JPWO2017175614A1 - Resin composition and manufacturing method thereof, prepreg, resin sheet, laminate, metal foil-clad laminate, and printed wiring board - Google Patents

Abstract

  In the present invention, amino-modified silicone (A), maleimide compound (B), and one or more selected from the group consisting of carboxylic acid (C) and carboxylic anhydride (D) are reacted. A resin composition containing the obtained reaction product (P) is provided.

Description

  The present invention relates to a resin composition and a production method thereof, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, 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).

  In addition to lowering the thermal expansion of the printed wiring board, methods for suppressing the warpage of the semiconductor plastic package include increasing the rigidity of the laminated board (higher rigidity) and increasing the glass transition temperature of the laminated board (high Tg). (For example, see 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 peel strength of a laminated board in which a metal foil is laminated or chemical resistance to a strong alkaline cleaning liquid, for example. Since it is difficult to achieve compatibility with other characteristics such as (desmear resistance), there remains a problem that warps the semiconductor plastic package 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 is generated by reacting, for example, an amino-modified silicone and a thermosetting component as a low elastic component. An amino-modified polymer can be included. However, amino-modified polymers generally have the property of further polymerizing reaction between polymers or with other resin components. For this reason, it may be impossible to obtain excellent storage stability due to the fact that the amino-modified polymer further undergoes a polymerization reaction during storage or molding of the resin composition or prepreg.

  Then, this invention is made | formed in order to solve the above-mentioned subject, and it aims at providing the resin composition which has the outstanding storage stability, containing the amino-modified polymer.

（式（１）中、複数のＲ_ａは、各々独立に水素原子、メチル基又はフェニル基を表し、複数のＲ_ｂは、各々独立に単結合、アルキレン基又はアリール基を表し、ｎは、１以上の整数を表す。）
［８］
前記反応生成物（Ｐ）における前記アミノ変性シリコーン（Ａ）のアミノ基当量が、１３０以上６０００以下である、
［１］〜［７］のいずれかに記載の樹脂組成物。
［９］
前記マレイミド化合物（Ｂ）は、ビス（４−マレイミドフェニル）メタン、２，２−ビス｛４−（４−マレイミドフェノキシ）−フェニル｝プロパン、ビス（３−エチル−５−メチル−４−マレイミドフェニル）メタン、ポリテトラメチレンオキシド−ビス（４−マレイミドベンゾエート）、及び下記一般式（２）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、
［１］〜［８］のいずれかに記載の樹脂組成物。

（式（２）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。）
［１０］
充填材（Ｊ）をさらに含む、
［１］〜［９］のいずれかに記載の樹脂組成物。
［１１］
前記充填材（Ｊ）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］に記載の樹脂組成物。
［１２］
前記樹脂組成物は、前記反応生成物（Ｐ）及び熱硬化性成分（Ｅ）の合計量１００質量部に対して、前記充填材（Ｊ）を５０質量部以上３００質量部以下含む、
［１０］又は［１１］に記載の樹脂組成物。
［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。
［２０］
アミノ変性シリコーン（Ａ）と、マレイミド化合物（Ｂ）と、を反応させて一次ポリマーを得る第一反応工程と、
前記一次ポリマーと、カルボン酸（Ｃ）又はカルボン酸無水物（Ｄ）の少なくともいずれかと、を反応させる第二反応工程と、を有する、
樹脂組成物の製造方法。That is, the present invention is as follows.
[1]
Amino-modified silicone (A);
A maleimide compound (B);
A reaction product (P) obtained by reacting at least one of carboxylic acid (C) and carboxylic acid anhydride (D),
Resin composition.
[2]
The amine value of the resin composition is 2.0 mgKOH / g or less,
The resin composition according to [1].
[3]
The reaction product (P) is obtained by reacting at least the carboxylic acid anhydride (D),
The carboxylic anhydride (D) is one or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride.
The resin composition according to [1] or [2].
[4]
The reaction product (P) is obtained by reacting at least the carboxylic acid (C),
The resin composition according to any one of [1] to [3], wherein the carboxylic acid (C) is one or more selected from the group consisting of maleic acid, phthalic acid, succinic acid, and acetic acid. .
[5]
Further comprising a thermosetting component (E),
The resin composition according to any one of [1] to [4].
[6]
The thermosetting component (E) is one or more selected from the group consisting of a maleimide compound (B), an epoxy resin (F), a cyanate ester compound (G), and an alkenyl-substituted nadiimide (H). Including,
[5] The resin composition according to [5].
[7]
The amino-modified silicone (A) in the reaction product (P) includes a compound represented by the following general formula (1).
The resin composition according to any one of [1] to [6].

(In the formula (1), a plurality of R _{a s} each independently represent a hydrogen atom, a methyl group or a phenyl group, a plurality of R _{b s} each independently represent a single bond, an alkylene group or an aryl group, and n is Represents an integer of 1 or more.)
[8]
The amino group equivalent of the amino-modified silicone (A) in the reaction product (P) is from 130 to 6000,
The resin composition according to any one of [1] to [7].
[9]
The maleimide compound (B) includes bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) ) Including one or more selected from the group consisting of methane, polytetramethylene oxide-bis (4-maleimidobenzoate), and a compound represented by the following general formula (2),
The resin composition according to any one of [1] to [8].

(In the formula (2), 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.)
[10]
Further comprising a filler (J),
The resin composition according to any one of [1] to [9].
[11]
The filler (J) includes one or more selected from the group consisting of silica, alumina, and aluminum nitride.
[10] The resin composition according to [10].
[12]
The resin composition includes 50 parts by mass or more and 300 parts by mass or less of the filler (J) with respect to 100 parts by mass of the total amount of the reaction product (P) and the thermosetting component (E).
The resin composition as described in [10] or [11].
[13]
A base material and the resin composition according to any one of [1] to [12] impregnated or coated on the base material,
Prepreg.
[14]
The substrate 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 prepreg according to [13].
[15]
A support and a resin composition according to any one of [1] to [12] disposed on the surface of the support,
Resin sheet.
[16]
The support is a resin sheet or a metal foil,
The resin sheet according to [15].
[17]
[13] or a plurality of one or more selected from the group consisting of the prepreg according to [14] and the resin sheet according to [15] or [16],
Laminated board.
[18]
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,
Metal foil-clad laminate.
[19]
[1] to [12] comprising an insulating layer containing the resin composition according to any one of the above, and a conductor layer formed on the surface of the insulating layer.
Printed wiring board.
[20]
A first reaction step in which an amino-modified silicone (A) and a maleimide compound (B) are reacted to obtain a primary polymer;
A second reaction step of reacting the primary polymer with at least one of carboxylic acid (C) or carboxylic acid anhydride (D).
A method for producing a resin composition.

  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.

(Resin composition)
The resin composition of this embodiment is a reaction product obtained by reacting amino-modified silicone (A), maleimide compound (B), and at least one of carboxylic acid (C) or carboxylic acid anhydride (D). Product (P) (prepolymer). Here, the reaction product (P) is a kind of the above-described amino-modified polymer.

  The resin composition of the present embodiment has excellent storage stability. This factor is inferred as follows (however, the factor is not limited to this). A conventional resin composition containing an amino-modified silicone and a thermosetting component has a structure in which an amino group, which is a reactive group of a raw material amino-modified silicone, is a prepolymer structure in an amino-modified polymer contained in the resin composition. A relatively large amount thereof remains, and the amino group further reacts with the thermosetting component, so that the resin composition (including varnish) and a molded body obtained from the resin composition (for example, prepreg and In the molded body), excellent storage stability cannot be obtained. For example, when the resin composition is stored at room temperature, due to the further progress of the reaction between the remaining amino groups and the thermosetting component, the resin composition has increased viscosity and molecular weight. Excellent storage stability cannot be obtained. Further, in the case of varnish, gelation occurs, and in the case of prepreg, moldability deteriorates due to an increase in prepreg viscosity, and excellent storage stability cannot be obtained. On the other hand, in the resin composition of the present embodiment, the amino group remaining after the reaction between the amino-modified silicone (A) and the maleimide compound (B) reacts with the carboxylic acid (C) and / or the carboxylic acid anhydride (D). By including the reaction product (P), excellent storage stability is obtained in the resin composition and a molded product obtained from the resin composition.

  The amine value of the resin composition is an amine value as the total amount of primary amine and secondary amine. The amine value is not particularly limited, but is preferably 2.0 mgKOH / g or less, more preferably 1.0 mgKOH / g or less, and further preferably 0.5 mgKOH / g or less. When the amine value is 2.0 mgKOH / g or less, an increase in viscosity of the resin composition, an increase in molecular weight, gelation of varnish, and an increase in prepreg viscosity tend to be suppressed. In addition, the smaller the amine value, the more the viscosity of the resin composition, the increase in molecular weight, etc. tend to be suppressed. The lower limit of the amine value is preferably 0 mgKOH / g. The amine value is measured by a method according to JIS K 7237: 1995.

[Reaction product (P)]
The reaction product (P) of this embodiment is obtained by reacting an amino-modified silicone (A), a maleimide compound (B), and at least one of a carboxylic acid (C) or a carboxylic acid anhydride (D). It is done.

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

  Although the weight average molecular weight (Mw) of reaction product (P) is not specifically limited, Preferably it is 5000 or more and 20000 or less, More preferably, it is 10,000 or more and 15000 or less. When the weight average molecular weight is 5000 or more, the coefficient of thermal expansion of the prepreg tends to decrease, and when the weight average molecular weight is 20000 or less, the viscosity of the resin composition increases, the molecular weight increases, and the varnish gelates. There is a tendency that an increase in the prepreg viscosity can be suppressed. In order to obtain a reaction product (P) having a weight average molecular weight of 5,000 or more and 20,000 or less, reaction conditions such as temperature may be controlled. The weight average molecular weight can be determined as a value measured by a gel permeation chromatography (GPC) method and converted using a standard polystyrene calibration curve. Specifically, it is measured by the method described in Examples described later.

  In the resin composition of the present embodiment, the content of the reaction product (P) is not particularly limited, but when combined with the thermosetting component (E), the reaction product (P) in the resin composition. And the total amount of the thermosetting component (E) (100% by mass; as a solid content not including the solvent / solvent component and filler (J)), preferably 10% by mass to 80% by mass, More preferably, they are 15 mass% or more and 70 mass% or less, and are 20 mass% or more and 60 mass% or less. Printed wiring board with excellent reaction properties (P), excellent moldability even when filled with filler, low thermal expansion coefficient, thermal elastic modulus, desmear resistance, and chemical resistance It tends to be.

式（１）中、複数のＲ_ａは、各々独立に水素原子、メチル基又はフェニル基を表し、中でもメチル基が好ましい。複数のＲ_ｂは、各々独立に単結合、アルキレン基又はアリール基を表し、中でもアルキレン基が好ましい。アルキレン基の炭素数は、その主鎖において１〜４であることが好ましい。具体的なアルキレン基は、特に限定されないが、メチレン基、エチレン基、トリメチレン基、又はテトラメチレン基であることがより好ましく、トリメチレン基であることがさらに好ましい。式（１）中、ｎは１以上の整数を表す。<Amino-modified silicone (A)>
The amino-modified silicone (A) used in the present embodiment is not particularly limited as long as it is a silicone having one or more amino groups in the molecule, but includes a compound represented by the following general formula (1). It is preferable.

In the formula (1), a plurality of R _a each independently represents a hydrogen atom, a methyl group or a phenyl group, and among them, a methyl group is preferable. Several _Rb represents a single bond, an alkylene group, or an aryl group each independently, and an alkylene group is preferable especially. The alkylene group preferably has 1 to 4 carbon atoms in the main chain. The specific alkylene group is not particularly limited, but is preferably a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group, and more preferably a trimethylene group. In formula (1), n represents an integer of 1 or more.

  Amino modified silicone (A) may be used individually by 1 type, and may mix and use 2 or more types.

  The amino group equivalent of the amino-modified silicone (A) is not particularly limited, but is preferably 130 or more and 6000 or less, more preferably 500 or more and 3000 or less, and further preferably 600 or more and 2500 or less. When the amino group equivalent of the amino-modified silicone (A) is within the above range, a printed wiring board having excellent metal foil peel strength and desmear resistance can be obtained. The amino group equivalent is measured by a method according to JIS K 7237: 1995.

  In the resin composition of the present embodiment, the content of the amino-modified silicone (A) is not particularly limited, but the total amount of the reaction product (P) in the resin composition (100% by mass; solvent / solvent component, filler) (J) is preferably 5.0% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 50% by mass or less, and further preferably 15% by mass or more. It is 45 mass% or less. The content of the amino-modified silicone (A) is such that when the reaction product (P) and the thermosetting component (E) are combined, the amino-modified silicone (A) used to produce the reaction product (P). ) And the total amount of the amino-modified silicone (A) contained as the thermosetting component (E), the total amount of the reaction product (P) and the thermosetting component (E) in the resin composition (100% by mass). The solid content not including solvent / solvent component) is preferably 1.0% by mass or more and 70% by mass or less, more preferably 3.0% by mass or more and 40% by mass or less, and still more preferably. It is 5.0 mass% or more and 20 mass% or less. Moreover, when the content of the amino-modified silicone (A) is within the above range, a printed wiring board that is excellent in metal foil peel strength and desmear resistance can be obtained. In addition, in addition to the amino modified silicone (A) used for preparation of the reaction product (P), the content of the amino modified silicone (A) referred to here is as a thermosetting component (E) described later. Amino-modified silicone (A) is also included.

<Maleimide compound (B)>
The maleimide compound (B) 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 general formula (2), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These can be used alone or in admixture of two or more.

  Among them, maleimide compounds (B) include bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-). It preferably contains one or more selected from the group consisting of maleimide phenyl) methane, polytetramethylene oxide-bis (4-maleimidobenzoate), and a maleimide compound represented by the following general formula (2). , 2-bis {4- (4-maleimidophenoxy) -phenyl} propane is more preferable.

式（２）中、複数のＲ_５は、各々独立に水素原子又はメチル基を示し、ｎ_１は、１以上の整数を示す。

In the formula (2), a plurality of R ₅ are each independently a hydrogen atom or a methyl group, n _one represents an integer of 1 or more.

In formula (2), several R < ₅ > shows a hydrogen atom or a methyl group each independently, and it is preferable to show a hydrogen atom especially.

In formula (2), n ₁ represents an integer of 1 or more. The upper limit value of n ₁ is preferably 10, more preferably 7.

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

  In the reaction product (P) of the present embodiment, the content ratio of the maleimide compound (B) to the amino-modified silicone (A) is not particularly limited, but is preferably 1.0 or more and 3.0 or less on a mass basis. More preferably, it is 1.0 or more and 2.5 or less, More preferably, it is 1.0 or more and 2.0 or less. When the content ratio is in the above range, the reaction product (P) productivity tends to be superior.

  In the resin composition of the present embodiment, the content of the maleimide compound (B) is not particularly limited, but the total amount of the reaction product (P) in the resin composition (100% by mass; solvent / solvent component, filler ( J) is preferably 10% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and further preferably 45% by mass or more and 75% by mass with respect to the solid content not including J). It is as follows. Further, the content of the maleimide compound (B) is such that when the reaction product (P) and the thermosetting component (E) are combined, the maleimide compound (B) used for producing the reaction product (P) and As the total amount of maleimide compound (B) contained as thermosetting component (E), the total amount of reaction product (P) and thermosetting component (E) (100% by mass; solvent / solvent component, filler ( J) is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass with respect to the solid content not including J). It is as follows. When the content of the maleimide compound (B) is within the above range, a printed wiring board excellent in moldability, thermal elastic modulus, desmear resistance, and chemical resistance tends to be obtained. In addition, in addition to the maleimide compound (B) used for the reaction product (P), the content of the maleimide compound (B) referred to here includes a maleimide compound (B) as a thermosetting component (E) described later. ) Is also included.

<Carboxylic acid (C), carboxylic acid anhydride (D)>
The carboxylic acid (C) used in the present embodiment is not particularly limited, but is preferably one or more selected from the group consisting of maleic acid, phthalic acid, succinic acid, acetic acid, and propionic acid. More preferably, one or more selected from the group consisting of acid, phthalic acid, succinic acid, and acetic acid, and one or more selected from the group consisting of maleic acid, phthalic acid, and succinic acid More preferably. Further, the carboxylic acid anhydride (D) used in the present embodiment is not particularly limited, but one or two selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, acetic anhydride, and propionic anhydride. It is preferably at least one species, more preferably one or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride, maleic anhydride, phthalic anhydride, And more preferably one or more selected from the group consisting of succinic anhydride.

  Carboxylic acid (C) and carboxylic acid anhydride (D) are monovalent carboxylic acid and monovalent carboxylic acid anhydride, or divalent carboxylic acid and divalent carboxylic acid anhydride, respectively. It is preferable that it is a divalent carboxylic acid and a divalent carboxylic anhydride. Carboxylic acid (C) and carboxylic acid anhydride (D) are a monovalent carboxylic acid and a monovalent carboxylic acid anhydride by being a divalent carboxylic acid and a divalent carboxylic acid anhydride, respectively. Compared to the case, the storage stability of the resin composition is excellent, and a decrease in insulation reliability when a printed wiring board is obtained tends to be suppressed. Although this factor is not particularly limited, when a divalent carboxylic acid or a divalent carboxylic acid anhydride is used, compared with the case where a monovalent carboxylic acid and a monovalent carboxylic acid anhydride are used. When the amino group of the amino-modified silicone (A) reacts with the carboxyl group of the divalent carboxylic acid or divalent carboxylic anhydride, the carboxyl group paired with the reacted carboxyl group is a free carboxylic acid. It is inferred that it is difficult to remain in the resin composition.

  Carboxylic acid (C) and carboxylic acid anhydride (D) may be used singly or as a mixture of two or more. In addition, the carboxylic acid (C) and the carboxylic acid anhydride (D) may be used alone or in combination.

  Moreover, in this embodiment, it is preferable to use only carboxylic carboxylic acid anhydride (D) compared with using only carboxylic acid (C). Thereby, it exists in the tendency which is excellent by storage stability by being excellent by the reactivity with amino modified silicone (A).

  In the reaction product (P) of the present embodiment, the content ratio of the carboxylic acid (C) and the carboxylic anhydride (D) to the amino-modified silicone (A) is not particularly limited, but is preferably 0.00 on the mass basis. It is 01 or more and 0.4 or less, More preferably, it is 0.01 or more and 0.2 or less, More preferably, it is 0.02 or more and 0.1 or less. When the content ratio is within the above range, the storage stability of the reaction product (P) tends to be more excellent.

  In the resin composition of the present embodiment, the content of the carboxylic acid (C) and the carboxylic acid anhydride (D) is not particularly limited, but the total amount of the reaction product (P) (100% by mass; solvent / solvent component, Preferably, it is 0.5% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and still more preferably with respect to the solid content not including the filler (J). It is 1.0 mass% or more and 5.0 mass% or less. Further, the content of the carboxylic acid (C) and the carboxylic acid anhydride (D) is determined when the reaction product (P) and the thermosetting component (E) are combined. Preferably, it is 0.05 mass% or more and 10 mass% or less with respect to the total amount (100 mass%; as a solid content amount which does not contain a solvent and a solvent component and a filler (J)) of the sex component (E). Preferably they are 0.1 mass% or more and 5.0 mass% or less, More preferably, they are 0.2 mass% or more and 2.0 mass% or less. When the content of the carboxylic acid (C) and the carboxylic acid anhydride (D) is within the above range, it is possible to obtain a printed wiring board that is more excellent in moldability, thermal elastic modulus, desmear resistance, and chemical resistance. It tends to be possible.

[Thermosetting component (E)]
It is preferable that the resin composition of this embodiment further contains a thermosetting component (E).

  The thermosetting component (E) used in the present embodiment is not particularly limited as long as it is a component that is cured by heat. Although it does not specifically limit as a thermosetting component (E), For example, in addition to the amino modified silicone (A) mentioned above and a maleimide compound (B), the epoxy resin (F) mentioned later and a cyanate ester compound (G) And alkenyl-substituted nadiimide (H). That is, the amino-modified silicone (A) and maleimide compound (B) used as the thermosetting component (E) can be the same as the amino-modified silicone (A) and maleimide compound (B) described above. . Among these, the thermosetting component (E) is one or two selected from the group consisting of a maleimide compound (B), an epoxy resin (F), a cyanate ester compound (G), and an alkenyl-substituted nadiimide (H). It is preferable to include the above, and it is more preferable to include a maleimide compound (B).

  In the resin composition of the present embodiment, the content of the thermosetting component (E) is not particularly limited, but when the reaction product (P) and the thermosetting component (E) are combined, the reaction product ( It is preferably 20% by mass or more and 85% by mass or less with respect to the total amount of P) and the thermosetting component (E) (100% by mass; solid content not including solvent / solvent component and filler (J)). Yes, more preferably 30% by mass to 85% by mass, and still more preferably 40% by mass to 80% by mass. When the content of the thermosetting component (E) is within the above range, it tends to be a printed wiring board that is excellent in moldability even when filled with a filler, and has excellent thermal modulus, desmear resistance, and chemical resistance. It is in.

<Epoxy resin (F)>
By including the epoxy resin (F), 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 (F) 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.

  Among these, the epoxy resin (F) is preferably at least one selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, a polyfunctional phenol type epoxy resin, and a naphthalene type epoxy resin. By including such an epoxy resin (F), the flame retardancy and heat resistance of the resulting cured product tend to be further improved.

  An epoxy resin (F) may be used individually by 1 type, and may mix and use 2 or more types.

  In the resin composition of the present embodiment, the content of the epoxy resin (F) is not particularly limited, but the total amount of the reaction product (P) and the thermosetting component (E) (100% by mass; solvent / solvent component) The solid content does not include the filler (J), preferably 1.0% by mass or more and 20% by mass or less, more preferably 1.0% by mass or more and 15% by mass or less, and still more preferably. Is 2.0 mass% or more and 10 mass% or less. When the content of the epoxy resin (F) is within the above range, it tends to be more excellent in adhesiveness and flexibility.

<Cyanate ester compound (G)>
Although it does not specifically limit as cyanate ester compound (G) used for this embodiment, For example, the naphthol aralkyl type | mold cyanate ester represented by following General formula (3), the novolak represented by following General formula (4) 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'-dicyanatobiphe Nyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2-bis (4-cyanatophenyl) propane.

  Among these, the naphthol aralkyl cyanate ester compound represented by the following general formula (3), the novolak cyanate ester and the biphenyl aralkyl cyanate ester represented by the following general formula (4) are excellent in flame retardancy, A naphthol aralkyl cyanate compound represented by the following general formula (3) and a novolac cyan represented by the following general formula (4) are preferable because of high curability and a low thermal expansion coefficient of the cured product. One or more selected from the group consisting of acid esters are more preferred.

式（３）中、複数のＲ_６は、各々独立に水素原子又はメチル基を示し、ｎ_２は、１以上の整数を示す。

In the formula (3), 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 formula (3), several R < ₆ > shows a hydrogen atom or a methyl group each independently, and it is preferable to show a hydrogen atom especially.

Wherein (3), _{n 2} represents an integer of 1 or more. The upper limit value of n ₂ is preferably 10, more preferably 6.

式（４）中、複数のＲ_７は、各々独立に水素原子又はメチル基を示し、複数のＲ_８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、ｎ_３は、１以上の整数を示す。

In the formula (4), each of the plurality of R ₇ independently represents a hydrogen atom or a methyl group, and each of the plurality of R ₈ independently represents 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.

In formula (4), several R < ₇ > shows a hydrogen atom or a methyl group each independently, and it is preferable to show a hydrogen atom especially.

In formula (4), several R < ₈ > shows a hydrogen atom or a C1-C4 alkyl group or alkenyl group each independently.

In formula (4), 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, it can be obtained by reacting a naphthol aralkyl type phenol resin represented by the following general formula (5) with cyanogen halide in an inert organic solvent in the presence of a basic compound. 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（５）中、複数のＲ_６は、各々独立に水素原子又はメチル基を示し、ｎ_４は、１以上の整数を示す。

In the formula (5), 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 formula (5), several R < ₆ > shows a hydrogen atom or a methyl group each independently, and a hydrogen atom is preferable especially.

Wherein (5), _{n 4} represents an integer of 1 or more. 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- It can be selected from those obtained by condensing naphthol aralkyl resin obtained by reaction with 2-propyl) benzene or the like and cyanic acid.

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

  In the resin composition of the present embodiment, the content of the cyanate ester compound (G) is not particularly limited, but the total amount of the reaction product (P) and the thermosetting component (E) (100% by mass; solvent · Preferably, it is 0.005% by mass or more and 5.0% by mass or less, and more preferably 0.005% by mass or more and 3.0% by mass with respect to the solid content not including the solvent component and filler (J). It is below, More preferably, they are 0.1 mass% or more and 1.0 mass% or less. When the content of the cyanate ester compound (G) 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 (H)>
The alkenyl-substituted nadiimide (F) 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 (6).

In formula (6), 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 (7) or (8).

In Formula (7), R ₃ represents a substituent represented by a methylene group, an isopropylidene group, CO, O, S, or SO ₂ .

In the formula (8), 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 (6). 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 (9), the compound represented by following formula (10) (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)).

  An alkenyl substituted nadiimide (H) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In the resin composition of the present embodiment, the content of the alkenyl-substituted nadiimide (H) is not particularly limited, but the total amount (100% by mass; solvent / solvent) of the reaction product (P) and the thermosetting component (E) Preferably, it is 5.0% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and still more preferably. It is 20 mass% or more and 40 mass% or less. When the content of the alkenyl-substituted nadiimide (H) 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 epoxy resin (F), cyanate ester compound (G), and alkenyl-substituted nadiimide (H) described above may be used as raw materials for the reaction product (P).

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

  Moreover, in the resin composition of this embodiment, it is also possible to add other resin in addition to the reaction product (P) and the thermosetting component (E) as long as the 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, properties such as metal adhesion and stress relaxation can be imparted.

[Filler (J)]
It is preferable that the resin composition of this embodiment further contains a filler (J). The filler (J) is not particularly limited as long as it has insulating properties. Examples thereof include silicas such as natural silica, fused silica, amorphous silica, and hollow silica; alumina, aluminum nitride, boron nitride, boehmite, and oxidation. Molybdenum, titanium oxide, zinc borate, zinc stannate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (glass fine powders such as E glass and D glass), hollow glass, And inorganic fillers such as spherical glass, and organic fillers such as silicone rubber and silicone composite powder. These can be used alone or in combination of two or more.

  Among these, the filler (J) preferably contains one or more selected from the group consisting of silica from the viewpoint of low thermal expansion, alumina from the viewpoint of high thermal conductivity, and aluminum nitride.

  The content of the filler (J) in the resin composition of the present embodiment is not particularly limited, but the reaction product (P) and heat in the case where the reaction product (P) and the thermosetting component (E) are combined. The total amount of the curable component (E) (100 parts by mass; as a solid content not including the solvent / solvent component and filler (J)) or the reaction product (P) when only the reaction product (P) is used. Including the filler (J) in an amount of 50 to 300 parts by mass with respect to the total amount (100 parts by mass; solid content not including the solvent / solvent component and filler (J)) From the viewpoint of characteristics such as conduction, it is more preferably 100 parts by mass or more and 300 parts by mass or less, and further preferably 100 parts by mass or more and 250 parts by mass or less.

[Silane coupling agent, wetting and dispersing agent]
In the resin composition of the present embodiment, a silane coupling agent and / or a wet dispersing agent can be used in combination in order to improve the dispersibility of the fine particles of the filler and the adhesive strength between the resin and the fine particles or the glass cloth. is there. 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; phenylaryls such as styrylsilane; Silane-based silane coupling agents can be mentioned, and one or two or more can be used in appropriate combination. The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for coatings. Specific examples include wet dispersing agents such as DISPER-BYK110, 111, 118, 180, 161, BYK-W996, W9010, and W903 under the trade names of Big Chemie Japan Co., Ltd.

[Curing accelerator]
In the resin composition of this embodiment, a curing accelerator can be used in combination as long as the 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]
The method for producing the resin composition of the present embodiment is obtained by reacting amino-modified silicone (A), maleimide compound (B), and at least one of carboxylic acid (C) or carboxylic anhydride (D). The obtained reaction product (P) can be obtained as a resin composition as it is. Moreover, the resin composition can be obtained by mixing the obtained reaction product (P) and the thermosetting component (B). Furthermore, other optional components may be mixed as necessary.

  Although the manufacturing method of the resin composition of this embodiment is not specifically limited, As a preferable aspect, the first reaction step (hereinafter, referred to as “primary polymer”) is obtained by reacting amino-modified silicone (A) with maleimide compound (B). Simply referred to as “first reaction step”), a second reaction step (hereinafter simply referred to as “second reaction step”) in which the primary polymer is reacted with at least one of carboxylic acid (C) and carboxylic acid anhydride (D). It is preferable from the viewpoint of obtaining better storage stability of the reaction product (P).

  The reaction temperature in the first reaction step is not particularly limited as long as the reaction between the amino-modified silicone (A) and the maleimide compound (B) proceeds, but is preferably 50 ° C to 200 ° C, preferably 100 ° C to More preferably, the temperature is 150 ° C.

  The viscosity of the primary polymer obtained by the first reaction step provided in the second reaction step is preferably 100 to 500 mPa · s from the viewpoint of obtaining better storage stability of the reaction product (P). 150 mPa · s to 400 mPa · s is more preferable. In addition, the measuring method of the viscosity of a primary polymer is not specifically limited, It can measure using a general viscometer. For example, it can be measured using a cone plate viscometer (for example, ICI viscometer).

  Although the reaction temperature in a 2nd reaction process is not specifically limited, It is preferable that it is 50 to 200 degreeC, and it is more preferable that it is 100 to 150 degreeC. Although reaction time is not specifically limited, Preferably it is 0.5 hour-5 hours, More preferably, it is 1.5 hours-3.5 hours.

  Naturally, in the method for producing the resin composition of the present embodiment, the amino-modified silicone (A), the maleimide compound (B), and at least one of the carboxylic acid (C) and the carboxylic acid anhydride (D) are reacted simultaneously. You may let them. That is, you may perform a 1st reaction process and a 2nd reaction process simultaneously.

  In the first step and the second step, the amino-modified silicone (A), the maleimide compound (B), at least one of the carboxylic acid (C) and the carboxylic acid anhydride (D), and the primary polymer have these handling properties. In order to improve, it is preferable to be diluted with a solvent. The type of the solvent is not particularly limited, and examples thereof include 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. Can be mentioned. A solvent can be used 1 type or in combination of 2 or more types.

  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. In uniformly dispersing the filler such as the filler (J), the dispersibility with respect to the resin composition is enhanced by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. 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 fillers and additive components) with respect to the total amount (100% by mass) of the prepreg is not particularly limited, but is 30% by mass to 90% by mass. A range 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); 2, 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 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. It is a resin sheet which apply | coated the above-mentioned resin composition to the single side | surface or both surfaces of a support body. Here, the resin sheet is used as one means of thinning, for example, a thermosetting resin (including a filler) used for a prepreg directly on a support such as a metal foil or a film. It can be produced by coating and drying.

  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 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, and then the required number of the above-mentioned prepregs are stacked on the inner layer circuit surface. 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.

式中、Ｎは、ポリマー分子の数を示し、Ｍは、分子量を示し、Ｃは、試料濃度を示す。試料濃度Ｃは、モノマーの単位数に比例するため、Ｃ＝Ｍ×Ｎとなる。[Weight average molecular weight]
The weight average molecular weight of the reaction product was measured by gel permeation chromatography (GPC) method using the resin compositions obtained in the following examples and comparative examples as samples, and converted using a standard polystyrene calibration curve. Calculated as Specifically, the relationship between the elution time from the column and the molecular weight is obtained in advance, and based on this, the elution time is replaced with the molecular weight. A graph showing “relation between elution time and molecular weight” used at this time is called “calibration curve” (or calibration curve). Since the “relationship between the elution time and the molecular weight” varies depending on the type of polymer, in principle, it is necessary to use a standard polymer having the same structure as the measurement object and a narrow molecular weight distribution with a known molecular weight. However, since practically most cases are difficult, a commercially available standard polymer is actually used. Here, polystyrene is used as the standard polymer. The molecular weight obtained in this way is referred to as a standard equivalent molecular weight. From this, the weight average molecular weight (Mw) is calculated from the following formula.

In the formula, N represents the number of polymer molecules, M represents the molecular weight, and C represents the sample concentration. Since the sample concentration C is proportional to the number of monomer units, C = M × N.

[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.

ｎ_４は、１以上の整数を示す。An α-naphthol aralkyl type phenol resin (SN485, OH group equivalent) in which R ₆ in Formula (5) all represents a hydrogen atom with stirring while maintaining 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.

n ₄ represents an integer of 1 or more.

  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 cyanate ester resin) was obtained.

[Example 1]
25 parts by mass of a maleimide compound (maleimide group equivalent 285 g / eq, trade name “BMI-80” manufactured by Kay Kasei Co., Ltd.) is heated to 40 parts by mass of propylene glycol monomethyl ether (KH Neochem) under conditions of heating to reflux 130 ° C. 15 parts by mass of diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, trade name “X-22-161B” manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in the solution dissolved below. A polymer was prepared. Thereafter, stirring was continued under the condition of a heating reflux temperature of 130 ° C., and when the viscosity of the primary polymer increased to 200 to 300 mPa · s with an ICI viscometer (cone plate viscometer, manufactured by Towa Industries Co., Ltd.), And a solution prepared by dissolving 1.0 part by mass of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) with 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by Dow Chemical Co., Ltd.) The reaction was allowed to proceed for several hours while leaving the resin composition containing the reaction product. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A part of the resin composition was stored for 7 days at 25 ° C., and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 2]
A reaction product having a weight average molecular weight of 13200 is contained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride is changed to 1.0 part by mass of acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). A resin composition was obtained. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A part of the resin composition was stored for 7 days at 25 ° C., and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 3]
A reaction product having a weight average molecular weight of 12500 was obtained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride was changed to 1.0 part by mass of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). A resin composition containing was obtained. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A part of the resin composition was stored for 7 days at 25 ° C., and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 4]
A reaction product having a weight average molecular weight of 12000 is contained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride is changed to 1.0 part by mass of maleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). A resin composition was obtained. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A part of the resin composition was stored for 7 days at 25 ° C., and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Example 5]
A resin composition containing a reaction product having a weight average molecular weight of 11710 was obtained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride was changed to 0.5 part by mass of maleic anhydride. . Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A part of the resin composition was stored for 7 days at 25 ° C., and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Comparative Example 1]
Resin composition containing a reaction product having a weight average molecular weight of 13900 by the same method as in Example 1 except that 1.0 part by weight of maleic anhydride and 22.5 parts by weight of propylene glycol monoethyl ether acetate were not used I got a thing. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A part of the resin composition was stored for 7 days at 25 ° C., and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

[Comparative Example 2]
A resin composition containing a reaction product having a weight average molecular weight of 14100 was obtained in the same manner as in Example 1 except that 1.0 part by mass of maleic anhydride was not used. Using a part of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A part of the resin composition was stored for 7 days at 25 ° C., and the weight average molecular weight of the reaction product after storage was measured. The results are shown in Table 1.

  In Table 1, “Increase rate” is the ratio (%) of the weight average molecular weight of the resin composition after storage for 7 days to the weight average molecular weight of the resin composition before storage. In addition, the “weight average molecular weight” of the resin composition before storage is not a value obtained by measurement immediately after obtaining each resin composition, but obtained by measurement on the day of obtaining each resin composition. Value. Therefore, the initial storage stability can be compared from the result of “weight average molecular weight” in Table 1.

[Example 6]
41.0 parts by mass of the resin composition obtained in Example 1, 30 parts by mass of a maleimide compound (maleimide group equivalent 186 g / eq, trade name “BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd.), and a biphenyl novolac type epoxy 4.5 parts by mass of resin (trade name “NC-3000FH” manufactured by Nippon Kayaku Co., Ltd.) and bisdiallyl nadiimide (alkenyl group equivalent 286 g / eq, trade name “BANI-M” manufactured by Maruzen Petrochemical Co., Ltd.) 25 0.5 parts by mass of cyanate esterified product of α-naphthol aralkyl type phenol resin obtained in Synthesis Example 1 above, and 200 parts by mass of slurry silica (trade name “SC-2050MB” manufactured by Admatechs) And 5 parts by mass of an epoxy silane coupling agent (trade name “Z6040” manufactured by Toray Dow Coating Co., Ltd.) and triphenylimi which is a curing accelerator Tetrazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed with 0.5 part by weight of the resin composition.

[Comparative Example 3]
A resin composition was obtained in the same manner as in Example 6 except that 41.0 parts by mass of the resin composition obtained in Example 1 was replaced with 40.0 parts by mass of the resin composition obtained in Comparative Example 2. It was.

[Amine value]
About each resin composition obtained in Example 6 and Comparative Example 3, the amine value was measured. Specifically, based on JIS K 7237: 1995, the amine value was measured as the total amount of primary amine and secondary amine of the resin composition. The results are shown in Table 2.

[Preparation of prepreg]
Varnishes were obtained by diluting the resin compositions obtained in Example 6 and Comparative Example 3 with methyl ethyl ketone. This varnish is impregnated and coated on a T glass cloth (T2118), dried by heating at 150 ° C. for 3 minutes, and the content of the resin composition so that the insulating layer has a thickness of 100 μm when the following laminate is obtained ( Mass%) was adjusted to obtain a prepreg.

[Varnish gel time]
A gel time (second) at 170 ° C. was measured using a part of each varnish obtained at the time of producing the prepreg described above as a sample. A part of the varnish was stored for 7 days at 25 ° C., and the gel time (seconds) after storage was measured in the same manner as described above. The results are shown in Table 2.

[Prepreg viscosity]
The resin content is obtained from the prepreg prepared by the above-mentioned method, and using a dynamic viscoelasticity measuring apparatus (trade name “AR2000” manufactured by TA Instruments Inc.), the angular velocity is 1 rad / s and the geometry gap is 1 mm. The viscosity (mPa · s) under the measurement condition of 120 ° C. was measured. Moreover, the prepreg mentioned above was preserve | saved for seven days on 25 degreeC conditions, resin content was acquired from the prepreg after preservation | save, and shear viscosity (mPa * s) was measured similarly to the above. The results are shown in Table 2.

[Laminated board]
A 12 μm thick electrolytic copper foil (trade name “3EC-III” manufactured by Mitsui Kinzoku Mining Co., Ltd.) is placed on the top and bottom of one prepreg obtained, and laminated molding is performed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes. To obtain a copper-clad laminate (molded before storage) having an insulating layer thickness of 100 μm. Further, the obtained prepreg was stored for 7 days under the condition of 25 ° C., and was laminated by the same method as described above using one prepreg after storage, and a copper-clad laminate (storage) having an insulating layer thickness of 100 μm After molding) was obtained.

[Coefficient of thermal expansion]
Each copper-clad laminate obtained (molded before storage and molded after storage) was etched on the entire surface to remove the copper foil, and then used at 40 to 340 ° C. using a thermomechanical analyzer (TA Instruments). The temperature was increased at a rate of 10 ° C. per minute until 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 results are shown in Table 3.

  This application consists of a Japanese patent application (Japanese Patent Application No. 2006-076144) filed with the Japan Patent Office on April 5, 2016, and a Japanese patent application filed with the Japan Patent Office on January 5, 2017. (Japanese Patent Application No. 2017-000666), the contents of which are incorporated herein by reference.

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

Claims (20)

Amino-modified silicone (A);
A maleimide compound (B);
A reaction product (P) obtained by reacting at least one of carboxylic acid (C) and carboxylic acid anhydride (D),
Resin composition.   The resin composition of Claim 1 whose amine value of the said resin composition is 2.0 mgKOH / g or less. The reaction product (P) is obtained by reacting at least the carboxylic acid anhydride (D),
The carboxylic anhydride (D) is one or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride.
The resin composition according to claim 1 or 2. The reaction product (P) is obtained by reacting at least the carboxylic acid (C),
The carboxylic acid (C) is one or more selected from the group consisting of maleic acid, phthalic acid, succinic acid, and acetic acid.
The resin composition as described in any one of Claims 1-3. Further comprising a thermosetting component (E),
The resin composition as described in any one of Claims 1-4. The thermosetting component (E) is one or more selected from the group consisting of a maleimide compound (B), an epoxy resin (F), a cyanate ester compound (G), and an alkenyl-substituted nadiimide (H). Including,
The resin composition according to claim 5. The amino-modified silicone (A) in the reaction product (P) includes a compound represented by the following general formula (1).
The resin composition as described in any one of Claims 1-6.

(In the formula (1), a plurality of R _{a s} each independently represent a hydrogen atom, a methyl group or a phenyl group, a plurality of R _{b s} each independently represent a single bond, an alkylene group or an aryl group, and n is Represents an integer of 1 or more.) The amino group equivalent of the amino-modified silicone (A) in the reaction product (P) is from 130 to 6000,
The resin composition as described in any one of Claims 1-7. The maleimide compound (B) includes bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) ) Including one or more selected from the group consisting of methane, polytetramethylene oxide-bis (4-maleimidobenzoate), and a compound represented by the following general formula (2),
The resin composition as described in any one of Claims 1-8.

(In the formula (2), 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.) Further comprising a filler (J),
The resin composition as described in any one of Claims 1-9. The filler (J) includes one or more selected from the group consisting of silica, alumina, and aluminum nitride.
The resin composition according to claim 10. The resin composition includes 50 parts by mass or more and 300 parts by mass or less of the filler (J) with respect to 100 parts by mass of the total amount of the reaction product (P) and the thermosetting component (E).
The resin composition according to claim 10 or 11. A base material and the resin composition according to any one of claims 1 to 12 impregnated or coated on the base material,
Prepreg. The substrate 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 prepreg according to claim 13. A support and a resin composition according to any one of claims 1 to 12 disposed on a surface of the support,
Resin sheet. The support is a resin sheet or a metal foil,
The resin sheet according to claim 15. 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,
Laminated board. One or two 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.
Metal foil-clad laminate. An insulating layer comprising the resin composition according to any one of claims 1 to 12, and a conductor layer formed on a surface of the insulating layer.
Printed wiring board. A first reaction step in which an amino-modified silicone (A) and a maleimide compound (B) are reacted to obtain a primary polymer;
A second reaction step of reacting the primary polymer with at least one of carboxylic acid (C) or carboxylic acid anhydride (D).
A method for producing a resin composition.