JP2017195334A - Resin composition for printed wiring board, prepreg, resin sheet, laminate board, metal foil-clad laminate board, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for a printed wiring board, which includes an organic filler and has superior moldability.SOLUTION: A resin composition for a printed wiring board comprises: a filler (A) including a polymer produced as a result of polymerization of one or more kinds selected from a group consisting of (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylonitrile, olefin and an aromatic vinyl compound and/or a silicone polymer; and a thermosetting component (B). In the filler (A), the content of filler of 3.0 μm or larger in particle diameter is 0.09 vol.% or less to a total volume of the resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for printed wiring boards, a prepreg, a resin sheet, a laminated board, a metal foil-clad laminated board, and a printed wiring board.

  In recent years, as semiconductor packages widely used in electronic devices, communication devices, personal computers, etc. have become more sophisticated and smaller in size, higher integration and higher density mounting of each component for semiconductor packages has been accelerated in recent years. ing. Among them, warpage of the semiconductor plastic package caused by the difference in coefficient of thermal expansion between the semiconductor element and the printed wiring board for the semiconductor plastic package is a problem, and various countermeasures have been taken.

  One countermeasure is to reduce the thermal expansion of the insulating layer used in the printed wiring board. This is a technique for suppressing warpage by bringing the thermal expansion coefficient of a printed wiring board close to the thermal expansion coefficient of a semiconductor element, and is currently being actively worked on (see, for example, Patent Documents 1 to 3).

  Besides lowering the thermal expansion of printed wiring boards, increasing the rigidity of the laminated board (higher rigidity) and raising the glass transition temperature of the laminated board (higher Tg) can reduce the warpage of the semiconductor plastic package. It is examined as a technique for suppressing (see, for example, Patent Documents 4 and 5).

JP 2013-216884 A Japanese Patent No. 3173332 JP 2009-035728 A JP 2013-001807 A JP 2011-177892 A

  However, even for a printed wiring board using a thermosetting resin composition as described in Patent Documents 1 to 5, the metal foil peel strength of a laminated board in which metal foils are laminated, for example, against a strongly alkaline cleaning liquid Since it is difficult to achieve compatibility with other characteristics such as chemical resistance (desmear resistance), the problem of warping of the semiconductor plastic package remains as a result.

  Here, in order to reduce the difference in the coefficient of thermal expansion and solve the problem of warping, the resin composition for a printed wiring board can contain polymer particles having a low elastic component as an organic filler. However, when such a resin composition for printed wiring boards is molded, there is a problem that molding unevenness occurs.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a printed wiring board resin composition having excellent moldability while containing an organic filler. Another object of the present invention is to provide a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, and a printed wiring board using the resin composition for a printed wiring board excellent in moldability and low thermal expansion. And

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have obtained a filler (A) containing a predetermined polymer and / or a silicone polymer and a thermosetting component (B). A resin composition for a printed wiring board in which the content of a filler whose particle diameter is a predetermined value or more in the filler (A) is not more than a specific value has excellent moldability The present invention has been found.

（式（１）中、複数のＲ₅は、各々独立に水素原子又はメチル基を示し、ｎ₁は、１以上の整数を示す。）
［９］
前記シアン酸エステル化合物（Ｅ）は、下記一般式（２）で表される化合物及び下記一般式（３）で表される化合物からなる群より選択される一種又は二種以上を含む、［７］又は［８］に記載のプリント配線板用樹脂組成物。

（式（２）中、複数のＲ₆は、各々独立に水素原子又はメチル基を示し、ｎ₂は、１以上の整数を示す。）

（式（３）中、複数のＲ₇は、各々独立に水素原子又はメチル基を示し、複数のＲ₈は、各々独立に水素原子又は炭素数が１〜４のアルキル基若しくはアルケニル基を示し、ｎ₃は、１以上の整数を示す。）
［１０］
無機充填材（Ｇ）をさらに含む、［１］〜［９］のいずれかに記載のプリント配線板用樹脂組成物。
［１１］
前記無機充填材（Ｇ）は、シリカ、アルミナ、及び窒化アルミニウムからなる群より選択される一種又は二種以上を含む、［１０］に記載のプリント配線板用樹脂組成物。
［１２］
前記樹脂組成物は、前記熱硬化性成分（Ｂ）１００質量部に対して、前記無機充填材（Ｇ）を５０質量部以上３００質量部以下含む、［１０］又は［１２］に記載のプリント配線板用樹脂組成物。
［１３］
基材と、該基材に含浸又は塗布された［１］〜［１２］のいずれかに記載のプリント配線板用樹脂組成物と、を有する、プリプレグ。
［１４］
前記基材は、Ｅガラスクロス、Ｔガラスクロス、Ｓガラスクロス、Ｑガラスクロス、及び有機繊維からなる群より選ばれる一種又は二種以上である、［１３］に記載のプリプレグ。
［１５］
支持体と、該支持体の表面に配された［１］〜［１２］のいずれかに記載のプリント配線板用樹脂組成物と、を有する、レジンシート。
［１６］
前記支持体は、樹脂シート又は金属箔である、［１５］に記載のレジンシート。
［１７］
［１３］又は［１４］に記載のプリプレグ、及び［１５］又は［１６］に記載のレジンシートからなる群より選択される一種又は二種以上を、複数備える積層板。
［１８］
［１３］又は［１４］に記載のプリプレグ、及び［１５］又は［１６］に記載のレジンシートからなる群より選択される一種又は二種以上と、金属箔と、を備える金属箔張積層板。
［１９］
［１］〜［１２］のいずれかに記載のプリント配線板用樹脂組成物を含む絶縁層と、該絶縁層の表面に形成された導体層と、を備えるプリント配線板。 That is, the present invention is as follows.
[1]
Of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, olefin, and polymer and / or silicone obtained by polymerizing one or more selected from the group consisting of aromatic vinyl compounds A filler (A) containing a polymer;
A thermosetting component (B), and a resin composition comprising:
The content of the filler having a particle diameter of 3.0 μm or more in the filler (A) is 0.09% by volume or less with respect to the total volume of the resin composition. Resin composition.
[2]
The resin material for printed wiring boards according to [1], wherein the filler (A) is a core-shell type particle having a core and a shell outside the core.
[3]
The core is a polymer obtained by polymerizing one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, olefin, and aromatic vinyl compound, and The resin composition for a printed wiring board according to [2], comprising a silicone polymer.
[4]
The shell is a polymer obtained by polymerizing one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, and aromatic vinyl compound, and / or polymethylsilsesquioxy. The resin composition for printed wiring boards according to [2] or [3], which is a core-shell type particle having a shell containing a polymer of Sun.
[5]
The core includes a polymer obtained by polymerizing one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, butadiene, and an aromatic vinyl compound,
The said shell is a resin composition for printed wiring boards as described in [2]-[4] containing the polymer obtained by polymerizing methacrylic acid ester.
[6]
[1] to [5], wherein the resin composition includes 5.0 parts by mass or more and 60 parts by mass or less of the filler (A) with respect to 100 parts by mass of the thermosetting component (B). The resin composition for printed wiring boards as described in 2.
[7]
The thermosetting component (B) includes one or more selected from the group consisting of a maleimide compound (C), an epoxy resin (D), a cyanate ester compound (E), and an alkenyl-substituted nadiimide (F). [1]-[6] The resin composition for printed wiring boards in any one of.
[8]
The maleimide compound (C) is bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) The print according to [7], comprising one or more selected from the group consisting of methane, polytetramethylene oxide-bis (4-maleimidobenzoate), and a maleimide compound represented by the following general formula (1): Resin composition for wiring boards.

(In the formula (1), a plurality of R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)
[9]
The cyanate ester compound (E) includes one or more selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3): [7 ] Or the resin composition for printed wiring boards as described in [8].

(In the formula (2), each of the plurality of R ₆ independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)

(In Formula (3), a plurality of R _{7 s} each independently represent a hydrogen atom or a methyl group, and a plurality of R _{8 s} each independently represent a hydrogen atom or an alkyl group or alkenyl group having 1 to 4 carbon atoms. N ₃ represents an integer of 1 or more.)
[10]
The resin composition for printed wiring boards according to any one of [1] to [9], further comprising an inorganic filler (G).
[11]
The said inorganic filler (G) is a resin composition for printed wiring boards as described in [10] containing 1 type, or 2 or more types selected from the group which consists of a silica, an alumina, and aluminum nitride.
[12]
The print according to [10] or [12], wherein the resin composition includes 50 to 300 parts by mass of the inorganic filler (G) with respect to 100 parts by mass of the thermosetting component (B). Resin composition for wiring boards.
[13]
The prepreg which has a base material and the resin composition for printed wiring boards in any one of [1]-[12] impregnated or apply | coated to this base material.
[14]
The prepreg according to [13], wherein the base material is one or more selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers.
[15]
The resin sheet which has a support body and the resin composition for printed wiring boards in any one of [1]-[12] distribute | arranged to the surface of this support body.
[16]
The resin sheet according to [15], wherein the support is a resin sheet or a metal foil.
[17]
A laminate comprising a plurality of one or more selected from the group consisting of the prepreg according to [13] or [14] and the resin sheet according to [15] or [16].
[18]
A metal foil-clad laminate comprising one or more selected from the group consisting of the prepreg according to [13] or [14] and the resin sheet according to [15] or [16], and a metal foil. .
[19]
A printed wiring board provided with the insulating layer containing the resin composition for printed wiring boards in any one of [1]-[12], and the conductor layer formed in the surface of this insulating layer.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for printed wiring boards which has the outstanding moldability can be provided, containing an organic filler. Moreover, the prepreg, resin sheet, laminated board, metal foil tension laminated board, and printed wiring board using this resin composition for printed wiring boards excellent in the moldability and the low thermal expansion property can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist. In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid corresponding thereto, and “(meth) acrylic ester” means acrylic ester and methacrylic acid corresponding thereto. By both esters, “(meth) acrylonitrile” means both acrylonitrile and the corresponding methacrylonitrile.

[Resin composition for printed wiring board]
The resin composition for a printed wiring board of the present embodiment (hereinafter also simply referred to as “resin composition”) includes (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, olefin, and aromatic vinyl. A filler (A) containing a polymer obtained by polymerizing one or more selected from the group consisting of compounds (hereinafter also referred to as “specific polymer”) and / or a silicone polymer; And a thermosetting component (B). Further, the content of the filler having a particle diameter of 3.0 μm or more in the filler (A) is 0% relative to the total volume (100% by volume) of the resin composition. 0.09% by volume or less.

  The resin composition for printed wiring boards of this embodiment has excellent moldability. This factor is inferred as follows (however, the factor is not limited to this). Since the organic filler contained in the resin composition is a low elastic component, the thermal expansion coefficient of the molded body containing the resin composition can be lowered. On the other hand, when the organic filler is included in the resin composition, the organic filler has a particle size distribution, so that the organic filler having a particle size of 3.0 μm or more exceeds 0.09% by volume. It will be contained in the resin composition to the extent. In general, even if an organic filler having a particle size slightly exceeding 3.0 μm is included, it is considered that the influence on the moldability of the resin composition is small. However, when such a resin composition is molded, moldability such as moldable thickness and molding unevenness as shown in Examples described later may be inferior. This is because when the thermosetting component contained in the resin composition is cured, the organic filler having a particle size of 3.0 μm or more inhibits the fluidity of the resin composition. Can be guessed. However, simply reducing the amount of the organic filler having a particle diameter of 3.0 μm or more cannot achieve both a low thermal expansion coefficient and a moldability of the obtained molded body. That is, the resin composition of the present embodiment has a resin composition containing a filler (A) containing a specific polymer and / or a silicone polymer and a thermosetting component (B), and the filler (A) When the content of the filler having a particle diameter of 3.0 μm or more is 0.09% by volume or less, both the low thermal expansion coefficient of the obtained molded body and the moldability can be achieved. This is a resin composition containing a filler (A) containing a specific polymer and / or a silicone polymer and a thermosetting component (B), and the particle diameter is 3.0 μm in the filler (A). When the content of the filler is 0.09% by volume or less, the resin is thermally cured at the time of thermosetting by the interaction between the filler (A) and the thermosetting component (B). It is presumed that the effect of the present invention is exhibited due to the excellent dispersibility of the filler (A) with respect to the thermosetting component (B).

[Filler (A)]
The filler (A) of the present embodiment is a particle containing the above-mentioned specific polymer and / or silicone polymer (hereinafter, the particle containing the specific polymer is also referred to as “organic filler”, and the particle containing the silicone polymer) Is also referred to as “silicone composite powder”, and is preferably a core-shell type particle having a core and a shell (hereinafter also simply referred to as “shell”) outside the core. Due to the fact that the filler (A) is a core-shell type particle, the aggregation of the filler (A) in the resin composition is suppressed as compared with the particle consisting of only the core component. The dispersibility of the material (A) tends to be good. Further, the moldability of the resin composition (for example, the property of suppressing flow lines and voids) tends to be more excellent. The core-shell type particle is a particle in which a core component and a shell component outside the core are different. In order to obtain the core-shell type particles, as will be described later, for example, emulsion polymerization may be performed in multiple stages, and the components used in the first stage and the components used in the second and subsequent stages may be different.

  When the filler (A) is a core-shell type particle, the core is not particularly limited, but the core is composed of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, olefin, and aromatic vinyl compound. It is preferable to include a polymer obtained by polymerizing one or more selected from the group and / or a polymer of silicone. In addition, a polymer obtained by polymerizing one or two or more types selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, and aromatic vinyl compound, and / or polymethylsilsesquioxy It is preferred to include a Sun polymer. Such core-shell type particles are preferable from the viewpoint of achieving both moldability and low thermal expansion. That is, when the core contains the polymer or the silicone polymer, it is more excellent in low thermal expansion. Moreover, it originates in having excellent compatibility with the filler (A) and thermosetting component (B) in a resin composition by including the polymer of the said polymer or polymethylsilsesquioxane in a shell. In addition, the dispersibility of the filler (A) is excellent. Furthermore, the moldability (for example, the property of suppressing flow lines and voids) of the resin composition tends to be more excellent.

  In addition, a polymer obtained by polymerizing one or more of cores selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, butadiene, and aromatic vinyl compounds. It is preferable that the shell contains a polymer obtained by polymerizing (meth) acrylic acid ester from the viewpoint of obtaining particularly excellent moldability.

  The (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylonitrile used in the present embodiment are not particularly limited as long as they have an acryl group or a methacryl group. Although it does not specifically limit as specific (meth) acrylic acid ester, For example, methyl (meth) acrylic acid ester, ethyl (meth) acrylic acid ester, propyl (meth) acrylic acid ester, butyl (meth) acrylic acid ester Among them, methyl (meth) acrylic acid ester is preferable.

  The olefin used in the present embodiment is not particularly limited as long as it is a compound having a skeleton of a hydrocarbon having a carbon-carbon double bond. Specific examples of the olefin include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, butadiene, isoprene, and pentadiene, and among them, butadiene is preferable.

  The aromatic vinyl compound used in the present embodiment is not particularly limited as long as it is an aromatic vinyl compound. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, and divinylbenzene. Among them, styrene is preferable.

  The specific polymer may be a homopolymer of the components described above or a copolymer containing two or more components.

式（Ａ１）中、複数のＲは、各々独立にアルキル基又はフェニル基を示し、ｎは、１以上の整数を示す。また、Ｒは、アルキル基を示すことが好ましく、炭素数１〜３のアルキル基を示すことがより好ましい。 The silicone polymer of the present embodiment is a polymer containing a bifunctional siloxane unit (D unit) represented by the following general formula (A1) as a repeating unit, or a polymethylsilsesquioxy as described below. Examples of the polymer that is a Sun polymer and includes a bifunctional siloxane unit (D unit) as a repeating unit include polyorganosiloxane.

In formula (A1), a plurality of R's each independently represents an alkyl group or a phenyl group, and n represents an integer of 1 or more. R preferably represents an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms.

The polymer of polymethylsilsesquioxane of this embodiment is not particularly limited as long as it is a polymer in which siloxane bonds are crosslinked in a three-dimensional network. The polymer of polymethylsilsesquioxane is, for example, an intermediate in which the composition of silica (SiO ₂ ) and the composition of the polymer containing the bifunctional siloxane unit (D unit) as a repeating unit are combined at 1: 1. It has the composition (RSiO _2/3 ).

  Although the average particle diameter of a filler (A) is not specifically limited, From a viewpoint of making the dispersibility of the filler (A) in a resin composition favorable, it is preferable that it is 0.05 micrometer or more and 3.0 micrometers or less. Here, an average particle diameter is a median diameter measured, for example with a laser diffraction type particle size distribution measuring apparatus. The median diameter refers to a particle diameter (D50 value) obtained from a cumulative distribution curve (volume basis) of particle diameter and having a height of 50% on the curve.

  The particle size distribution of the filler (A) is not particularly limited, but is preferably in the range of 0.01 μm to 5.0 μm, and more preferably in the range of 0.1 μm to 3.0 μm. The particle size distribution can be measured with, for example, a laser diffraction particle size distribution measuring apparatus.

  The manufacturing method of a filler (A) is not specifically limited, For example, the well-known method of manufacturing an organic resin particle can be utilized. Specific examples include, for example, an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. Among them, the emulsion polymerization method and the suspension polymerization method include the average particle diameter and This is preferable because particles having a controlled particle size distribution can be obtained. Moreover, when controlling an average particle diameter etc. directly by an emulsion polymerization method and a suspension polymerization method, an average particle diameter etc. are controlled by the polymerization conditions. On the other hand, after obtaining a polymer in a solid state by a bulk polymerization method or the like, the polymer was pulverized by a pulverizer such as a jet airflow pulverizer, a mechanical collision pulverizer, a roll mill, a hammer mill, an impeller breaker, etc. The average particle diameter and the like may be controlled by introducing the pulverized material into a classifier such as an air classifier or a sieve classifier and classifying it. In addition, a product having a known average particle size and the like can be appropriately selected and used from various commercially available organic resin particle products, and the average particle size and the like may be controlled by combining them. .

  A filler (A) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In the present embodiment, in the resin composition, the content of the filler (hereinafter also simply referred to as “specific coarse particles”) having a particle diameter of 3.0 μm or more in the filler (A) is the resin composition. It is 0.09 volume% or less with respect to the total volume (100 volume%) of a thing. When the content of the specific coarse particles is 0.09% by volume or less, a resin composition having good moldability can be obtained. This factor is because, in addition to the excellent dispersibility of the filler (A) with respect to the thermosetting component (B) during the curing of the resin composition, the content of the specific coarse particles is within the above range, for example, It is surmised that the particles are sandwiched between the bump-shaped irregularities and the glass cloth that are arranged to give adhesion to the resin on the copper foil mat surface and do not impede the fluidity of the resin ( However, the factor is not limited to this.) Here, the “total amount of the resin composition” is the total amount of the resin composition including the content of the inorganic filler (G) described later and not including the solvent.

  In order to obtain a resin composition in which the content of the specific coarse particles is within the above range, the particle size distribution is determined by a polymerization method such as emulsion polymerization or a method of classifying a once finely divided polymer as described above. A controlled filler (A) may be used. Moreover, you may filter a specific coarse particle, after manufacturing the resin composition containing a filler (A).

  The content of the specific coarse particles of the present embodiment is obtained from the result obtained by measuring the ratio of particles having a specific particle size (at least 3.0 μm) or more by, for example, a Coulter counter method, a laser diffraction method, or a particle image analysis method. Can do. Specifically, it can be determined by the method described in the examples.

  Although the resin composition of this embodiment is not specifically limited, It is preferable that 5.0 mass parts or more and 60 mass parts or less of a filler (A) are included with respect to 100 mass parts of thermosetting components (B) mentioned later. From the viewpoint of suppressing deterioration of moldability and dispersibility, 5.0 parts by mass or more and 30 parts by mass or less are more preferable, and 5.0 parts by mass or more and 20 parts by mass or less are more preferable.

[Thermosetting component (B)]
The thermosetting component (B) of the present embodiment is not particularly limited as long as it is a component that is cured by heat, but the maleimide compound (C), the epoxy resin (D), the cyanate ester compound (E), and the alkenyl-substituted nadiimide. It is preferable to include one or more selected from the group consisting of (F).

  In the resin composition of the present embodiment, the content of the thermosetting component (B) is not particularly limited, but is preferably 10% by mass or more and 90% by mass with respect to the total amount (100% by mass) of the resin composition. Or less, more preferably 20% by mass or more and 70% by mass or less, and further preferably 20% by mass or more and 60% by mass or less. When the content of the thermosetting component (B) is within the above range, the resin composition tends to be excellent in moldability and chemical resistance. Here, the “total amount of the resin composition” is the total amount of the resin composition including the content of the inorganic filler (G) and not including the solvent.

<Maleimide compound (C)>
The maleimide compound (C) that can be used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3 , 5-Dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, polytetramethylene oxide-bis (4-maleimidobenzoate), maleimide compounds represented by the following formula (6), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These may be used singly or in appropriate combination of two or more.

  Among them, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, polytetra One or more selected from the group consisting of methylene oxide-bis (4-maleimidobenzoate) and a maleimide compound represented by the following general formula (1) are preferred, and maleimide represented by the following general formula (1) Compounds are more preferred.

式（１）中、複数のＲ₅は、各々独立に水素原子又はメチル基を示し、ｎ₁は、１以上の整数を示す。

In the formula (1), a plurality of R ₅ are each independently a hydrogen atom or a methyl group, n ₁ represents an integer of 1 or more.

In formula (1), several R < ₅ > shows a hydrogen atom or a methyl group each independently, and it is preferable to show a hydrogen atom especially.

In the formula (1), n ₁ represents an integer of 1 or more. The upper limit of n ₁ is preferably 10, more preferably 7.

  In the resin composition of the present embodiment, the content of the maleimide compound (C) is not particularly limited, but is preferably 5.0% by mass or more with respect to the total amount (100% by mass) of the thermosetting component (B). It is 90 mass% or less, More preferably, it is 10 mass% or more and 60 mass% or less, More preferably, it is 20 mass% or more and 40 mass% or less. When the content of the maleimide compound (C) is within the above range, a printed wiring board having excellent moldability, thermal elastic modulus, desmear resistance, and chemical resistance can be obtained.

<Epoxy resin (D)>
By including the epoxy resin (D), the resin composition of the present embodiment tends to be more excellent in adhesiveness, moisture absorption heat resistance, flexibility, and the like. The epoxy resin (D) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolak type epoxy resin, xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, Trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, triglycidyl isocyanurate, glycidyl ester epoxy resin, alicyclic Poxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, di Cyclopentadiene-type epoxy resins, polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, epoxidized compounds such as butadiene, compounds obtained by reaction of hydroxyl-containing silicone resins with epichlorohydrin, and halogens thereof A compound. These epoxy resins (D) can be used singly or in appropriate combination of two or more.

  Among these, the epoxy resin (D) is one or more selected from the group consisting of biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins. Is preferred. By including such an epoxy resin (D), there exists a tendency for the flame retardance and heat resistance of the hardened | cured material obtained to improve more.

  In the resin composition of the present embodiment, the content of the epoxy resin (D) is not particularly limited, but is preferably 5.0% by mass or more with respect to the total amount (100% by mass) of the thermosetting component (B). It is 90 mass% or less, More preferably, it is 10 mass% or more and 60 mass% or less, More preferably, it is 20 mass% or more and 40 mass% or less. When the content of the epoxy resin (D) is within the above range, the adhesiveness and flexibility tend to be more excellent.

<Cyanate ester compound (E)>
The cyanate ester compound (E) that can be used in the present embodiment is not particularly limited. For example, a naphthol aralkyl cyanate ester represented by the following general formula (2), represented by the following general formula (3): Novolak-type cyanate ester, biphenylaralkyl-type cyanate ester, bis (3,3-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1, 4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2, 6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanato Biphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2-bis (4-cyanatophenyl) propane. These can be used individually by 1 type or in mixture of 2 or more types as appropriate.

  Among these, the naphthol aralkyl cyanate ester compound represented by the following general formula (2), the cyanate ester represented by the following general formula (3), and the biphenyl aralkyl cyanate ester are excellent in flame retardancy and are curable. The naphthol aralkyl type cyanate ester compound represented by the following general formula (2) and the novolak type cyanate ester represented by the following general formula (3) One or more selected from the group consisting of:

式（２）中、複数のＲ₆は、各々独立に水素原子又はメチル基を示し、ｎ₂は、１以上の整数を示す。

In the formula (2), a plurality of R ₆ are each independently a hydrogen atom or a methyl group, n ₂ represents an integer of 1 or more.

In the formula (2), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group, and preferably a hydrogen atom.

Wherein (2), n ₂ represents an integer of 1 or more. The upper limit value of n ₂ is preferably 10, more preferably 6.

式（３）中、複数のＲ₇は、各々独立に水素原子又は炭素数が１〜４のアルキル基を示し、複数のＲ₈は、各々独立に水素原子又は炭素数が１〜４のアルキル基若しくはアルケニル基を示し、ｎ₃は、１以上の整数を示す。

In formula (3), a plurality of R _{7 s} each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R _{8 s} independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A group or an alkenyl group, and n ₃ represents an integer of 1 or more.

In formula (3), several R < ₇ > shows a hydrogen atom or a C1-C4 alkyl group each independently, and it is preferable to show a methyl group especially.

In formula (3), a plurality of R ₈ each independently represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 4 carbon atoms, and preferably represents a hydrogen atom.

In formula (3), n ₃ represents an integer of 1 or more. The upper limit value of n ₃ is preferably 10, more preferably 7.

  The method for producing these cyanate ester compounds is not particularly limited, and may be produced by any existing method as a cyanate ester synthesis method. Specifically, by reacting a naphthol aralkyl type phenol resin represented by the following general formula (4) with cyanogen halide in an inert organic solvent in the presence of a basic compound, the above general formula (2 Naphthol aralkyl type cyanate ester compound represented by Alternatively, a similar naphthol aralkyl type phenol resin and a salt of a basic compound may be formed in a solution containing water, and then a two-phase interface reaction with cyanogen halide may be performed for synthesis. it can.

式（４）中、複数のＲ₆は、各々独立に水素原子又はメチル基を示し、ｎ₄は、１以上の整数を示す。

In the formula (4), a plurality of R ₆ are each independently a hydrogen atom or a methyl group, n ₄ represents an integer of 1 or more.

In the formula (4), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.

In formula (4), n ₄ represents an integer of 1 or more. The upper limit of n ₄ is preferably 10, more preferably 6.

  Naphthol aralkyl cyanate compounds include naphthols such as α-naphthol and β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, 1,4-di (2-hydroxy- A product obtained by condensing a naphthol aralkyl resin obtained by reaction with 2-propyl) benzene or the like and cyanic acid can also be used.

  In the resin composition of the present embodiment, the content of the cyanate ester compound (E) is not particularly limited, but is preferably 5.0 mass with respect to the total amount (100 mass%) of the thermosetting component (B). % To 90% by mass, more preferably 10% to 70% by mass, and still more preferably 30% to 50% by mass. When the content of the cyanate ester compound (E) is within the above range, a printed wiring board excellent in moldability, thermal elastic modulus, desmear resistance, and chemical resistance tends to be obtained.

<Alkenyl-substituted nadiimide (F)>
The alkenyl-substituted nadiimide (F) that can be used in the present embodiment is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadiimide groups in the molecule. Specific examples thereof include compounds represented by the following general formula (5).

In formula (5), a plurality of R ₁ 's each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, or a naphthylene. Or a group represented by the following general formula (6) or (7).

In formula (6), R ₃ represents a substituent represented by a methylene group, an isopropylidene group, CO, O, S, or SO ₂ .

In the formula (7), a plurality of R ₄ represents each independently an alkylene group having 1 to 4 carbon atoms, or a cycloalkylene group having a carbon number of 5-8.

  Moreover, a commercially available thing can also be used for the alkenyl substituted nadiimide (F) represented by Formula (5). Although it does not specifically limit as what is marketed, For example, the compound (BANI-M (made by Maruzen Petrochemical Co., Ltd.)) represented by following formula (8), the compound represented by following formula (9) (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)). These may be used alone or in combination of two or more.

  In the resin composition of the present embodiment, the content of the alkenyl-substituted nadiimide (F) is not particularly limited, but is preferably 5.0% by mass with respect to the total amount (100% by mass) of the thermosetting component (B). It is 90 mass% or less, More preferably, it is 10 mass% or more and 70 mass% or less, More preferably, it is 30 mass% or more and 50 mass% or less. When the content of the alkenyl-substituted nadiimide (F) is within the above range, a printed wiring board excellent in moldability, thermal elastic modulus, desmear resistance, and chemical resistance tends to be obtained.

  The various thermosetting components (B) described above may be used singly or in combination of two or more, or may be used as a prepolymer. The prepolymer of this embodiment is a polymer of one or more selected from the group consisting of the maleimide compound (C), epoxy resin (D), cyanate ester compound (E), and alkenyl-substituted nadiimide (F) described above. It is preferable that it is the reaction product obtained by doing this. From the viewpoint of using the reaction product as a resin composition, it is more preferable that the reaction product can be dissolved or dispersed in an organic solvent as a prepolymer.

  Moreover, in the resin composition of this embodiment, it is also possible to add other resin in addition to the thermosetting component (B) as long as desired characteristics are not impaired. Although it will not specifically limit about the kind of the said other resin if it has insulation, For example, a thermoplastic resin is mentioned. By appropriately using a thermoplastic resin or the like, it is possible to impart characteristics such as metal adhesion and stress relaxation.

[Inorganic filler (G)]
The resin composition of the present embodiment may further include an inorganic filler (G) within a range that does not impair the effects of the present invention. The inorganic filler (G) is not particularly limited as long as it has an insulating property. Examples thereof include silicas such as natural silica, fused silica, amorphous silica, and hollow silica; alumina, aluminum nitride, boron nitride, boehmite, Molybdenum oxide, titanium oxide, zinc borate, zinc stannate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fiber (glass fine powders such as E glass and D glass), hollow glass And spherical glass. These can be used individually by 1 type or in mixture of 2 or more types as appropriate.

  Among these, it is preferable to use silica from the viewpoint of low thermal expansion and alumina or aluminum nitride from the viewpoint of high thermal conductivity.

  The resin composition of the present embodiment is not particularly limited, but it may contain 50 to 300 parts by mass of the inorganic filler (G) with respect to 100 parts by mass of the thermosetting component (B). From the viewpoint of characteristics such as high thermal conductivity, it is more preferable to include 100 parts by mass or more and 250 parts by mass.

[Silane coupling agent, wetting and dispersing agent]
The resin composition of the present embodiment may be used in combination with a silane coupling agent and / or a wet dispersant in order to improve the dispersibility of the inorganic filler fine particles and the adhesive strength between the resin and the inorganic filler fine particles and the glass cloth. Is possible. These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for inorganic surface treatment. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane. Acrylic silanes such as γ-acryloxypropyltrimethoxysilane; cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane silane cups A ring agent is mentioned, It is also possible to use 1 type individually or in combination of 2 or more types as appropriate. The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for coatings. Specific examples include wet dispersants such as DISPER-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 under the trade names of Big Chemie Japan Co., Ltd.

[Curing accelerator]
The resin composition of the present embodiment can be used in combination with a curing accelerator as long as desired properties are not impaired. Although it does not specifically limit as a hardening accelerator, For example, the organic peroxide illustrated by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate etc. Azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, Tertiary amines such as N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, lead stearate , Naphth Organic metal salts such as zinc oxide, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate and acetylacetone iron; these organic metal salts are dissolved in hydroxyl group-containing compounds such as phenol and bisphenol Inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; Dioctyl tin oxide, other organic tin compounds such as alkyl tin and alkyl tin oxide, and triphenylimidazole (TPIZ).

〔Organic solvent〕
The resin composition of the present embodiment may contain a solvent as necessary. For example, when an organic solvent is used, the viscosity at the time of preparing the resin composition is lowered, the handling property is improved, and the impregnation property to the glass cloth is enhanced. The kind of solvent will not be specifically limited if it can melt | dissolve part or all of resin in a resin composition. Specific examples thereof include, but are not particularly limited to, for example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and acetate thereof Is mentioned. A solvent can be used 1 type or in combination of 2 or more types.

[Other ingredients]
In the resin composition of the present embodiment, various polymer compounds such as other thermosetting resins, thermoplastic resins and oligomers thereof, elastomers, etc., as long as the desired characteristics are not impaired These compounds can be used in combination with additives. These are not particularly limited as long as they are generally used. For example, in a flame-retardant compound, nitrogen-containing compounds such as melamine and benzoguanamine, and oxazine ring-containing compounds are exemplified. Additives include UV absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface conditioners, brighteners, polymerization Inhibitors and the like can be used in appropriate combinations as desired.

[Method for producing resin composition for printed wiring board]
The method for producing the resin composition for a printed wiring board of the present embodiment is not particularly limited, and can be produced, for example, by mixing the filler (A) and the thermosetting component (B), Other optional components may be mixed as necessary.

  During the production of the resin composition, a known process (such as stirring, mixing, and kneading process) for uniformly dissolving or dispersing each component can be performed. Dispersibility to the resin composition by performing agitation and dispersion treatment using a stirrer equipped with a stirrer having an appropriate agitation ability for uniform dispersion of the filler (filler (A) and inorganic filler (G)). Is increased. The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill or a bead mill for mixing, or a revolving or rotating mixing device.

[Prepreg]
The prepreg of this embodiment has a base material and the resin composition of this embodiment impregnated or applied to the base material. The manufacturing method of a prepreg can be performed according to a conventional method, and is not specifically limited. For example, after impregnating or applying the above resin composition to a substrate, it is semi-cured (B-staged) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. The method of obtaining is mentioned. In the present embodiment, the content of the resin composition (including the inorganic filler) with respect to the total amount (100% by mass) of the prepreg is not particularly limited, but is in the range of 30% by mass to 90% by mass. It is preferable.

  The substrate used in the prepreg of the present embodiment is not particularly limited, and known materials used for various printed wiring board materials are appropriately selected and used depending on the intended use and performance. be able to. Specific examples thereof are not particularly limited. For example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, and T glass; inorganic fibers other than glass such as quartz; polyparaphenylene Totally aromatic polyamides such as terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene 3,4′oxydiphenylene terephthalamide (Technola (registered trademark), manufactured by Teijin Techno Products); Polyesters such as 6-hydroxynaphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.); polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), and organic fibers such as polyimide Can be mentioned.

  Among these, from the viewpoint of low thermal expansibility, one or more selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers are preferable.

Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, and a surfacing mat are mentioned. The weaving method of the woven fabric is not particularly limited, and for example, plain weave, Nanako weave, and twill weave are known, and these can be appropriately selected and used depending on the intended use and performance. Moreover, the thing which spread-processed these, and the glass woven fabric surface-treated with the silane coupling agent etc. are used suitably. Although the thickness and mass of the substrate are not particularly limited, those having a thickness of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the base material is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less, and a glass woven fabric made of glass fibers such as E glass, S glass, and T glass. Is more preferable.

  The laminated board of this embodiment can be obtained by, for example, stacking and curing a plurality of the above-described prepregs. Moreover, the metal foil tension laminated board of this embodiment can be obtained by laminating | stacking and hardening the above-mentioned prepreg and metal foil, for example.

Specifically, the metal foil-clad laminate of the present embodiment can be obtained, for example, by laminating at least one or more of the prepregs described above, and arranging and molding the metal foil on one or both sides thereof. More specifically, by laminating one or more of the above prepregs, and optionally placing a metal foil such as copper or aluminum on one or both sides of the prepreg, this is laminated and formed as necessary. A metal foil-clad laminate can be produced. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. The thickness of the metal foil is not particularly limited, but is preferably 1.0 μm or more and 70 μm or less, and more preferably 1.5 μm or more and 35 μm or less. There are no particular limitations on the method for forming the metal foil-clad laminate and the molding conditions thereof, and general methods and conditions for a laminate for a printed wiring board and a multilayer board can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of forming a metal foil-clad laminate. In forming a metal foil-clad laminate, the temperature is generally 100 to 300 ° C., the pressure is a surface pressure of 2.0 to 100 kgf / cm ² , and the heating time is generally in the range of 0.05 to 5 hours. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. Also, a multilayer board can be formed by laminating and combining the above-described prepreg and a separately prepared wiring board for an inner layer.

  The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal foil-clad laminate of this embodiment has a low coefficient of thermal expansion, good formability, metal foil peel strength, and chemical resistance (particularly desmear resistance), and a semiconductor that requires such performance. It can be used particularly effectively as a printed wiring board for a package.

  Moreover, in this embodiment, it can also be set as the form of the embedding sheet of the form which apply | coated the above-mentioned resin composition to metal foil or a film other than the form of the prepreg mentioned above.

[Resin sheet]
The resin sheet of this embodiment has a support body and the resin composition of this embodiment distribute | arranged to the surface of this support body. For example, it is a resin sheet in which the above-described resin composition is applied to one side or both sides of a support. Here, the resin sheet is used as one means of thinning, for example, a thermosetting resin (including an inorganic filler) used for a prepreg directly on a support such as a metal foil or a film. Can be applied and dried.

  Although the support body used when manufacturing the resin sheet of this embodiment is not specifically limited, the well-known thing used for various printed wiring board materials can be used, and it is a resin sheet or metal foil. It is preferable. Examples of the resin sheet and metal foil include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, and a resin sheet such as a polyethylene (PE) film, And metal foils such as aluminum foil, copper foil, and gold foil. Among these, electrolytic copper foil and PET film are preferable.

  The resin sheet of the present embodiment is preferably one obtained by applying the above-described resin composition to a support and then semi-curing (B-stage). In general, the method for producing the resin sheet of this embodiment is preferably a method for producing a composite of a B-stage resin and a support. Specifically, for example, after the resin composition is applied to a support such as a copper foil, it is semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes to produce a resin sheet. The method of doing is mentioned. The amount of the resin composition attached to the support is preferably in the range of 1.0 to 300 μm in terms of the resin thickness of the resin sheet.

  The resin sheet of this embodiment can be used as a build-up material for a printed wiring board.

  The laminated board of this embodiment can be obtained, for example, by stacking and curing one or more of the above-described resin sheets.

  Moreover, the metal foil tension laminated board of this embodiment can be obtained by laminating | stacking and hardening the above-mentioned resin sheet and metal foil, for example.

Specifically, the metal foil-clad laminate of the present embodiment can be obtained by, for example, using the above-described resin sheet and arranging and laminating metal foils on one side or both sides thereof. More specifically, for example, one of the above-mentioned resin sheets or a plurality of the ones from which the support is peeled off are stacked, and a metal foil such as copper or aluminum is arranged on one or both sides thereof. A metal foil-clad laminate can be produced by laminating as necessary. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. There are no particular limitations on the method for forming the metal foil-clad laminate and the molding conditions thereof, and general methods and conditions for a laminate for a printed wiring board and a multilayer board can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of forming a metal foil-clad laminate. Further, at the time of forming the metal foil-clad laminate, the temperature is generally 100 to 300 ° C., the pressure is a surface pressure of 2.0 to 100 kgf / cm ² , and the heating time is generally 0.05 to 5 hours. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C.

  The laminate of this embodiment may be a laminate provided with a plurality of resin sheets and / or prepregs, or may be a metal foil-clad laminate provided with resin sheets and / or prepregs and metal foils. These laminates are obtained by stacking and curing a resin sheet, a prepreg, and a metal foil.

  In this embodiment, when a conductor layer to be a circuit is formed to produce a printed wiring board, a method of electroless plating can also be used if the form of a metal foil-clad laminate is not taken.

[Printed wiring board]
The printed wiring board of the present embodiment includes an insulating layer containing the resin composition of the present embodiment and a conductor layer formed on the surface of the insulating layer.

  The printed wiring board according to the present embodiment is manufactured, for example, by forming a conductive layer serving as a circuit on an insulating layer by metal foil or electroless plating. The conductor layer is generally made of copper or aluminum. The insulating layer for printed wiring board on which the conductor layer is formed can be suitably used for a printed wiring board by forming a predetermined wiring pattern. And the printed wiring board of this embodiment maintains the elastic modulus excellent also under the reflow temperature at the time of semiconductor mounting because an insulating layer contains the above-mentioned resin composition, and effectively warps a semiconductor plastic package. Since it suppresses and is excellent in metal foil peel strength and desmear resistance, it can be used particularly effectively as a printed wiring board for semiconductor packages.

  Specifically, the printed wiring board of this embodiment can be manufactured by the following method, for example. First, the metal foil-clad laminate (such as a copper-clad laminate) is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate. If necessary, surface treatment is performed on the inner layer circuit surface of the inner layer substrate to increase the adhesive strength, then the required number of the prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is laminated on the outer side. Then, it is integrally molded by heating and pressing. In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after this multi-layer laminate is subjected to drilling for through holes and via holes, desmear treatment is performed to remove smears, which are resin residues derived from the resin component contained in the cured product layer. . After that, a plated metal film is formed on the wall surface of this hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and the outer layer circuit is formed by etching the metal foil for the outer layer circuit to produce a printed wiring board. Is done.

  In the printed wiring board of the present embodiment, for example, the above-described prepreg (base material and the above-described resin composition attached thereto), the above-described resin sheet (the support and the above-described resin composition attached thereto), The resin composition layer of the metal foil-clad laminate (layer made of the above-described resin composition) constitutes an insulating layer containing the above-described resin composition.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.

[Average particle diameter, ratio of particles larger than specific particle diameter]
The average particle diameter (median diameter) of various organic fillers and silicone composite powders used as the filler (A) in the examples and the ratio of particles having a specific particle diameter (5.0 μm, 3.0 μm, 1.0 μm) or more are as follows: It was measured with a laser diffraction particle size distribution meter. Specifically, the median diameter is obtained by measuring the particle size distribution of the filler (A) in the methyl ethyl ketone (MEK) dispersion medium, and is obtained from a cumulative distribution curve (volume basis) of the particle diameter. The particle diameter (D50 value) was determined. The specific particle size is determined by measuring the particle size distribution of the filler (A) in the MEK dispersion medium, integrating the volume from large particles, and converting the volume up to 5.0 μm and the volume converted to 3.0 μm. The ratio of particles converted to a volume up to 1.0 μm was determined.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl-type cyanate ester resin A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was cooled in advance to 0 to 5 ° C. with brine, and chlorinated there. 7.47 g (0.122 mol) of cyanide, 9.75 g (0.0935 mol) of 35% hydrochloric acid, 76 ml of water, and 44 ml of methylene chloride were charged. An α-naphthol aralkyl type phenol resin (SN485, OH group equivalent) in which R ₆ in the formula (4) is all hydrogen atoms with stirring while keeping the temperature in the reactor at −5 to + 5 ° C. and the pH at 1 or less. : 214 g / eq Softening point: 86 ° C., manufactured by Nippon Steel Chemical Co., Ltd.) 20 g (0.0935 mol) and triethylamine 14.16 g (0.14 mol) dissolved in 92 ml of methylene chloride were added to a 1 It dropped over time, and after completion | finish of dripping, 4.72 g (0.047 mol) of triethylamine was further dripped over 15 minutes. After completion of dropping, the reaction solution was separated after stirring at the same temperature for 15 minutes, and the organic layer was separated. The obtained organic layer was washed twice with 100 ml of water, and then methylene chloride was distilled off under reduced pressure using an evaporator. Finally, the mixture was concentrated to dryness at 80 ° C. for 1 hour, and an α-naphthol aralkyl type phenol resin cyanide was obtained. 23.5 g of acid esterified product (α-naphthol aralkyl type cyanate ester resin) was obtained.

[Example 1]
As filler (A), organic filler [MMA shell-MBS core] (TMS-2670: trade name manufactured by Dow Chemical Japan Ltd.), 10 parts by mass, maleimide compound (BMI-2300: Daiwa Kasei Kogyo Co., Ltd.) Trade name, maleimide group equivalent 186 g / eq.) 30 parts by mass, α-naphthol aralkyl-type cyanate ester resin (cyanate equivalent 261 g / eq.) Prepared in Synthesis Example 1, 40 parts by mass, polyoxynaphthylene type 30 parts by mass of epoxy resin (HP6000: trade name made by DIC Corporation), spherical silica (SC-2050MB: trade name made by Admatechs), particles having an average particle size of 0.5 μm and a particle size of 5.0 μm or more 200 parts by mass, silane coupling agent (KBM-403: trade name of Shin-Etsu Silicone Co., Ltd.) 5.0 parts by mass And 0.3% by mass of a wetting and dispersing agent (DISPERBYK-2009: trade name manufactured by Big Chemie Japan), and the content of the filler (A) having a particle size of 3.0 μm or more is 0.00 vol%. A certain resin composition was obtained. The organic filler [MMA shell-MBS core] is a particle having a core made of a methyl methacrylate-butadiene-styrene copolymer (MBS) and a shell made of a methyl methacrylate polymer (MMA). . The average particle diameter of the organic filler [MMA shell-MBS core] is 0.151 μm, the ratio of particles having a particle diameter of 5.0 μm or more is 0.00%, the ratio of particles having a particle diameter of 3.0 μm or more is 0.00%, and the particle diameter The ratio of particles having a size of 1.0 μm or more was 0.00%.

[Example 2]
Except for replacing 10 parts by weight of the organic filler [MMA shell-MBS core] (TMS-2670) with 20 parts by weight of the organic filler [MMA shell-MBS core] (TMS-2670), the same method as in Example 1 was used. A resin composition in which the content of the filler (A) having a particle diameter of 3.0 μm or more was 0.00% by volume was obtained.

[Example 3]
Except that 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) was replaced with 25 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670), the same method as in Example 1 was performed. A resin composition in which the content of the filler (A) having a particle diameter of 3.0 μm or more was 0.00% by volume was obtained.

[Example 4]
10 parts by weight of organic filler [MMA shell-MBS core] (TMS-2670) is replaced with 10 parts by weight of organic filler [MMA shell-BA core] (EXL-2315: trade name of Dow Chemical Japan Co., Ltd.) In the same manner as in Example 1, except that the content of the filler (A) having a particle size of 3.0 μm or more was 0.00 vol%. The organic filler [MMA shell-BA core] is a particle having a core made of a butyl acrylate polymer (BA) and a shell made of a methyl methacrylate polymer (MMA). The average particle size of the organic filler [MMA shell-BA core] is 0.153 μm, the proportion of particles having a particle size of 5.0 μm or more is 0.00%, the proportion of particles having a particle size of 3.0 μm or more is 0.00%, and the particle size The ratio of particles having a size of 1.0 μm or more was 0.00%.

[Example 5]
Except that 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) was replaced by 20 parts by mass of the organic filler [MMA shell-BA core] (EXL-2315), the same method as in Example 1 was performed. A resin composition in which the content of the filler (A) having a particle diameter of 3.0 μm or more was 0.00% by volume was obtained.

[Example 6]
Except for replacing 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) with 25 parts by mass of the organic filler [MMA shell-BA core] (EXL-2315), the same method as in Example 1 was used. A resin composition in which the content of the filler (A) having a particle diameter of 3.0 μm or more was 0.00 vol% was obtained.

[Example 7]
10 parts by mass of organic filler [MMA shell-MBS core] (TMS-2670) is mixed with organic filler [MMA shell-MBS core] (methyl methacrylate-butadiene-styrene copolymer (MBS) core and methyl methacrylate). Particles having a shell made of a polymer (MMA), trade name “EXL-2655” manufactured by Dow Chemical Japan Co., Ltd.) A resin composition in which the content of the filler (A) having a diameter of 3.0 μm or more was 0.00% by volume was obtained. The average particle size of the organic filler [MMA shell-MBS core] is 0.094 μm, the proportion of particles having a particle size of 5.0 μm or more is 0.00%, the proportion of particles having a particle size of 3.0 μm or more is 0.00%, and the particle size The ratio of particles having a size of 1.0 μm or more was 0.00%.

[Example 8]
Except for replacing 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) with 20 parts by mass of the organic filler [MMA shell-MBS core] (EXL-2655), the same method as in Example 1 was used. A resin composition in which the content of the filler (A) having a particle diameter of 0.3 μm or more was 0.00% by volume was obtained.

[Example 9]
Except that 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) was replaced with 25 parts by mass of the organic filler [MMA shell-MBS core] (EXL-2655), the same method as in Example 1 was performed. A resin composition in which the content of the filler (A) having a particle diameter of 0.3 μm or more was 0.00% by volume was obtained.

[Example 10]
10 parts by mass of an organic filler [MMA shell-MBS core] (TMS-2670) has a silicone composite powder [silsesquioxane shell-silicone core] (a silicone polymer core and a silsesquioxane shell). Particles, trade name “X-52-7030” manufactured by Shin-Etsu Silicone Co., Ltd.) Except for changing to 10 parts by mass, a filler having a particle diameter of 0.3 μm or more (A ) Content of 0.05% by volume was obtained. The average particle diameter of the silicone composite powder [silsesquioxane shell-silicone core] is 0.863 μm, the ratio of particles having a particle diameter of 5.0 μm or more is 0.00%, and the ratio of particles having a particle diameter of 3.0 μm or more is 0.85. %, The proportion of particles having a particle size of 1.0 μm or more was 26.4%, and the particle size distribution was 0.2 to 2.0 μm.

[Example 11]
Example 1 except that 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) was replaced with 20 parts by mass of the silicone composite powder [silsesquioxane shell-silicone core] (X-52-7030). By the same method, the resin composition whose content of a filler (A) with a particle diameter of 0.3 micrometer or more is 0.09 volume% was obtained.

[Comparative Example 1]
Example 1 except that 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) was replaced with 25 parts by mass of the silicone composite powder [silsesquioxane shell-silicone core] (X-52-7030). By the same method, the resin composition whose content of a filler (A) with a particle diameter of 0.3 micrometer or more is 0.10 volume% was obtained.

[Comparative Example 2]
10 parts by mass of an organic filler [MMA shell-MBS core] (TMS-2670) has a silicone composite powder [silsesquioxane shell-silicone core] (a silicone polymer core and a silsesquioxane shell). Content of the filler (A) having a particle diameter of 0.3 μm or more by the same method as in Example 1 except that the particle was changed to 10 parts by mass, trade name “KMP605” manufactured by Shin-Etsu Silicone Co., Ltd. A resin composition having 1.11% by volume was obtained. The average particle diameter of the silicone composite powder [silsesquioxane shell-silicone core] is 2.166 μm, the ratio of particles having a particle diameter of 5.0 μm or more is 4.72%, and the ratio of particles having a particle diameter of 3.0 μm or more is 20.99. %, The proportion of particles having a particle size of 1.0 μm or more was 95.71%, and the particle size distribution was 0.7 to 5.0 μm.

[Comparative Example 3]
The same method as in Example 1 except that 10 parts by mass of the organic filler [MMA shell-MBS core] (TMS-2670) was replaced by 20 parts by mass of the silicone composite powder [silsesquioxane shell-silicone core] (KMP605). Thus, a resin composition in which the content of the filler (A) having a particle diameter of 0.3 μm or more was 2.11% by volume was obtained.

[Content of specific coarse particles]
The content (content of specific coarse particles) of the filler (A) having a specific particle size (5.0 μm, 3.0 μm, 1.0 μm) or more is determined from the composition of the resin composition and the ratio corresponding to the composition. It was. Specifically, the average specific gravity of the thermosetting component and additive (silane coupling agent, wetting and dispersing agent) in the resin composition is 1.2 parts by mass / volume, and the average specific gravity of the spherical silica is 2.2 parts by mass. The average specific gravity of the organic filler was 1.1 parts by mass / volume and the average specific gravity of the silicone composite powder was 1.0 part by mass / volume.
Specific coarse particles = (Organic filler or silicone composite powder (parts by mass) × Particle ratio (%) greater than specific particle size) / {(Total (parts by mass) of thermosetting components and additives in the resin composition) / 1 .2) + (spherical silica (parts by mass) /2.2) + (organic filler (parts by mass) /1.1) + (silicone composite powder (parts by mass) /1.0)}

[Prepreg]
A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated with T glass cloth (T2118) and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg. At that time, the content (% by mass) of the resin composition in the varnish was adjusted so that the insulating layer had a thickness of 100 μm when the following laminate was used, to obtain a prepreg.

[Laminated board]
One sheet of the obtained prepreg is placed up and down with 12 μm thick electrolytic copper foil (trade name “3EC-III” manufactured by Mitsui Mining & Mining Co., Ltd.), and laminated for 120 minutes at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. Then, a copper clad laminate having an insulating layer thickness of 100 μm was obtained.

[Moldability: Moldable thickness]
After removing the copper foil from the double-sided copper clad laminates obtained in Examples and Comparative Examples by etching the entire surface, the surface was visually observed to confirm the presence or absence of voids. If voids are confirmed, copper-clad laminates with an insulating layer thickness increased by 1 μm are made in order until no voids are confirmed, and the thickness of the insulating layer where voids are not confirmed can be formed. The evaluation value was (μm). In addition, the copper clad laminated board which increased the thickness of the insulating layer by 1 micrometer unit was produced by adjusting content of the resin composition in a varnish in preparation of the prepreg mentioned above.

[Moldability: Molding unevenness]
After removing the copper foil from the double-sided copper clad laminates obtained in the examples and comparative examples by etching the entire surface, the surface was visually observed to check for the presence of flow lines (striated patterns). If no flow streak is confirmed, the length is evaluated as 0 cm. If one flow streak is confirmed, the length is determined. If a plurality of flow streaks are confirmed, the length of the longest one is determined as the molding unevenness (cm ).

[Coefficient of thermal expansion]
After removing the copper foil from the double-sided copper-clad laminates obtained in Examples and Comparative Examples by etching the entire surface, a thermomechanical analyzer (manufactured by TA Instruments Co., Ltd.) was used at 40 ° C. to 340 ° C. at 10 ° C. per minute. The temperature was raised, the linear expansion coefficient in the plane direction from 60 ° C. to 120 ° C. was measured, and the obtained value was taken as the evaluation value of the coefficient of thermal expansion (ppm / degC). The measurement direction was the longitudinal direction (Warp) of the glass cloth of the laminate.

  The resin composition and printed wiring board of the present invention can be suitably used as members of various electronic devices such as personal computers and communication devices.

Claims (19)

Of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, olefin, and polymer and / or silicone obtained by polymerizing one or more selected from the group consisting of aromatic vinyl compounds A filler (A) containing a polymer;
A thermosetting component (B), and a resin composition comprising:
The content of the filler having a particle diameter of 3.0 μm or more in the filler (A) is 0.09% by volume or less with respect to the total volume of the resin composition. Resin composition.   The resin composition for a printed wiring board according to claim 1, wherein the filler (A) is a core-shell type particle having a core and a shell outside the core.   The core is a polymer obtained by polymerizing one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, olefin, and aromatic vinyl compound, and The resin composition for printed wiring boards according to claim 2, comprising a polymer of silicone.   The shell is a polymer obtained by polymerizing one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, and aromatic vinyl compound, and / or polymethylsilsesquioxy. The resin composition for printed wiring boards according to claim 2 or 3, comprising a sun polymer. The core includes a polymer obtained by polymerizing one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, butadiene, and an aromatic vinyl compound,
The said shell is a resin composition for printed wiring boards as described in any one of Claims 2-4 containing the polymer obtained by polymerizing methacrylic acid ester.   The said resin composition contains 5.0 mass parts or more and 60 mass parts or less of the said filler (A) with respect to 100 mass parts of said thermosetting components (B). The resin composition for printed wiring boards as described in 2.   The thermosetting component (B) includes one or more selected from the group consisting of a maleimide compound (C), an epoxy resin (D), a cyanate ester compound (E), and an alkenyl-substituted nadiimide (F). The resin composition for printed wiring boards as described in any one of Claims 1-6. The maleimide compound (C) is bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) 8) The print according to claim 7, comprising one or more selected from the group consisting of methane, polytetramethylene oxide-bis (4-maleimidobenzoate), and a maleimide compound represented by the following general formula (1). Resin composition for wiring boards.

(In the formula (1), a plurality of R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.) The cyanate ester compound (E) includes one or more selected from the group consisting of a compound represented by the following general formula (2) and a compound represented by the following general formula (3). The resin composition for printed wiring boards according to 7 or 8.

(In the formula (2), each of the plurality of R ₆ independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)

(In Formula (3), a plurality of R _{7 s} each independently represent a hydrogen atom or a methyl group, and a plurality of R _{8 s} each independently represent a hydrogen atom or an alkyl group or alkenyl group having 1 to 4 carbon atoms. N ₃ represents an integer of 1 or more.)   The resin composition for printed wiring boards according to any one of claims 1 to 9, further comprising an inorganic filler (G).   The said inorganic filler (G) is a resin composition for printed wiring boards of Claim 10 containing 1 type, or 2 or more types selected from the group which consists of a silica, an alumina, and aluminum nitride.   The printed wiring board according to claim 10 or 11, wherein the resin composition contains 50 to 300 parts by mass of the inorganic filler (G) with respect to 100 parts by mass of the thermosetting component (B). Resin composition.   The prepreg which has a base material and the resin composition for printed wiring boards as described in any one of Claims 1-12 impregnated or apply | coated to this base material.   The prepreg according to claim 13, wherein the base material is one or more selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers.   The resin sheet which has a support body and the resin composition for printed wiring boards as described in any one of Claims 1-12 distribute | arranged to the surface of this support body.   The resin sheet according to claim 15, wherein the support is a resin sheet or a metal foil.   A laminate comprising a plurality of one or more selected from the group consisting of the prepreg according to claim 13 or 14 and the resin sheet according to claim 15 or 16.   A metal foil-clad laminate comprising one or more selected from the group consisting of the prepreg according to claim 13 or 14 and the resin sheet according to claim 15 or 16, and a metal foil.   A printed wiring board provided with the insulating layer containing the resin composition for printed wiring boards as described in any one of Claims 1-12, and the conductor layer formed in the surface of this insulating layer.