphosphine and p-benzoquinone was blended.
(Preparation Example 3)
Instead of the component (D) of Preparation Example 1, it was the same as Preparation Example 1 except that an adduct of tris (4-methylphenyl) phosphine and p-benzoquinone was added as a curing accelerator.
(Preparation Example 4)
Instead of the component (D) of Preparation Example 1, it was the same as Preparation Example 1 except that an addition reaction product of tri-n-butylphosphine and p-benzoquinone was added as a curing accelerator.

(Comparative Preparation Example 1)
Instead of the component (D) of Preparation Example 1, it was the same as Preparation Example 1 except that 2-phenylimidazole (2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was blended as a curing accelerator.
(Comparative Preparation Example 2)
It was the same as that of Preparation Example 1 except that 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was blended as a curing accelerator instead of the component (D) of Preparation Example 1. .

Example 1
The glossy surface of the copper foil (NC-WC-10, manufactured by Furukawa Electric Co., Ltd., trade name) whose surface is untreated with the varnish of the resin composition for the adhesion auxiliary layer of the above adjustment example is 3 μm after drying. And dried at 190 ° C. for 3 minutes to obtain an adhesion auxiliary layer for plating process with copper foil.
Subsequently, the laminated board for wiring boards was manufactured as follows. Four 0.10 mm thick prepregs for wiring boards (GEA-679FG (R), manufactured by Hitachi Chemical Co., Ltd., trade name) are stacked, and the copper foil is on the outer side of the adhesion auxiliary layer for the plating process with copper foil on both sides. Then, the end plate and the cushion paper were further stacked, and the resin composition for the adhesion auxiliary layer and the prepreg for the wiring board were cured by heating at 4.0 MPa and 185 ° C. for 1 hour using a press machine. . After cooling, the copper foil was etched to obtain a laminated board for wiring board.
The multilayer wiring board was manufactured as follows. In order to chemically roughen the produced laminated board for wiring boards, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, NaOH: 5 g / L was prepared as a swelling liquid, heated to 80 ° C. and immersed for 10 minutes. . Next, an aqueous solution of KMnO ₄ : 60 g / L and NaOH: 40 g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 15 minutes. Subsequently, an aqueous solution of a neutralizing solution (SnCl ₂ : 30 g / L, HCl: 300 ml / L) was prepared, heated to 40 ° C. and immersed for 5 minutes to reduce KMnO ₄ .
In order to form a circuit layer on the obtained multilayer wiring board, first, activator Neogant 834 (trade name, manufactured by Atotech Japan Co., Ltd.), which is an electroless plating catalyst containing PdCl ₂ , is heated to 35 ° C. Then, it was immersed in a plating solution print Gantt MSK-DK (trade name, manufactured by Atotech Japan Co., Ltd.) for electroless copper plating for 15 minutes at room temperature, and further subjected to copper sulfate electrolytic plating. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a circuit layer having a thickness of 20 μm.

(Example 2)
Example 1 was the same as Example 1 except that Preparation Example 2 was used instead of the varnish of Preparation Example 1.
(Example 3)
Example 1 was the same as Example 1 except that Preparation Example 3 was used instead of the varnish of Preparation Example 1.
Example 4
Example 1 was the same as Example 1 except that Preparation Example 4 was used instead of the varnish of Preparation Example 1.

(Comparative Example 1)
Example 1 was the same as Example 1 except that the varnish of Comparative Preparation Example 1 was used.
(Comparative Example 2)
Example 1 was the same as Example 1 except that the varnish of Comparative Preparation Example 2 was used.

[Evaluation method and results]
For the multilayer wiring board produced by the above method, the B stage reactivity of the adhesion auxiliary layer for the plating process of the adhesion auxiliary layer for the plating process with copper foil, the adhesive strength between the circuit layer and the adhesion auxiliary layer for the plating process, for the plating process The surface roughness of the adhesion auxiliary layer was measured. The results are shown in Tables 1 and 2. The measurement method is as follows.
<B stage reactivity of adhesion auxiliary layer for plating process>
The B stage reactivity of the adhesion auxiliary layer for the plating process was determined by scraping 10 mg of the adhesion auxiliary layer for the plating process from the obtained copper foil of the adhesion auxiliary layer for the plating process with copper foil, and using a differential scanning calorimeter (TEA-IN). The calorific value ΔH (J / g) was measured under the measurement conditions of a temperature increase rate of 10 ° C./min and 40 to 300 ° C. under a nitrogen atmosphere using a trade name, Q200) manufactured by Strument. The calorific value ΔH is obtained by connecting the point where the exothermic peak separates from the low temperature side baseline of the DSC curve obtained under the above measurement conditions and the point where the exothermic peak returns to the high temperature side baseline by a straight line. Desired. The calorific value ΔH ₀ (J / g) was also calculated in the same manner for the adhesion auxiliary layer for plating process produced by changing the drying conditions to 140 ° C. for 5 minutes. Using the calorific values ΔH ₀ and ΔH, the reactivity (reaction rate α) of the B stage of the adhesion auxiliary layer for plating process prepared from the following formula was calculated.
α = {(ΔH ₀ −ΔH) / ΔH ₀ } × 100
As an evaluation standard, a reaction rate α of 85% or more was evaluated as ◯ (good), and less than 85% was evaluated as x (defective).
<Adhesive strength between circuit layer (plated copper) and adhesion auxiliary layer for plating process>
A part having a width of 10 mm and a length of 100 mm is formed on the circuit layer of the multilayer wiring board obtained in each of the examples and comparative examples by etching, and one end thereof is peeled off at the interface of the circuit layer / adhesion auxiliary layer for plating process. The load was measured when it was grabbed with a tool and peeled in the vertical direction at a pulling rate of about 50 mm / min at room temperature. In addition, Shimadzu Corporation autograph AG-100C was used for the measuring apparatus.
<Surface roughness of adhesion auxiliary layer for plating process>
The circuit layer of the multilayer wiring board obtained in each Example and Comparative Example was removed by etching treatment, and the surface roughness Ra of the obtained adhesion auxiliary layer for plating process was measured using WYKO NT9100 manufactured by Veeco.

  From Tables 1 and 2, the multilayer wiring boards of Comparative Examples 1 and 2 that do not include the adhesion auxiliary layer for plating process according to the present invention have the same adhesive strength as Example 1, but the B-stage reaction The surface property Ra is large. That is, since the multilayer wiring board according to the present invention has better B-stage reactivity than the multilayer wiring boards shown in Comparative Examples 1 and 2, each component of the prepreg and the process adhesion auxiliary layer is on the other side. It was found that a smooth resin surface having a surface roughness Ra of 0.4 μm or less was formed without being dispersed, and showed high adhesive strength with plated copper.

Claims (14)

(A) a polyfunctional epoxy resin, (B) an epoxy resin curing agent, (C) a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin, and (D) a phosphorus-based curing accelerator, ) A resin composition for an adhesion auxiliary layer for a plating process, wherein the phosphorus curing accelerator is an adduct of a tertiary phosphine and a quinone. The resin composition for an adhesion auxiliary layer for a plating process according to claim 1, wherein the (A) polyfunctional epoxy resin has a biphenyl structure. The resin composition for an adhesion auxiliary layer for a plating process according to claim 1 or 2, wherein the (A) polyfunctional epoxy resin is an aralkyl novolac type epoxy resin. Furthermore, the resin composition for adhesion auxiliary layers for plating processes as described in any one of Claims 1-3 containing an inorganic filler. The adhesion auxiliary layer for plating processes containing the resin composition for adhesion auxiliary layers for plating processes as described in any one of Claims 1-4.   The adhesion auxiliary layer for plating process according to claim 5, wherein the adhesion auxiliary layer for plating process has a thickness of 1 to 10 μm.   The adhesion auxiliary layer for plating process according to claim 5 or 6, wherein the surface roughness Ra after the roughening treatment of the adhesion auxiliary layer for plating process is 0.4 µm or less.   An adhesion auxiliary layer for a plating process with a support, wherein the adhesion auxiliary layer for a plating process according to any one of claims 5 to 7 is disposed on a support.   It has the adhesion auxiliary layer for plating processes as described in any one of Claims 5-7, and the prepreg for wiring boards, It is piled up so that this adhesion auxiliary layer and the surface of this prepreg for wiring boards may touch. A laminated board for a wiring board.   The adhesion auxiliary layer for a plating process with a support according to claim 8 is overlaid so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact with each other, the support and the end plate are overlaid, press-molded, and after molding, A method for producing a laminated board for wiring board, wherein the end plate and the support are removed.   The adhesion auxiliary layer for a plating process with a support according to claim 8 is laminated so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact with each other, laminated by heating and pressing with a laminator, and cured after lamination, A method for producing a laminated board for a wiring board, wherein the support is removed after curing.   The multilayer wiring board containing the layer by which the adhesion auxiliary layer for plating processes as described in any one of Claims 5-7, the prepreg for wiring boards, and the wiring board by which circuit processing was performed are arrange | positioned in this order.   9. A wiring board wherein the support auxiliary layer for plating process with support according to claim 8 is stacked so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact with each other, and the back surface of the prepreg for wiring board is subjected to circuit processing. A method of manufacturing a multilayer wiring board, wherein the substrate and the end plate are stacked so as to be in contact with each other, press-molded, and the end plate and the support are removed after molding.   9. A wiring board wherein the support auxiliary layer for plating process with support according to claim 8 is stacked so that the adhesion auxiliary layer and the surface of the prepreg for wiring board are in contact with each other, and the back surface of the prepreg for wiring board is subjected to circuit processing. A method for producing a multilayer wiring board, wherein the layers are laminated so as to be in contact with each other, heated and pressurized with a laminator, laminated, cured after lamination, and the support is removed after curing.