JP2023116516A - Resin composition and method for producing the same, prepreg, resin sheet, laminate, metal-foil-clad laminate, and printed wiring board - Google Patents

Abstract

To provide a resin composition having high storage stability while comprising an amino-modified polymer.SOLUTION: The present invention provides a resin composition including a reaction product (P) obtained by reacting an amino-modified silicone (A), a maleimide compound (B), and one or more selected from the group consisting of carboxylic acids (C) and carboxylic anhydrides (D).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a resin composition and its manufacturing method, a prepreg, a resin sheet, a laminate, a metal foil-clad laminate, and a printed wiring board.

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

One of the countermeasures is to reduce the thermal expansion of insulating layers used in printed wiring boards. This is a method of suppressing warpage by bringing the coefficient of thermal expansion of a printed wiring board closer to that of a semiconductor element, and is currently being actively pursued (see Patent Documents 1 to 3, for example).

In addition to lowering the thermal expansion of the printed wiring board, methods for suppressing warping of semiconductor plastic packages include increasing the rigidity of the laminate (high rigidity) and increasing the glass transition temperature of the laminate (high Tg (for example, see Patent Documents 4 and 5).

JP 2013-216884 A Japanese Patent No. 3173332 Japanese Patent Application Laid-Open No. 2009-035728 JP 2013-001807 A JP 2011-178992 A

However, even in printed wiring boards using thermosetting resin compositions as described in Patent Documents 1 to 5, the peel strength of laminates laminated with metal foils and chemical resistance to, for example, strong alkaline cleaning solutions Since it is difficult to achieve compatibility with other properties such as (anti-desmear property), there remains the problem of warping of 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, a low elastic component such as an amino-modified silicone and a thermosetting component are added to the resin composition by reacting with each other. can contain an amino-modified polymer that However, amino-modified polymers generally have the property of further polymerizing with each other or with other resin components. For this reason, excellent storage stability may not be obtained due to further polymerization reaction of the amino-modified polymer during storage or molding of the resin composition or prepreg.

Accordingly, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a resin composition containing an amino-modified polymer and having excellent storage stability.

（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、１
３０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 a carboxylic acid (C) or a carboxylic 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 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),
[1] The resin composition according to any one of [4].
[6]
The thermosetting component (E) is one or more selected from the group consisting of maleimide compounds (B), epoxy resins (F), cyanate ester compounds (G), and alkenyl-substituted nadimides (H). include,
The resin composition according to [5].
[7]
The amino-modified silicone (A) in the reaction product (P) has the following general formula (1)
Including the compound represented by
The resin composition according to any one of [1] to [6].

(In formula (1), a plurality of R _a each independently represents a hydrogen atom, a methyl group or a phenyl group, a plurality of R _b each independently represents a single bond, an alkylene group or an aryl group, n is represents an integer greater than or equal to 1.)
[8]
The amino group equivalent of the amino-modified silicone (A) in the reaction product (P) is 1
30 or more and 6000 or less,
[1] The resin composition according to any one of [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)methane, polytetramethylene oxide-bis(4-maleimidobenzoate), and one or more selected from the group consisting of compounds represented by the following general formula (2),
[1] The resin composition according to any one of [8].

(In 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);
[1] The resin composition according to any one of [9].
[11]
The filler (J) contains one or more selected from the group consisting of silica, alumina, and aluminum nitride.
The resin composition according to [10].
[12]
The resin composition contains 50 parts by mass or more and 300 parts by mass or less of the filler (J) with respect to the total amount of 100 parts by mass of the reaction product (P) and the thermosetting component (E).
The resin composition according to [10] or [11].
[13]
Having a base material and the resin composition according to any one of [1] to [12] impregnated or applied to 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]
Having a support and the 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 metal foil,
The resin sheet according to [15].
[17]
prepreg according to [13] or [14] and 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]
An insulating layer containing the resin composition according to any one of [1] to [12], and a conductor layer formed on the surface of the insulating layer,
printed wiring board.
[20]
a first reaction step of reacting an amino-modified silicone (A) with a maleimide compound (B) to obtain a primary polymer;
a second reaction step of reacting the primary polymer with at least one of carboxylic acid (C) or carboxylic anhydride (D);
A method for producing a resin composition.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated 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 and implemented within the scope of the gist thereof.

[Resin composition]
The resin composition of the present embodiment comprises an amino-modified silicone (A) and a maleimide compound (B)
with at least one of carboxylic acid (C) or carboxylic acid anhydride (D), reaction product (P) (prepolymer) obtained by reacting. Here, the reaction product (P) is one of the above amino-modified polymers.

The resin composition of this 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 prepolymer structure in which amino groups, which are reactive groups of the starting amino-modified silicone, are present in the amino-modified polymer contained in the resin composition. A relatively large amount remains in the resin composition (
(including varnish) and molded articles obtained from the resin composition (for example, prepregs and molded articles thereof) do not exhibit excellent storage stability. For example, when the resin composition is stored at room temperature, due to further progress of the reaction between the remaining amino groups and the thermosetting component,
The resin composition cannot obtain excellent storage stability due to an increase in viscosity and an increase in molecular weight. Moreover, in the case of varnish, gelation occurs, and in the case of prepreg, the viscosity of the prepreg increases, resulting in poor moldability and poor storage stability. On the other hand, in the resin composition of the present embodiment, the amino groups remaining after the reaction between the amino-modified silicone (A) and the maleimide compound (B) react with the carboxylic acid (C) and/or the carboxylic anhydride (D). By containing the reaction product (P), the resin composition and the molded article obtained from the resin composition have excellent storage stability.

The amine value of the resin composition is the total amount of primary amine and secondary amine. Although the amine value is not particularly limited, it is preferably 2.0 mgKOH/g or less, more preferably 1.0 mgKOH/g or less, and still more preferably 0.5 mgKOH/g or less. When the amine value is 2.0 mgKOH/g or less, it tends to be possible to suppress an increase in the viscosity of the resin composition, an increase in the molecular weight, gelation of the varnish, and an increase in the prepreg viscosity.
In addition, the smaller the amine value, the more likely it is that an increase in the viscosity of the resin composition and an increase in the molecular weight can be suppressed. The lower limit of the amine value is preferably 0 mgKOH/g. The amine value is JI
It is measured by a method according to S K 7237:1995.

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

The reaction product (P) may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the reaction product (P) is not particularly limited, but preferably 50
It is 00 or more and 20000 or less, more preferably 10000 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.
It tends to suppress increase in molecular weight, varnish gelation, and increase in prepreg viscosity. In order to obtain a reaction product (P) having a weight average molecular weight of 5000 or more and 20000 or less, reaction conditions such as temperature may be controlled. The weight average molecular weight can be obtained 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 the solid content not including the solvent/solvent component and the filler (J)), preferably 10% by mass or more and 80% by mass or less, More preferably, it is 15% by mass or more and 70% by mass or less, and 20% by mass or more and 60% by mass or less. The content of the reaction product (P) is within the above range, so that the printed wiring board has excellent moldability even when the filler is filled, and has a low coefficient of thermal expansion, a thermal elastic modulus, desmear resistance, and excellent chemical resistance. 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 compounds represented by the following general formula (1). is preferred.

In formula (1), a plurality of R _a 's each independently represent a hydrogen atom, a methyl group or a phenyl group, with a methyl group being preferred. A plurality of _Rb 's each independently represents a single bond, an alkylene group or an aryl group, with an alkylene group being preferred. The number of carbon atoms in the alkylene group is 1 in its main chain
~4 is preferred. A specific alkylene group is not particularly limited, but is more preferably a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group, and still more preferably a trimethylene group. In formula (1), n represents an integer of 1 or more.

Amino-modified silicone (A) may be used alone or in combination of two or more.

The amino group equivalent of the amino-modified silicone (A) is not particularly limited, but preferably 13
It is 0 or more and 6000 or less, more preferably 500 or more and 3000 or less, and still more preferably 600 or more and 2500 or less. When the amino group equivalent of the amino-modified silicone (A) is within the above range, it is possible to obtain a printed wiring board that is more excellent in metal foil peel strength and desmear resistance. An amino group equivalent is measured by the method based on JISK7237:1995.

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,
It 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 still more preferably 15% by mass, based on the solid content not including the filler (J). % or more and 45 mass % or less. In addition, the content of the amino-modified silicone (A) is the amino-modified silicone (A ) 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 ; preferably 1.0% by mass or more and 70% by mass or less, more preferably 3.0% by mass, based on the amount of solid content not including solvent / solvent component)
40 mass % or less, more preferably 5.0 mass % or more and 20 mass % or less.
In addition, when the content of the amino-modified silicone (A) is within the above range, it is possible to obtain a printed wiring board that is more excellent in metal foil peel strength and desmear resistance. The content of the amino-modified silicone (A) referred to here includes the amino-modified silicone (A) used in the preparation of the reaction product (P), as well as the thermosetting component (E) described later. Amino-modified silicones (A) are also included.

<Maleimide compound (B)>
The maleimide compound (B) used in this 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), a maleimide compound represented by the following general formula (2), a prepolymer of these maleimide compounds,
and prepolymers of maleimide compounds and amine compounds. These may be used singly or in admixture of two or more.

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

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 formula (2), a plurality of _R5 's each independently represents a hydrogen atom or a methyl group, and _n1 represents an integer of 1 or more.

In formula (2), a plurality of R ₅ each independently represent a hydrogen atom or a methyl group, preferably a hydrogen atom.

In formula (2), _n1 represents an integer of 1 or more. The upper limit of _n1 is preferably 10, more preferably 7.

The maleimide compound (B) may be used alone or in combination of two or more.

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 1.0 or more and 2.5 or less, and still more preferably 1.0.
It is 0 or more and 2.0 or less. When the content ratio is within the above range, the productivity of the reaction product (P) tends to be more excellent.

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 still more preferably 45
It is more than mass % and below 75 mass %. In addition, the content of the maleimide compound (B) is the maleimide compound (B) and the Maleimide compound (
B) as the total amount of the reaction product (P) and the total amount of the thermosetting component (E) (100% by mass
; as the solid content not including the solvent/solvent component and filler (J)), 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 even more preferably 30% by mass or more and 70% by mass or less. When the content of the maleimide compound (B) is within the above range, it tends to be possible to obtain a printed wiring board that is more excellent in moldability, thermal elastic modulus, desmear resistance, and chemical resistance. The content of the maleimide compound (B) referred to here includes the maleimide compound (B) used in the reaction product (P) and the maleimide compound (B) as a thermosetting component (E) described later. ) are also included.

<Carboxylic Acid (C), Carboxylic 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. It is 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. is more preferable. In addition, the carboxylic 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 one or more species, more preferably one or two or more selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride, maleic anhydride, phthalic anhydride, and succinic anhydride.

Carboxylic acid (C) and carboxylic anhydride (D) are monovalent carboxylic acid and monovalent carboxylic anhydride, or divalent carboxylic acid and divalent carboxylic anhydride among those mentioned above, respectively. is preferred, and divalent carboxylic acids and divalent carboxylic acid anhydrides are more preferred. Carboxylic acid (C) and carboxylic anhydride (D) are respectively a divalent carboxylic acid and a divalent carboxylic anhydride, thereby being a monovalent carboxylic acid and a monovalent carboxylic anhydride Compared with the case, the storage stability of the resin composition is more excellent, and there is a tendency that deterioration in insulation reliability when used as a printed wiring board can be suppressed. This factor is not particularly limited, but when using a divalent carboxylic acid or a divalent carboxylic anhydride, compared to using a monovalent carboxylic acid and a monovalent carboxylic anhydride , When the amino group of the amino-modified silicone (A) reacts with the carboxyl group of the divalent carboxylic acid or divalent carboxylic acid anhydride, the carboxyl group paired with the reacted carboxyl group becomes a free carboxylic acid. It is speculated that this is due to the fact that it is difficult to remain in the resin composition as.

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

Moreover, in the present embodiment, using only the carboxylic acid anhydride (D) is preferable to using only the carboxylic acid (C). As a result, the reactivity with the amino-modified silicone (A) is improved, and the storage stability tends to be improved.

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.
It is preferably 0.01 or more and 0.4 or less, more preferably 0.01 or more and 0.2 or less, and still more preferably 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 contents of carboxylic acid (C) and carboxylic anhydride (D) are not particularly limited, but the total amount of reaction product (P) (100% by mass; solvent/solvent component, Preferably 0.5 mass% or more 20
% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and still more preferably 1.0% by mass or more and 5.0% by mass or less. In addition, the contents of the carboxylic acid (C) and the carboxylic anhydride (D) can be Based on the total amount of the organic component (E) (100% by mass; as the solid content excluding solvent/solvent component and filler (J)), preferably 0.05% by mass or more1
It is 0 mass % or less, more preferably 0.1 mass % or more and 5.0 mass % or less, and still more preferably 0.2 mass % or more and 2.0 mass % or less. When the contents of the carboxylic acid (C) and the carboxylic anhydride (D) are within the above ranges, it is possible to obtain a printed wiring board having excellent moldability, thermal elastic modulus, desmear resistance, and chemical resistance. tend to be able.

[Thermosetting component (E)]
The resin composition of the present embodiment preferably 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. The thermosetting component (E) is not particularly limited.
cyanate ester compounds (G), and alkenyl-substituted nadimides (H). That is, as the amino-modified silicone (A) and the maleimide compound (B) used as the thermosetting component (E), the same amino-modified silicone (A) and maleimide compound (B) as described above can be used. . Among them, the thermosetting component (E) is a maleimide compound (B
), epoxy resin (F), cyanate ester compound (G), and alkenyl-substituted nadimide (H). more preferred.

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

<Epoxy resin (F)>
By containing 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. 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 include 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 phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkyl novolac type epoxy resin resins, naphthol aralkyl novolac type epoxy resins, aralkyl novolac type epoxy resins, biphenylaralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, butadiene, etc. Compounds obtained by epoxidizing double bonds, compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin, and halides thereof can be mentioned.

Among these, the epoxy resin (F) is preferably 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. Including such an epoxy resin (F) tends to further improve the flame retardancy and heat resistance of the obtained cured product.

Epoxy resin (F) may be used alone or in combination of two or more.

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 , as a solid content not including the filler (J)), preferably 1.0% by mass or more 20
% by mass or less, more preferably 1.0% by mass or more and 15% by mass or less, and still more preferably 2.0% by mass or more and 10% by 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)>
The cyanate ester compound (G) used in the present embodiment is not particularly limited. type cyanate, biphenyl aralkyl type cyanate, 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'-dicyanatobiphenyl, 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 represented by the following general formula (4), and the biphenyl aralkyl cyanate ester have excellent flame retardancy. The naphthol aralkyl-type cyanate ester compound represented by the following general formula (3) and the novolac-type cyanide compound represented by the following general formula (4) are preferable because of their high curability and low coefficient of thermal expansion of the cured product. More preferably, one or more selected from the group consisting of acid esters.

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 formula (3), a plurality of _R6 's each independently represents a hydrogen atom or a methyl group, and _n2 represents an integer of 1 or greater.

In formula (3), a plurality of R ₆ each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In formula (3), _n2 represents an integer of 1 or more. The upper limit of _n2 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 formula (4), a plurality of R ₇ each independently represent a hydrogen atom or a methyl group, a plurality of R ₈ each independently represent a hydrogen atom or an alkyl or alkenyl group having 1 to 4 carbon atoms, _n3 represents an integer of 1 or more.

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

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

In formula (4), _n3 represents an integer of 1 or more. The upper limit of _n3 is preferably 10, more preferably 7.

The method for producing these cyanate ester compounds is not particularly limited, and they may be produced by any existing method for synthesizing cyanate esters. As a specific example, the following general formula (5)
It can be obtained by reacting a naphthol aralkyl-type phenol resin represented by with cyanogen halide in an inert organic solvent in the presence of a basic compound. Alternatively, a similar naphthol-aralkyl-type phenolic resin and a salt of a basic compound are formed in a solution containing water, and then subjected to a two-phase interfacial reaction with a cyanogen halide to synthesize the resin. 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 formula (5), a plurality of _R6 's each independently represents a hydrogen atom or a methyl group, and _n4 represents an integer of 1 or greater.

In formula (5), a plurality of _R6 's each independently represent a hydrogen atom or a methyl group, with a hydrogen atom being preferred.

In formula (5), _n4 represents an integer of 1 or more. The upper limit of _n4 is preferably 10, more preferably 6.

Further, the naphthol aralkyl-type cyanate ester compound is α-naphthol or β
- naphthols such as naphthol and p-xylylene glycol, α,α'-dimethoxy-p
-xylene, 1,4-di(2-hydroxy-2-propyl)benzene, or the like, and those obtained by condensing a naphtholaralkyl resin with cyanic acid.

The cyanate ester compound (G) may be used alone or in combination of two or more.

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 component, solid content not including filler (J)), preferably 0.005
% by mass or more and 5.0% by mass or less, more preferably 0.005% by mass or more and 3.0% by mass
or less, more preferably 0.1% by mass or more and 1.0% by mass or less. When the content of the cyanate ester compound (G) is within the above range, it tends to be possible to obtain a printed wiring board that is more excellent in moldability, thermal elastic modulus, desmear resistance, and chemical resistance.

<Alkenyl-substituted nadimide (H)>
The alkenyl-substituted nadimide (F) used in this embodiment is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in the molecule. Specific examples thereof include compounds represented by the following general formula (6).

In formula (6), a plurality of R ₁ each independently represents 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 naphthylene. group, or a group represented by the following general formula (7) or (8).

In formula (7), _R3 represents a substituent represented by a methylene group, an isopropylidene group, CO, O, S, or _SO2 .

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

A commercially available alkenyl-substituted nadimide (F) represented by formula (6) can also be used. Commercially available products are not particularly limited, but for example, the following formula (9)
(BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)), a compound (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)) represented by the following formula (10), and the like.

Alkenyl-substituted nadimide (H) may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of alkenyl-substituted nadimide (H) is not particularly limited, but the total amount of reaction product (P) and thermosetting component (E) (100% by mass; solvent/solvent It is preferably 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, based on the solid content amount not including the component and filler (J),
More preferably, it is 20% by mass or more and 40% by mass or less. alkenyl-substituted nadimide (H
) is within the above range, it tends to be possible to obtain a printed wiring board that is more excellent in moldability, thermal elastic modulus, desmear resistance, and chemical resistance.

The epoxy resin (F), cyanate ester compound (G), and alkenyl-substituted nadimide (H) described above may be used as raw materials for the reaction product (P).

The thermosetting component (E) may be used alone or in combination of two or more.

Further, in the resin composition of the present embodiment, other resins can be added in addition to the reaction product (P) and the thermosetting component (E) within a range that does not impair the desired properties. .
The type of the other resin is not particularly limited as long as it has insulating properties, and examples thereof include thermoplastic resins. Properties such as metal adhesion and stress relaxation can be imparted by appropriately using a thermoplastic resin together.

[Filler (J)]
Preferably, the resin composition of the present embodiment further contains a filler (J). Filler (J)
The material is not particularly limited as long as it has insulating properties. Examples 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 fibers (
Glass fine powders such as E glass and D glass), inorganic fillers such as hollow glass and spherical glass, and organic fillers such as silicone rubber and silicone composite powder.
These can be used singly or in admixture 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 and alumina and aluminum nitride from the viewpoint of high thermal conductivity.

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 when combining the reaction product (P) and the thermosetting component (E) Total amount of curable component (E) (100 parts by mass; solvent/solvent component, solid content not including filler (J)) or reaction product (P) when using only reaction product (P) With respect to the total amount (100 parts by mass; solid content not including solvent/solvent component and filler (J)), containing 50 parts by mass or more and 300 parts by mass or less of filler (J) is effective for low thermal expansion and high heat It is preferable from the viewpoint of properties such as conductivity, 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]
A silane coupling agent and/or a wetting and dispersing agent can be used in combination with the resin composition of the present embodiment in order to improve the dispersibility of the fine particles of the filler and the adhesive strength between the resin and fine particles or glass cloth. be. These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances. Specific examples include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-
aminosilanes such as γ-aminopropyltrimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane; acrylsilanes such as γ-acryloxypropyltrimethoxysilane; N-β-(N-vinylbenzyl aminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; and phenylarylsilane-based silane coupling agents such as styrylsilane. It is possible. The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include DISPER-BYK110, 111, 118, and 180 under the trade name of Big Chemie Japan Co., Ltd.
, 161, BYK-W996, W9010 and W903.

[Curing accelerator]
In the resin composition of the present embodiment, it is possible to use a curing accelerator as long as the intended properties are not impaired. Although the curing accelerator is not particularly limited, for example,
Organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate; azo compounds such as azobisnitrile; dimethylbenzylamine, N,
N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N- tertiary amines such as methyl piperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, naphthenic acid manganese, cobalt naphthenate,
Organic metal salts such as iron acetylacetonate; products obtained by dissolving these organic metal salts in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyltin oxide and other alkyltins , organotin compounds such as alkyltin oxides, and triphenylimidazole (TPIZ).

〔Organic solvent〕
The resin composition of this embodiment may contain a solvent, if necessary. For example, the use of an organic solvent lowers the viscosity during preparation of the resin composition, improves the handleability, and enhances the ability to impregnate the glass cloth. The type of solvent is not particularly limited as long as it can dissolve part or all of the resin in the resin composition. Specific examples thereof include, but are not limited to, 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 its acetate. A solvent can be used 1 type, or in combination of 2 or more types.

[Other ingredients]
The resin composition of the present embodiment includes various polymer compounds such as other thermosetting resins, thermoplastic resins and their oligomers, and elastomers, as long as the desired properties are not impaired; compound; additives and the like can also be used in combination. These are not particularly limited as long as they are commonly used. Examples of flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, and oxazine ring-containing compounds. As an additive,
UV absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, etc. It is also possible to use them in combination as desired.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment comprises amino-modified silicone (A), maleimide compound (B), at least one of carboxylic acid (C) or carboxylic acid anhydride (D),
The reaction product (P) obtained by reacting can be obtained as it is as a resin composition. A resin composition can also be obtained by mixing the obtained reaction product (P) with the thermosetting component (B). Furthermore, other arbitrary ingredients may be mixed as necessary.

The method for producing the resin composition of the present embodiment is not particularly limited, but as a preferred embodiment, a first reaction step (hereinafter referred to as Also simply referred to as “first reaction step”) and a second reaction step (hereinafter simply referred to as “second reaction step ) and are preferable from the viewpoint of obtaining better storage stability of the reaction product (P).

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

The viscosity of the primary polymer obtained in the first reaction step, which is subjected to 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. In addition,
A method for measuring the viscosity of the primary polymer is not particularly limited, and it can be measured using a general viscometer. For example, it can be measured using a cone-plate viscometer (eg, ICI viscometer).

The reaction temperature in the second reaction step is not particularly limited, but is preferably 50°C to 200°C, more preferably 100°C to 150°C. Although the reaction time is not particularly limited, it is preferably 0.5 hours to 5 hours, more preferably 1.5 hours to 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 anhydride (D) are simultaneously reacted. You may let That is, the first reaction step and the second reaction step may be performed simultaneously.

In the first and second steps, amino-modified silicone (A), maleimide compound (B
), at least one of the carboxylic acid (C) or the carboxylic anhydride (D), and the primary polymer are preferably diluted with a solvent in order to improve their handling properties. The type of solvent is not particularly limited, and examples include ketones such as acetone, methyl ethyl ketone and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; mentioned. A solvent can be used 1 type, or in combination of 2 or more types.

During the production of the resin composition, known treatments (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be performed. In uniformly dispersing the filler such as the filler (J), a stirring and dispersing treatment is performed using a stirring tank equipped with a stirrer having an appropriate stirring ability.
Dispersibility in the resin composition is enhanced. The above stirring, mixing, and kneading treatments can be appropriately performed using, for example, a device for mixing such as a ball mill or a bead mill, or a known device such as a revolution or rotation type mixing device.

[Prepreg]
The prepreg of the present embodiment has a substrate and the resin composition of the present embodiment impregnated or applied to the substrate. A method for producing the prepreg is not particularly limited and can be carried out according to a conventional method. For example, after impregnating or applying the above resin composition to a substrate, the
A prepreg is obtained by semi-curing (to B stage) by heating in a dryer for 1 to 30 minutes. In the present embodiment, the content of the resin composition (including fillers and additive components) relative to the total amount of prepreg (100% by mass) is not particularly limited, but is 30% by mass or more and 90% by mass or less. A range is preferred.

The base material used in the prepreg of the present embodiment is not particularly limited, and known materials used in 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, but for example, E
Glass fibers such as glass, D glass, S glass, Q glass, spherical glass, NE glass, and T glass; Inorganic fibers other than glass such as quartz; Polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont) , wholly aromatic polyamides such as copolyparaphenylene/3,4'oxydiphenylene/terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products Co., Ltd.); 2,6-hydroxynaphthoic acid/parahydroxybenzoic acid (Vectran (registered (trademark), manufactured by Kuraray Co., Ltd.); organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide;

Among these, one or more selected from the group consisting of E-glass cloth, T-glass cloth, S-glass cloth, Q-glass cloth, and organic fibers is preferred from the viewpoint of low thermal expansion.

The shape of the substrate is not particularly limited, but examples thereof include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, and surfacing mats. Although the weaving method of the woven fabric is not particularly limited, for example, plain weave, Nanako weave, and twill weave are known, and it is possible to appropriately select and use from these known ones depending on the intended use and performance. Also,
Glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are not particularly limited, but usually about 0.01 to 0.3 mm is suitably used. In particular, from the viewpoint of strength and water absorption, the base material has a thickness of 20
A woven glass fabric having a mass of 0 μm or less and a mass of 250 g/m ² or less is preferable, and a woven glass fabric made of glass fibers such as E glass, S glass, and T glass is more preferable.

The laminate of the present embodiment can be obtained, for example, by stacking a plurality of the prepregs described above and curing them. Moreover, the metal foil-clad laminate of the present embodiment can be obtained, for example, by laminating and curing the above-described prepreg and metal foil.

Specifically, the metal foil-clad laminate of the present embodiment can be obtained, for example, by stacking at least one sheet of the prepreg described above, disposing a metal foil on one or both sides of the stack, and laminating and molding the stack. More specifically, one or more of the above prepregs are stacked, and if desired, a metal foil such as copper or aluminum is placed on one or both sides of the prepreg, and if necessary, laminated molding is performed. , metal foil clad laminates can be produced. The metal foil used here is not particularly limited as long as it is used for printed wiring board materials, but known copper foils such as rolled copper foil and electrolytic copper foil are preferred. The thickness of the metal foil is not particularly limited, but is preferably 1.0 μm or more and 70 μm or less, more preferably 1.5 μm or more and 35 μm or less. The molding method and molding conditions for the metal foil-clad laminate are not particularly limited, either, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a metal foil-clad laminate. In molding the metal foil-clad laminate, the temperature is 100 to 300° C., the pressure is 2.0 to 100 kgf/cm ² , and the heating time is 0.05 to 5.
Time ranges are common. Furthermore, if desired, post-curing can be performed at a temperature of 150-300°C. Moreover, it is also possible to form a multi-layer board by combining the above-mentioned prepreg and a wiring board for an inner layer separately prepared and performing lamination molding.

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

Moreover, in this embodiment, in addition to the form of the prepreg described above, the form of an embedded sheet in which the resin composition described above is applied to a metal foil or film can also be used.

[Resin sheet]
The resin sheet of this embodiment has a support and the resin composition of this embodiment arranged on the surface of the support. It is a resin sheet obtained by coating one side or both sides of a support with the resin composition described above. Here, the resin sheet is used as one means of thinning the sheet. It can be manufactured by coating and drying.

The support used in producing the resin sheet of the present embodiment is not particularly limited, but can be a known one used for various printed wiring board materials, such as a resin sheet or metal foil. is preferred. Examples of resin sheets and metal foils include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, etc. and metal foils such as aluminum foil, copper foil and gold foil. Among them, electrolytic copper foil and PET film are preferable.

The resin sheet of the present embodiment is preferably obtained by applying the resin composition described above to a support and then semi-curing it (making it B-stage). The method for producing the resin sheet of the present embodiment is generally preferably a method for producing a composite of a B-stage resin and a support. Specifically, for example,
After applying the resin composition to a support such as a copper foil, in a dryer at 100 to 200 ° C., 1 to
A method of semi-curing by heating for 60 minutes or the like to produce a resin sheet may be mentioned. The adhesion amount of the resin composition to the support is 1.0 μm or more in terms of resin thickness of the resin sheet.
A range of 00 μm or less is preferred.

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

The laminate of the present embodiment can be obtained, for example, by stacking one or more of the resin sheets described above and curing them.

Moreover, the metal foil-clad laminate of the present embodiment can be obtained, for example, by laminating and curing the resin sheet described above and a metal foil.

Specifically, for example, the metal foil-clad laminate of the present embodiment uses the resin sheet described above,
It can be obtained by arranging a metal foil on one side or both sides thereof and forming a laminate. More specifically, for example, one sheet of the above-mentioned resin sheet or, if desired, a plurality of sheets 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 lamination-molding this as necessary.
The metal foil used here is not particularly limited as long as it is used for printed wiring board materials, but known copper foils such as rolled copper foil and electrolytic copper foil are preferable. The molding method and molding conditions for the metal foil-clad laminate are not particularly limited, either, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a metal foil-clad laminate. In molding the metal foil-clad laminate, the temperature is 100 to 300°C and the pressure is 2.0.
It is generally up to 100 kgf/cm ² and the heating time is in the range of 0.05 to 5 hours. moreover,
Post-curing can also be carried out at temperatures between 150 and 300° C., if desired.

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

In the present embodiment, when a printed wiring board is produced by forming a conductor layer to form a circuit, electroless plating can be used if the printed wiring board is not in the form of a metal foil-clad laminate.

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

The printed wiring board of the present embodiment is produced, for example, by forming a conductor layer, which becomes a circuit, on an insulating layer by metal foil or electroless plating. The conductor layer is generally composed of copper or aluminum. A printed wiring board insulating layer having a conductor layer formed thereon can be suitably used for a printed wiring board by forming a predetermined wiring pattern. In the printed wiring board of the present embodiment, since the insulating layer contains the above-described resin composition, an excellent elastic modulus is maintained even under the reflow temperature at the time of semiconductor mounting, so that the warp of the semiconductor plastic package can be effectively prevented. It can be particularly effectively used as a printed wiring board for a semiconductor package because it suppresses the peeling strength of the metal foil and is excellent in desmear resistance.

Specifically, the printed wiring board of this embodiment can be manufactured, for example, by the following method. First, the aforementioned metal foil-clad laminate (copper-clad laminate, etc.) is prepared. An inner layer circuit is formed by subjecting the surface of the metal foil-clad laminate to an etching treatment to prepare an inner layer substrate. The surface of the inner layer circuit of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of prepregs are laminated on the surface of the inner layer circuit, and a metal foil for the outer layer circuit is laminated on the outer side. Then, heat and pressurize to integrally mold. In this manner, a multilayer laminate is produced in which an insulating layer composed of the base material and the cured product of the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multilayer laminate, desmear treatment is performed to remove smear, which is a resin residue 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 metal foil for the inner layer circuit and the outer layer circuit, and the metal foil for the outer layer circuit is etched to form the outer layer circuit, and the printed wiring board is manufactured. be done.

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

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to 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 is measured by gel permeation chromatography (GPC) 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 determined in advance, and based on this, the elution time is replaced with the molecular weight.
A graph showing the "relationship between elution time and molecular weight" used at this time is called a "calibration curve" (or calibration curve). Since the "relationship between elution time and molecular weight" differs depending on the type of polymer, it is necessary, in principle, to use a standard polymer having the same structure as the object to be measured, a known molecular weight and a narrow molecular weight distribution. However, in most cases, it is practically difficult to do so, and in practice, standard commercially available polymers are used. Here, polystyrene is used as the standard polymer. Molecular weights thus obtained are referred to as standard reduced molecular weights. From this, the weight average molecular weight (Mw) is calculated from the following formula.

where N denotes the number of polymer molecules, M denotes the molecular weight, and C denotes 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
After cooling to ~5°C, 7.47 g (0.122 mol) of cyanogen chloride, 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。 While maintaining the temperature in the reactor at -5 to +5 ° C. and the pH at ₁ or less, α-naphthol aralkyl phenolic resin (SN4
85, OH group equivalent: 214 g/eq. Softening point: 86 ° C., manufactured by Nippon Steel Chemical Co., Ltd.) 20 g (0
. 0935 mol) and 14.16 g (0.14 mol) of triethylamine dissolved in 92 ml of methylene chloride were added dropwise over 1 hour using a dropping funnel. dripped.

_n4 represents an integer of 1 or more.

After the dropwise addition was completed, the mixture was stirred at the same temperature for 15 minutes, and the reaction liquid was separated to separate the organic layer. After the obtained organic layer was washed twice with 100 mL of water, methylene chloride was distilled off under reduced pressure using an evaporator, and finally concentrated to dryness at 80° C. for 1 hour to obtain cyanogen of the α-naphthol aralkyl phenolic resin. Acid ester (α-naphthol aralkyl type cyanate ester resin) 2
3.5 g was obtained.

[Example 1]
Maleimide compound (maleimide group equivalent 285 g / eq, trade name manufactured by K-I Kasei Co., Ltd.
BMI-80") was dissolved in 40 parts by mass of propylene glycol monomethyl ether (manufactured by KH Neochem) at a heating reflux temperature of 130 ° C., and a diamino-modified silicone (X-22-161B, amino group A primary polymer was prepared by dissolving 15 parts by mass of X-22-161B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., equivalent weight: 1500 g/eq). After that, stirring is continued at a heating reflux temperature of 130° C., and when the viscosity of the primary polymer increases to 200 to 300 mPa s with an ICI viscometer (cone plate type viscometer, manufactured by Towa Kogyo Co., Ltd.), the primary polymer , Add a solution obtained by dissolving 1.0 part by mass of maleic anhydride (manufactured by Tokyo Kasei Co., Ltd.) in 22.5 parts by mass of propylene glycol monoethyl ether acetate (manufactured by Dow Chemical Co., Ltd.), and heat under reflux temperature of 130 ° C. A resin composition containing a reaction product was obtained by allowing the reaction to proceed for several hours. Using a portion of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A portion of the resin composition was stored at 25° C. for 7 days, and the weight average molecular weight of the reaction product after storage was measured. Results are shown in Table 1.

[Example 2]
Including a reaction product having a weight average molecular weight of 13,200 in the same manner as in Example 1, except that 1.0 part by mass of maleic anhydride was replaced with 1.0 part by mass of acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) A resin composition was obtained. Using a portion of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Also, a part of the resin composition is stored for 7 days under conditions of 25 ° C.,
The weight average molecular weight of the reaction product after storage was measured. Results are shown in Table 1.

[Example 3]
A reaction product having a weight average molecular weight of 12,500 was obtained in the same manner as in Example 1, except that 1.0 part by mass of maleic anhydride was replaced with 1.0 part by mass of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). A resin composition containing Using a portion of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A portion of the resin composition was stored at 25° C. for 7 days, and the weight average molecular weight of the reaction product after storage was measured. Results are shown in Table 1.

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

[Example 5]
Example 1 except that 1.0 parts by mass of maleic anhydride was replaced with 0.5 parts by mass of maleic anhydride
A resin composition containing a reaction product having a weight-average molecular weight of 11,710 was obtained by the same method. Using a portion of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A portion of the resin composition was stored at 25° C. for 7 days, and the weight average molecular weight of the reaction product after storage was measured. Results are shown in Table 1.

[Comparative Example 1]
A resin composition containing a reaction product having a weight average molecular weight of 13,900 was prepared in the same manner as in Example 1, except that 1.0 parts by mass of maleic anhydride and 22.5 parts by mass of propylene glycol monoethyl ether acetate were not used. got stuff Using a portion of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. Moreover, a part of the resin composition was heated at 25°C.
and the weight average molecular weight of the reaction product after storage was measured. Results are shown in Table 1.

[Comparative Example 2]
A resin composition containing a reaction product having a weight average molecular weight of 14,100 was obtained in the same manner as in Example 1, except that 1.0 parts by mass of maleic anhydride was not used. Using a portion of the obtained resin composition as a sample, the weight average molecular weight of the reaction product was measured. A portion of the resin composition was stored at 25° C. for 7 days, and the weight average molecular weight of the reaction product after storage was measured. Results are shown in Table 1.

In Table 1, "rate of increase" 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. The "weight average molecular weight" of the resin composition before storage is not the value obtained by measuring immediately after obtaining each resin composition, but the value obtained by measuring on the day when each resin composition was obtained. was value. Therefore, the initial storage stability can be compared from the results 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 (a maleimide group equivalent of 186 g/eq, trade name "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd.), and a biphenyl novolac type epoxy Resin (trade name "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.) 4
. 5 parts by mass, 25 parts by mass of bisdiallyl nadimide (alkenyl group equivalent weight 286 g/eq, trade name "BANI-M" manufactured by Maruzen Petrochemical Co., Ltd.), and the α-naphthol aralkyl-type phenol obtained in Synthesis Example 1. 0.5 parts by mass of cyanate ester of resin, 200 parts by mass of slurry silica (trade name "SC-2050MB" manufactured by Admatechs), and an epoxy silane coupling agent (trade name manufactured by Toray Dow Coating Co., Ltd. Z6040") 5 parts by mass,
Mix 0.5 parts by mass of triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator,
A resin composition was obtained.

[Comparative Example 3]
41.0 parts by mass of the resin composition obtained in Example 1 was mixed with 40.0 parts by mass of the resin composition obtained in Comparative Example 2.
A resin composition was obtained in the same manner as in Example 6, except that the content was changed to 0 parts by mass.

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

[Production of prepreg]
A varnish was obtained by diluting each resin composition obtained in Example 6 and Comparative Example 3 with methyl ethyl ketone. This varnish was impregnated on a T-glass cloth (T2118) and coated at 150°C for 3 hours.
A prepreg was obtained by adjusting the content (% by mass) of the resin composition so that the thickness of the insulating layer would be 100 μm when the prepreg was heated and dried for a minute to form the laminate described below.

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

[Prepreg viscosity]
The resin content was obtained from the prepreg prepared by the above method, and
A product name "AR2000" manufactured by A Instruments Co., Ltd.) was used, and the angular velocity was 1 rad/s,
Viscosity (mPa·s) was measured at 120° C. with a geometry gap of 1 mm. Also, the prepreg described above was stored at 25° C. for 7 days, the resin content was obtained from the prepreg after storage, and the shear viscosity (mPa·s) was measured in the same manner as described above. Table 2
shown in

[Laminate]
A 12 μm-thick electrolytic copper foil (trade name “3EC-III” manufactured by Mitsui Kinzoku Mining Co., Ltd.) was placed above and below one sheet of the obtained prepreg, and laminate molding was performed at a pressure of 30 kgf/cm ² and a temperature of 220° C. for 120 minutes. was performed to obtain a copper-clad laminate (molded before storage) having an insulating layer thickness of 100 μm. In addition, the obtained prepreg was stored at 25° C. for 7 days, and one sheet of the prepreg after storage was laminated in the same manner as described above to obtain a copper-clad laminate having an insulating layer thickness of 100 μm (stored post-molding) was obtained.

[Thermal expansion coefficient]
After removing the copper foil by etching the entire surface of each copper-clad laminate (pre-storage molding and post-storage molding), using a thermomechanical analyzer (manufactured by TA Instruments) from 40 ° C. to 340 ° C. The temperature was raised at a rate of 10°C per minute up to 60°C to 120°C, and the coefficient of linear expansion in the surface direction was measured. The direction of measurement was the longitudinal direction (Warp) of the glass cloth of the laminate. The results are shown in Table 3.

This application is a Japanese patent application filed with the Japan Patent Office on April 5, 2016 (Japanese Patent Application No. 201
6-076144), and a Japanese patent application (Japanese Patent Application No. 2017-000666) filed with the Japan Patent Office on January 5, 2017, the contents of which are incorporated herein by reference.

The resin composition of the present invention and printed wiring boards obtained from the resin composition can be suitably used as members of various electronic devices including 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 a carboxylic acid (C) or a carboxylic anhydride (D),
Resin composition. 2. The resin composition according to claim 1, wherein the resin composition has an amine value of 2.0 mgKOH/g or less. The reaction product (P) is obtained by reacting at least the carboxylic 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 according to any one of claims 1 to 3. further comprising a thermosetting component (E),
The resin composition according to any one of claims 1-4. The thermosetting component (E) is one or more selected from the group consisting of maleimide compounds (B), epoxy resins (F), cyanate ester compounds (G), and alkenyl-substituted nadimides (H). include,
The resin composition according to claim 5. The amino-modified silicone (A) in the reaction product (P) has the following general formula (1)
Including the compound represented by
The resin composition according to any one of claims 1-6.

(In formula (1), a plurality of R _a each independently represents a hydrogen atom, a methyl group or a phenyl group, a plurality of R _b each independently represents a single bond, an alkylene group or an aryl group, n is represents an integer greater than or equal to 1.) The amino group equivalent of the amino-modified silicone (A) in the reaction product (P) is 1
30 or more and 6000 or less,
The resin composition according to 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)methane, polytetramethylene oxide-bis(4-maleimidobenzoate), and one or more selected from the group consisting of compounds represented by the following general formula (2),
The resin composition according to any one of claims 1-8.

(In 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 according to any one of claims 1-9. The filler (J) contains one or more selected from the group consisting of silica, alumina, and aluminum nitride.
The resin composition according to claim 10. The resin composition contains 50 parts by mass or more and 300 parts by mass or less of the filler (J) with respect to the total amount of 100 parts by mass of the reaction product (P) and the thermosetting component (E).
The resin composition according to claim 10 or 11. Having a base material and the resin composition according to any one of claims 1 to 12 impregnated or applied to 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. Having a support and the resin composition according to any one of claims 1 to 12 disposed on the surface of the support,
resin sheet. The support is a resin sheet or 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 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 containing the resin composition according to any one of claims 1 to 12, and a conductor layer formed on the surface of the insulating layer,
printed wiring board. a first reaction step of reacting an amino-modified silicone (A) with a maleimide compound (B) to obtain a primary polymer;
a second reaction step of reacting the primary polymer with at least one of carboxylic acid (C) or carboxylic anhydride (D);
A method for producing a resin composition.