JP2016060882A - Mixture, thermosetting resin composition, prepreg, laminate, printed wiring board, and semiconductor package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg, a laminate, a printed wiring board and a semiconductor package which are formed using a thermosetting resin composition containing a modified silicone compound having a high glass transition temperature and excellent solder heat resistance.SOLUTION: A mixture contains a modified silicone compound formed by reacting a siloxane compound (A) which is represented by formula (1) and has an amino group in a molecule terminal, a maleimide compound (B) having an N-substituted maleimide group, an amine compound (C) which is represented by formula (C-1) and has an acidic substituent, and an amine compound (D) having at least two primary amino groups in one molecule.SELECTED DRAWING: None

Description

  The present invention relates to a mixture containing a modified silicone compound suitable for semiconductor packages and printed wiring boards, a thermosetting resin composition, a prepreg, a laminate, a printed wiring board, and a semiconductor package.

Along with the trend toward miniaturization and higher performance of electronic devices in recent years, the advancement of wiring density and higher integration have progressed in printed wiring boards, and reliability has been improved by improving the heat resistance of laminated boards for printed wiring boards. The demand is getting stronger. In particular, semiconductor packages are required to have both excellent heat resistance and low thermal expansion coefficient (low linear expansion coefficient).
As a laminated board for a printed wiring board, a resin composition mainly composed of an epoxy resin and a glass woven fabric are cured and integrally molded. Epoxy resins have an excellent balance of insulation, heat resistance, cost, etc., but in order to meet the demand for improved heat resistance due to recent high-density mounting and multilayer construction of printed wiring boards, There are limits to improvement. Furthermore, since an epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring or by highly filling an inorganic filler such as silica. However, if the amount of the inorganic filler is increased in the resin composition for laminated boards, the insulation reliability decreases due to moisture absorption and the adhesion between the resin layer and the wiring layer becomes insufficient, and molding defects during press are likely to occur. .

Polybismaleimide resin is widely used for high-density packaging and highly multilayered laminates, but although its heat resistance is very good, it has high hygroscopicity and is difficult to adhere. Furthermore, the polybismaleimide resin requires a high temperature and a long time for lamination as compared with the epoxy resin, and has a disadvantage that productivity is poor. That is, in general, an epoxy resin can be cured at a temperature of 180 ° C. or lower, but when a polybismaleimide resin is laminated, a high temperature of 220 ° C. or higher and a long time treatment are required.
Another example of a resin that can be used is a modified imide resin. The modified imide resin improves moisture resistance and adhesion, but the modified imide resin is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group in order to ensure solubility in general-purpose solvents such as methyl ethyl ketone. The heat resistance of the imide resin is significantly inferior to that of the polybismaleimide resin.
Then, the method of improving the heat resistance of a laminated board is proposed by using the modified silicone compound which has a specific structure (refer patent document 1).

International Publication No. 2012/099133

However, further investigations by the present inventors have revealed that the modified silicone compound described in Patent Document 1 does not necessarily have a satisfactory heat resistance.
Therefore, an object of the present invention is to provide a mixture containing a modified silicone compound that can provide a thermosetting resin composition having a high glass transition temperature and excellent solder heat resistance, and thermosetting containing the mixture. An object of the present invention is to provide a prepreg, a laminated board, a printed wiring board, and a semiconductor package, which are made of a conductive resin composition.

  As a result of studying the present inventors, by adjusting the weight average molecular weight of the modified silicone compound-containing mixture produced using a specific raw material, the above problems are solved, and the glass transition temperature is high and stable. It has been found that a thermosetting resin composition exhibiting excellent heat resistance (solder heat resistance) can be obtained. The present invention has been completed based on such findings.

（式中、Ｒ¹及びＲ²は、それぞれ独立に、炭素数１〜５のアルキル基、フェニル基又は置換フェニル基を示す。）

（式中、Ｒ³は、水酸基、カルボキシル基及びスルホン酸基から選択される酸性置換基を示す。Ｒ⁴は、炭素数１〜５のアルキル基又はハロゲン原子を示す。ｘは１〜５の整数、及びｙは０〜４の整数であり、且つ、１≦ｘ＋ｙ≦５を満たす。但し、ｘが２〜５の整数の場合、複数のＲ³は同一であってもよいし、異なっていてもよい。また、ｙが２〜４の整数の場合、複数のＲ⁴は同一であってもよいし、異なっていてもよい。）
［２］シロキサン化合物（Ａ）が分子両末端に１個ずつアミノ基を有する、上記［１］に記載の混合物。
［３］前記一般式（１）中、Ｒ¹及びＲ²がいずれも炭素数１〜５のアルキル基である、上記［１］又は［２］に記載の混合物。
［４］シロキサン化合物（Ａ）が下記一般式（Ａ−１）で表される、上記［１］又は［２］に記載の混合物。

（式中、Ｒ¹及びＲ²は前記定義の通りである。ｎは、２〜１００の整数である。複数のＲ¹は、それぞれ同一であってもよいし、異なっていてもよい。また、複数のＲ²は、それぞれ同一であってもよいし、異なっていてもよい。
Ｒ⁵及びＲ⁶は、それぞれ独立に、Ｒ¹及びＲ²の定義と同じである。
Ｘ¹及びＸ²は、それぞれ独立に、２価の有機基を示す。）
［５］前記一般式（Ａ−１）中、Ｒ¹、Ｒ²、Ｒ⁵及びＲ⁶がいずれも炭素数１〜５のアルキル基であり、且つＸ¹及びＸ²がいずれも炭素数１〜５の飽和炭化水素基である、上記［４］に記載の混合物。
［６］前記一般式（Ｃ−１）中、Ｒ³が水酸基である、上記［１］〜［５］のいずれか１つに記載の混合物。
［７］上記［１］〜［６］のいずれか１つに記載の混合物を含有する熱硬化性樹脂組成物。
［８］さらにエポキシ樹脂を含有する、上記［７］に記載の熱硬化性樹脂組成物。
［９］さらに無機充填剤を含有する、上記［７］又は［８］に記載の熱硬化性樹脂組成物。
［１０］上記［７］〜［９］のいずれか１つに記載の熱硬化性樹脂組成物が、シート状補強基材に含浸又は塗工されてなるプリプレグ。
［１１］絶縁樹脂層を有する積層板であって、該絶縁樹脂層が上記［７］〜［９］のいずれか１つに記載の熱硬化性樹脂組成物又は上記［１０］に記載のプリプレグを用いて形成された積層板。
［１２］上記［１１］に記載の積層板を用いて得られるプリント配線板。
［１３］上記［１２］に記載のプリント配線板に半導体素子を搭載してなる半導体パッケージ。 The present invention provides the following [1] to [13].
[1] A siloxane compound (A) having a structural unit represented by the following general formula (1) and having an amino group at the molecular end,
A maleimide compound (B) having at least two N-substituted maleimide groups in one molecule;
An amine compound (C) having an acidic substituent represented by the following general formula (C-1), and an amine compound (D) having at least two primary amino groups in one molecule
A mixture having a weight-average molecular weight of 1100 to 1550, which contains a modified silicone compound obtained by reacting.

(In the formula, R ¹ and R ² each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.)

(In the formula, R ³ represents an acidic substituent selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. X represents 1 to 5) The integer and y are integers of 0 to 4 and satisfy 1 ≦ x + y ≦ 5, provided that when x is an integer of 2 to 5, a plurality of R ³ may be the same or different. In addition, when y is an integer of 2 to 4, a plurality of R ⁴ may be the same or different.
[2] The mixture according to [1] above, wherein the siloxane compound (A) has one amino group at each of both ends of the molecule.
[3] The mixture according to the above [1] or [2], wherein both R ¹ and R ^{2 in the} general formula (1) are alkyl groups having 1 to 5 carbon atoms.
[4] The mixture according to [1] or [2], wherein the siloxane compound (A) is represented by the following general formula (A-1).

(In the formula, R ¹ and R ² are as defined above. N is an integer of 2 to 100. The plurality of R ¹ may be the same or different from each other. The plurality of R ² may be the same or different.
R ⁵ and R ⁶ are independently the same as defined for R ¹ and R ² .
X ¹ and X ² each independently represent a divalent organic group. )
[5] In the general formula (A-1), R ¹ , R ² , R ⁵ and R ⁶ are all alkyl groups having 1 to 5 carbon atoms, and X ¹ and X ² are all 1 carbon atoms. The mixture according to the above [4], which is a saturated hydrocarbon group of ˜5.
[6] The mixture according to any one of [1] to [5], wherein R ³ is a hydroxyl group in the general formula (C-1).
[7] A thermosetting resin composition containing the mixture according to any one of [1] to [6].
[8] The thermosetting resin composition according to [7], further including an epoxy resin.
[9] The thermosetting resin composition according to [7] or [8], further including an inorganic filler.
[10] A prepreg obtained by impregnating or coating a sheet-like reinforcing base material with the thermosetting resin composition according to any one of [7] to [9].
[11] A laminate having an insulating resin layer, wherein the insulating resin layer is the thermosetting resin composition according to any one of [7] to [9] or the prepreg according to [10]. A laminated board formed using
[12] A printed wiring board obtained using the laminated board according to [11].
[13] A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to [12].

According to the mixture of the present invention, a thermosetting resin composition having a high glass transition temperature and excellent heat resistance (solder heat resistance) can be provided. Furthermore, the prepreg, laminated board, printed wiring board, and semiconductor package which use this thermosetting resin composition can be provided.
Furthermore, the laminate of the present invention has both heat resistance and a low coefficient of thermal expansion, and is useful for printed wiring boards and semiconductor packages.

Hereinafter, embodiments of the present invention will be described in detail.
[Mixture containing modified silicone compound]
The present invention includes a siloxane compound (A) having a structural unit represented by the following general formula (1) and having an amino group at the molecular end [hereinafter referred to as a siloxane compound (A) or (A) component].
Maleimide compound (B) having at least two N-substituted maleimide groups in one molecule [hereinafter referred to as maleimide compound (B) or (B) component]
An amine compound (C) having an acidic substituent represented by the following general formula (C-1) [hereinafter referred to as an amine compound (C) or (C) component], and at least two first compounds in one molecule Amine compound (D) having a primary amino group [hereinafter referred to as amine compound (D) or (D) component]
Is a mixture having a weight-average molecular weight of 1100 to 1550, which contains a modified silicone compound obtained by reacting.

（式中、Ｒ¹及びＲ²は、それぞれ独立に、炭素数１〜５のアルキル基、フェニル基又は置換フェニル基を示す。）

(In the formula, R ¹ and R ² each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.)

（式中、Ｒ³は、水酸基、カルボキシル基及びスルホン酸基から選択される酸性置換基を示す。Ｒ⁴は、炭素数１〜５のアルキル基又はハロゲン原子を示す。ｘは１〜５の整数、及びｙは０〜４の整数であり、且つ、１≦ｘ＋ｙ≦５を満たす。但し、ｘが２〜５の整数の場合、複数のＲ³は同一であってもよいし、異なっていてもよい。また、ｙが２〜４の整数の場合、複数のＲ⁴は同一であってもよいし、異なっていてもよい。）

(In the formula, R ³ represents an acidic substituent selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. X represents 1 to 5) The integer and y are integers of 0 to 4 and satisfy 1 ≦ x + y ≦ 5, provided that when x is an integer of 2 to 5, a plurality of R ³ may be the same or different. In addition, when y is an integer of 2 to 4, a plurality of R ⁴ may be the same or different.

The mixture of the present invention is a mixture of compounds obtained by reacting the maleimide group of the component (B) with the amino group of the components (A), (C) and (D) in any combination. The mixture of the present invention may contain unreacted components.
Hereafter, each component used for reaction is demonstrated in detail in order.
(Siloxane compound (A))
The siloxane compound (A) is a siloxane compound having a structural unit represented by the following general formula (1) and having an amino group at the molecular end.

In the general formula (1), R ¹ and R ² each independently represent an alkyl group, a phenyl group or a substituted phenyl group having 1 to 5 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
As a substituent of the substituted phenyl group which R < ¹ > and R < ² > show, a C1-C5 alkyl group, a hydroxyl group, an amino group, a vinyl group, a carboxyl group etc. are mentioned, for example. Examples of the alkyl group include the same alkyl groups as described above, and preferred ones are also the same.
R ¹ and R ² are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably as described above.

From the viewpoint of heat resistance, the siloxane compound (A) preferably has the amino group at both molecular ends, more preferably at least one amino group at both molecular ends. It is more preferable that one amino group is present at both ends.
Moreover, it is preferable that the siloxane compound (A) has 2 to 100 structural units represented by the general formula (1), more preferably 2 to 50, and 10 to 50. It is more preferable to have one. At this time, the plurality of R ¹ may be the same or different. Moreover, several R < ² > may be the same respectively, and may differ.

The siloxane compound (A) is preferably a siloxane compound represented by the following general formula (A-1) from the viewpoint of heat resistance.

In the general formula (A-1), R ¹ and R ² are as defined for R ¹ and R ^{2 in} the general formula (1). n is an integer of 2 to 100. The plurality of R ¹ may be the same or different. Moreover, several R < ² > may be the same respectively, and may differ.
R ⁵ and R ⁶ are independently the same as defined for R ¹ and R ² .
X ¹ and X ² each independently represent a divalent organic group.

In the general formula (A-1), for R ¹ and R ² are as described for R ¹ and R ² in the general formula (1). n is preferably an integer of 2 to 50, more preferably an integer of 10 to 50.
The preferred R ⁵ and R ⁶ are the same as the preferred R ¹ and R ² .
Examples of the divalent organic group represented by X ¹ and X ² include an alkylene group, an arylene group-alkylene group (an alkylene group is bonded to NH ₂ ), and the like. Carbon number of an alkylene group becomes like this. Preferably it is 1-5, More preferably, it is 1-3, More preferably, it is 3. Carbon number which forms the ring of an arylene group becomes like this. Preferably it is 6-12, More preferably, it is 6-10, More preferably, it is 6. Examples of the alkylene group include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Examples of the arylene group include a phenylene group and a naphthylene group.
As a siloxane compound represented by the general formula (A-1), R ¹ , R ² , R ⁵ and R ⁶ are all alkyl groups having 1 to 5 carbon atoms and X ¹ from the viewpoint of heat resistance. And X ² are each preferably a saturated hydrocarbon group having 1 to 5 carbon atoms.

A siloxane compound (A) may be used individually by 1 type, and may use 2 or more types together.
A commercially available product can be used as the siloxane compound (A). Examples of commercially available products include “KF-8010” (amine equivalent 430), “X-22-161A” (amine equivalent 800), “X-22-161B” (amine equivalent 1500), “KF-8012” ( Amine equivalent 2200), "X-22-9409" (amine equivalent 700), "X-22-1660B-3" (amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.); "BY-16-853U" (Amine equivalent 460), “BY-16-853” (amine equivalent 650), “BY-16-853B” (amine equivalent 2200) (above, manufactured by Toray Dow Corning Co., Ltd.) and the like.
Among these, X-22-161A, X-22-161B, and KF-8012 are preferable from the viewpoint of heat resistance and a coefficient of thermal expansion, and X-22-161A is more preferable.

(Maleimide compound (B))
The maleimide compound (B) is a maleimide compound having at least two N-substituted maleimide groups in one molecule.
The maleimide compound (B) is preferably a compound containing an aromatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups [hereinafter referred to as an aromatic hydrocarbon group-containing maleimide]. . The aromatic hydrocarbon group-containing maleimide only needs to contain an aromatic hydrocarbon group between any combination of two maleimide groups selected arbitrarily.
The maleimide compound (B) is preferably a maleimide compound having 2 to 5 N-substituted maleimide groups in one molecule from the viewpoint of heat resistance. Furthermore, the maleimide compound (B) is more preferably an aromatic hydrocarbon group-containing maleimide represented by any of the following general formulas (B-1) to (B-4) from the viewpoint of heat resistance. .

In said formula, R < ¹¹ > -R < ¹³ > shows a C1-C5 aliphatic hydrocarbon group each independently. X ¹¹ represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, —O— or a sulfonyl group. p, q, and r are each independently an integer of 0-4. m is an integer of 0-10.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^{11 to} R ¹³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, An n-pentyl group and the like can be mentioned. From the viewpoint of heat resistance, the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ¹¹ include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group, from the viewpoint of heat resistance.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ¹¹ include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoint of heat resistance.
X ¹¹ is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
p, q, and r are each independently an integer of 0 to 4, and from the viewpoint of availability, all are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. .
m is an integer of 0 to 10, and is preferably 0 to 5 and more preferably 0 to 3 from the viewpoint of availability. In particular, the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (B-3) is preferably a mixture of m = 0 to 3.

The maleimide compound (B) is a maleimide compound having at least two N-substituted maleimide groups in one molecule and not having an aromatic hydrocarbon group (hereinafter referred to as a so-called aromatic hydrocarbon group-free maleimide compound and May be used). The non-aromatic hydrocarbon group-containing maleimide compound does not contain an aromatic hydrocarbon group between any combination of two arbitrarily selected maleimide groups.
As an aromatic hydrocarbon group-free maleimide compound, a group having two N-substituted maleimide groups in one molecule and a group between the two N-substituted maleimide groups having 1 to 15 carbon atoms It is preferably a hydrocarbon group, and more preferably a bismaleimide compound represented by the following general formula (B-5).

In the general formula (B-5), X ¹² represents an aliphatic hydrocarbon group having 1 to 15 carbon atoms.
Examples of the aliphatic hydrocarbon group having 1 to 15 carbon atoms represented by X ¹² include a methylene group, a 1,1-ethanediyl group, a 1,2-ethanediyl group, a 1,3-propanediyl group, and a 1,4-butanediyl group. Alkylene group having 1 to 15 carbon atoms such as 1,5-pentanediyl group, 1,6-hexanediyl group, 1,8-octanediyl group, 1,10-decanediyl group; cyclopentylene group, cyclohexylene group And a cycloalkylene group having 3 to 8 carbon atoms such as a cyclooctylene group; a group formed by linking these groups. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 2 to 4 carbon atoms, more preferably an aliphatic hydrocarbon group having 3 carbon atoms, and a 1,3-propanediyl group from the viewpoint of heat resistance. Further preferred.

  As the maleimide compound (B), for example, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3- (2-methylphenylene)] bismaleimide, N, N′— [1,3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) Methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis ( -Maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1 -Bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) ) Phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimi) Phenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4- Maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [ 4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- 3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone Bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl Benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, , 4-Bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl- α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3- Maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimide (for example, manufactured by Daiwa Kasei Co., Ltd., trade name: BMI-2300, etc.) , N′-methylene bismaleimide, N, N′-ethylene bismaleimide, N, N′-prolene bismaleimide, N, N′-butylene bismaleimide, N, N′-pentylene bismaleimide, N, '-Hexylene bismaleimide, N, N'-(2,2-dimethyl) hexylene bismaleimide, N, N '-(2,2-dimethyl-4-methyl) hexylene bismaleimide, bis (4-maleimide) Examples include aromatic hydrocarbon group-free maleimides such as (cyclohexyl) methane and 1,4-bis (maleimidomethyl) cyclohexane.

Among these, aromatic hydrocarbon group-containing maleimide is preferable from the viewpoint of high reactivity and further improved heat resistance, and bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, and polyphenylmethanemaleimide are more preferable, and considering solubility in a solvent, Bis (4-maleimidophenyl) methane is more preferred.
A maleimide compound (B) may be used individually by 1 type, and may use 2 or more types together.

(Amine compound having an acidic substituent (C))
The amine compound (C) having an acidic substituent is an amine compound represented by the following general formula (C-1), and more preferably the following general formula (C-2) or (C- The amine compound represented by 3), and more preferably the amine compound represented by the following general formula (C-2).

In the above general formula, R ³ represents an acidic substituent selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. x is an integer of 1 to 5, and y is an integer of 0 to 4, and 1 ≦ x + y ≦ 5 is satisfied. However, when x is an integer of 2-5, several R < ³ > may be the same and may differ. Further, if y is 2 to 4 integer, to a plurality of R ⁴ may be the same or different.
The acidic substituent represented by R ³ is preferably a hydroxyl group or a carboxyl group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
x is an integer of 1 to 5, and is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1 from the viewpoint of heat resistance.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the halogen atom represented by R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
y is an integer of 0 to 4, and from the viewpoint of heat resistance, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.

Examples of the amine compound (C) having an acidic substituent include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o- Aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. Among these, from the viewpoint of solubility and reactivity, o-aminophenol, m-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and heat resistance Considering the properties, m-aminophenol and p-aminophenol are more preferable.
The amine compound (C) having an acidic substituent may be used alone or in combination of two or more.

(Amine compound (D))
Further, as the component (D), an amine compound (D) having at least two primary amino groups in one molecule [hereinafter abbreviated as amine compound (D)] is used. The amine compound (D) is distinguished from the siloxane compound (A). Specifically, the amine compound (D) is an amine compound having no structural unit represented by the general formula (1).
The number of primary amino groups possessed by the amine compound (D) is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2 from the viewpoint of heat resistance.
The amine compound (D) is preferably a diamine compound represented by any one of the following general formulas (D-1) to (D-3) from the viewpoint of heat resistance. ) Or a diamine compound represented by (D-3), more preferably a diamine compound represented by the following general formula (D-1).

In the above formula, X ¹³ represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a keto group, a fluorenediyl group or a phenylenedioxy group. . R ¹⁴ and R ¹⁵ each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group or a hydroxyl group. s and t are each independently an integer of 0 to 4.
X ^{14 to} X ¹⁶ each independently represent a single bond, an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, —O— or a sulfonyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ¹³ include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, and the like. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably a methylene group, from the viewpoint of heat resistance.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ¹³ include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoint of heat resistance.
Examples of the fluorenediyl group represented by X ¹³ include fluorene-1,8-diyl group, fluorene-1,7-diyl group, fluorene-1,6-diyl group, fluorene-1,5-diyl group, and fluorene. -2,7-diyl group, fluorene-2,6-diyl group, fluorene-2,5-diyl group, fluorene-3,6-diyl group, fluorene-3,5-diyl group, fluorene-4,5- A diyl group etc. are mentioned.
The phenylene group which X ¹³ represents, 1,4-phenylene group, 1,3-phenylene group, and a 1,2-phenylene group.
X ¹³ is preferably an alkylene group having 1 to 5 carbon atoms, —O—, or a sulfonyl group, and more preferably an alkylene group having 1 to 5 carbon atoms or a sulfonyl group among the above options.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ¹⁴ and R ¹⁵ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, An n-pentyl group and the like can be mentioned. From the viewpoint of heat resistance, the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, and still more preferably an ethyl group.
s and t are integers of 0 to 4, and are each preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 1, from the viewpoint of heat resistance.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^{14 to} X ¹⁶ include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and 1,5-penta. A methylene group etc. are mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance.
X ^{14 to} X ¹⁶ are each preferably an isopropylidene group among the above options.

  Examples of the amine compound (D) include m-phenylenediamine, p-phenylenediamine, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4-diaminomesitylene, m-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene 2,4-bis (amino-tert-butyl) toluene, 2,4-diaminoxylene, 2,4-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminodurene, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 3-bis (3-aminobenzyl) benzene, 4-bis (4-aminobenzyl) benzene 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-amino) Phenoxy) benzene, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 4-bis (4- (4-aminophenoxy) phenoxy) benzene, 3-bis (3- (3- (3-aminophenoxy) ) Phenoxy) phenoxy) benzene, 4-bis (4- (4- (4-aminophenoxy) phenoxy) phenoxy) benzene, 3-bis (α, α-dimethyl-3-aminobenzyl) benzene, 1,4-bis (Α, α-dimethyl-3-aminobenzyl) benzene, 3-bis (α, α-dimethyl-4-aminobenzyl) benzene, bis (4-methylaminopentyl) ben P-bis (2-methyl-4-aminopentyl) benzene, 1,4-bis (3-aminopropyldimethylsilyl) benzene, bis [(4-aminophenyl) -2-propyl] 1,4-benzene 2,5-diaminobenzenesulfonic acid, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5 ′ -Tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl, 5,5'-diethyl-4,4'-diaminodiphenylmethane, 4, , 4'-methylene-bis (2-chloroaniline), 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylethane, 2,2'-diaminodiphenylpropane, 3,3'-diamy Diphenylpropane, 4,4′-diaminodiphenylpropane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 3- (2 ′, 4′-diaminophenoxy) propanesulfonic acid, bis (4-aminophenyl) diethylsilane, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diamino Diphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, bis (4-amino-tert-butylphenyl) ether, 4,4′-diaminodiphenyl ether-2, 2′-disulfonic acid, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis [4- (4- Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, benzidine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′- Diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl-6,6′-disulfonic acid, 2,2 ′, 5,5 ′ -Tetrachloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-bis (4 -Aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, 1,5-diaminonaphthalene, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene , 9,9'- Bis (4-aminophenyl) fluorene, 9,9′-bis (4-aminophenyl) fluorene-2,7-disulfonic acid, 9,9′-bis (4-aminophenoxyphenyl) fluorene, diaminoanthraquinone, 3, An aromatic group-containing amine such as 7-diamino-2,8-dimethyldibenzothiophenesulfone;

Ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5- Dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane Aliphatic amines such as 2,5-diamino-1,3,4-oxadiazol, bis (4-aminocyclohexyl) methane; melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s Guanamine such as triazine, 2,4-diamino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl-s-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine System compounds and the like.

Among these, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, benzidine, 4,4′-bis (4-aminophenoxy) biphenyl, 4, 4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, and benzoguanamine are preferred. From the viewpoint of production cost, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4 3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and benzoguanamine are preferred. From the viewpoint of low toxicity and solubility in organic solvents, 3,3 ' -Diaminodiphenylsulfone, 3,3′-diethyl-4,4′-diaminodiphenylmethane is more preferred.
An amine compound (D) may be used individually by 1 type, and may use 2 or more types together.

(Organic solvent)
The mixture of the present invention is obtained by reacting the above components (A) to (D). The reaction of components (A) to (D) is preferably carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents; ester solvents such as ethyl acetate and γ-butyrolactone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Nitrogen atom-containing solvent including a system solvent; Sulfur atom-containing solvent including a sulfoxide solvent such as dimethyl sulfoxide; Ester solvent including a lactone solvent such as γ-butyrolactone Is mentioned. Among these, alcohol-based solvents, ketone-based solvents, and ester-based solvents are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are preferable from the viewpoint of low toxicity and high volatility and easy removal. Dimethylacetamide is more preferable, and propylene glycol monomethyl ether is more preferable.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, From a viewpoint of solubility and reaction efficiency, the total content of (A)-(D) component becomes like this. Preferably it is 20-80 mass%, More preferably, it is 20-60 mass%. More preferably, the content may be 30 to 60% by mass.

(Reaction catalyst)
You may implement reaction of (A)-(D) component in presence of a reaction catalyst from a viewpoint of reaction efficiency. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine, and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine.
A reaction catalyst may be used individually by 1 type, and may use 2 or more types together.

(Reaction temperature)
The reaction of the components (A) to (D) is preferably performed at 70 to 150 ° C, more preferably 90 to 140 ° C, and still more preferably 100 to 130 ° C from the viewpoint of reaction efficiency and yield.

(Amount used for each component)
The amount of each component used in the reaction of the components (A) to (D) is the sum of the primary amino group equivalents of the components (A), (C) and (D) [the sum of the equivalents of —NH ₂ groups And the carbon-carbon double bond group equivalent [denoted as C = C group equivalent] in the maleimide group of the component (B) preferably satisfies the following formula.
0.1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 10
By setting [C = C group equivalent] / [-NH ₂ group equivalent] to 0.1 or more, gelation and heat resistance do not decrease, and by setting it to 10 or less, an organic solvent This is preferable because the solubility and the heat resistance in water are not lowered.
From the same viewpoint, more preferably,
1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 9
More preferably,
1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 8
More preferably,
1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 5
Particularly preferably,
2 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 5.
(D) The usage-amount of a component satisfy | fills the said relational expression, 20-500 mass parts is preferable with respect to 100 mass parts of (A) component, 30-200 mass parts is more preferable, 40-100 mass parts is further preferable. The heat resistance does not decrease when the amount is 20 parts by mass or more, and the coefficient of thermal expansion can be kept low when the amount is 500 parts by mass or less.
Furthermore, the usage-amount of (C) component satisfy | fills the said relational expression, 1-500 mass parts is preferable with respect to 100 mass parts of (A) component, 5-200 mass parts is more preferable, 5-100 mass parts Is more preferable, and 10 to 50 parts by mass is particularly preferable. By setting it to 1 part by mass or more, the heat resistance does not decrease, and by setting it to 500 parts by mass or less, the coefficient of thermal expansion can be kept low.

By the reaction of the components (A) to (D), a mixture having a weight average molecular weight (Mw) of 1100 to 1550 containing the modified silicone compound is obtained. Here, in description of this specification and a claim, a weight average molecular weight is the value measured by the method as described in an Example.
The mixture containing a modified silicone compound is a thermosetting resin and has good thermosetting reactivity by itself. Therefore, the thermosetting resin composition containing the mixture can provide a laminate having both heat resistance and a low coefficient of thermal expansion. In addition, various characteristics, such as heat resistance, adhesiveness, and mechanical strength, can be improved by using together with another thermosetting resin as needed. Here, when using an epoxy resin together as another thermosetting resin, the said mixture of this invention can function also as a hardening | curing agent of an epoxy resin.

[Thermosetting resin composition]
The content of the mixture of the present invention in the thermosetting resin composition is 100 masses of solid content of the thermosetting resin composition (that is, all components excluding the organic solvent) from the viewpoints of heat resistance, low water absorption and coefficient of thermal expansion. In part, Preferably it is 20-100 mass parts, More preferably, it is 20-90 mass parts.
Hereinafter, the thermosetting resin composition containing the mixture of the present invention will be described in detail.
Other thermosetting resins that can be used in combination with the mixture of the present invention are not particularly limited. For example, epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins , Unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin and the like. These may use 1 type and may use 2 or more types together. Among these, an epoxy resin and a phenol resin are preferable from the viewpoints of moldability and heat resistance.

The epoxy resin is classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among these, a glycidyl ether type epoxy resin is preferable.
Epoxy resins are classified into various epoxy resins depending on the difference in the main skeleton. In each of the above types of epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are also included. Epoxy resin: Novolak type epoxy resin such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin; stilbene type epoxy resin; triazine skeleton containing epoxy resin; fluorene skeleton containing epoxy resin Resin; Naphthalene type epoxy resin; Triphenolmethane type epoxy resin; Biphenyl type epoxy resin; Biphenyl aralkyl type epoxy resin; Xylylene type epoxy Fats; it is classified into an alicyclic epoxy resins such as dicyclopentadiene type epoxy resin. Furthermore, the phosphorus containing epoxy resin which introduce | transduced the phosphorus compound to at least 1 sort (s) of these is also mentioned.
Among these, naphthalene type epoxy resin and biphenyl aralkyl type epoxy resin are preferable from the viewpoint of heat resistance and flame retardancy. The naphthalene type epoxy resin may be an epoxy resin containing a naphthalene skeleton, and includes, for example, a naphthol cresol novolac type epoxy resin.
An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

Examples of the phenol resin include novolak type phenol resin, naphthalene type phenol resin, high ortho type novolac phenol resin, terpene modified phenol resin, terpene phenol modified phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, salicyl. Examples include aldehyde type phenol resins and benzaldehyde type phenol resins.
Among these, from the viewpoint of heat resistance, a novolak type phenol resin and a naphthalene type phenol resin are preferable, and a naphthalene type phenol resin is more preferable.
A phenol resin may be used individually by 1 type, and may use 2 or more types together.
When the thermosetting resin composition of the present invention contains another thermosetting resin, the content is preferably 0 with respect to 100 parts by mass of the mixture of the present invention from the viewpoint of heat resistance and flame retardancy. -50 mass parts, More preferably, it is 0-40 mass parts, More preferably, it is 5-40 mass parts, Most preferably, it is 10-40 mass parts.

(Other ingredients)
The thermosetting resin composition of the present invention includes a curing agent, a curing accelerator, an inorganic filler, a flame retardant, a functional resin, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, and a fluorescent whitening as necessary. An agent, an adhesion improver, an organic solvent, and the like may be contained. One of these may be contained alone, or two or more may be contained. By appropriately blending these materials into the thermosetting resin composition of the present invention, various properties of the prepreg and insulating layer used in the laminate can be improved.
In particular, the thermosetting resin composition of the present invention preferably contains at least one selected from a curing accelerator and an inorganic filler, and more preferably contains both a curing accelerator and an inorganic filler.

(Curing accelerator)
Examples of the curing accelerator include zinc metal naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), imidazole compounds and derivatives thereof. , Organic phosphorus compounds, secondary amines, tertiary amines and quaternary ammonium salts. Among these, imidazole compounds and derivatives thereof are preferable from the viewpoints of heat resistance and flame retardancy.
Specific examples of the imidazole compound and derivatives thereof include, for example, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl. -1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Ethyl -Methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2 , 4-Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')] ethyl-s- An imidazole compound such as triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)] ethyl-s-triazine; an addition reaction product of the imidazole compound and trimellitic acid; Addition reaction product of imidazole compound and isocyanuric acid; addition reaction product of imidazole compound and hydrobromic acid; imidazole compound and epoxy resin Addition reaction product of an; and addition reaction products thereof with the imidazole compound and the cyanate resin. Among these, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, or an addition reaction product of any of these with a cyanate resin 2-ethyl-4-methylimidazole or an addition reaction product of 2-ethyl-4-methylimidazole and a cyanate resin is more preferable.
A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
The content of the curing accelerator in the thermosetting resin composition of the present invention is preferably from 0 to 7 parts by mass, more preferably from 100 parts by mass of the mixture of the present invention, from the viewpoints of heat resistance and flame retardancy. It is 0-5 mass parts, More preferably, it is 0.1-5 mass parts.

(Inorganic filler)
By including an inorganic filler in the thermosetting resin composition of the present invention, the coefficient of thermal expansion can be reduced, the elastic modulus can be increased, and the heat resistance and flame retardancy can be improved. Examples of the inorganic filler include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, and barium sulfate. , Aluminum borate, potassium titanate, short glass fiber, fine glass powder, hollow glass and the like. Preferred examples of the glass include E glass, T glass, and D glass. Among these, silica, alumina, mica, and talc are preferable from the viewpoints of heat resistance and flame retardancy, and silica and alumina are more preferable, and silica is more preferable from the viewpoint of high heat dissipation. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused silica (fused spherical silica).
When fused silica is used as the inorganic filler, the average particle size is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, still more preferably 0.1 to 2 μm, particularly preferably. 0.2-1 μm. By making the average particle diameter of the fused silica 0.1 μm or more, the fluidity at the time of high filling can be kept good, and by making it 10 μm or less, the mixing probability of coarse particles is reduced and coarse particles It is possible to suppress the occurrence of defects due to. Here, the average particle size is a particle size at a point corresponding to a volume of just 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.
An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

  The content of the inorganic filler in the thermosetting resin composition of the present invention is 100 masses of the mixture of the present invention from the viewpoint of reducing the coefficient of thermal expansion, increasing the elastic modulus, and improving the heat resistance and flame retardancy. The amount is preferably 0 to 300 parts by mass, more preferably 50 to 270 parts by mass, still more preferably 100 to 250 parts by mass, and particularly preferably 150 to 230 parts by mass.

(Organic solvent)
The thermosetting resin composition of the present invention may be made into a varnish state by adding an organic solvent from the viewpoint of facilitating handling by dilution and easy manufacture of a prepreg described later. A varnish is preferred.
Examples of the organic solvent include, but are not limited to, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran Ether solvents such as toluene; aromatic solvents such as toluene, xylene and mesitylene; nitrogen-containing solvents including amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; including sulfoxide solvents such as dimethyl sulfoxide Sulfur atom-containing solvents; ester solvents containing lactone solvents such as γ-butyrolactone.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, propylene glycol monomethyl ether, and cyclohexanone are more preferable, and methyl ethyl ketone, methyl isobutyl. Ketones and cyclohexanone are more preferred, and methyl ethyl ketone and cyclohexanone are particularly preferred.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
The content of the organic solvent in the thermosetting resin composition of the present invention may be appropriately adjusted to such an extent that the thermosetting resin composition can be easily handled. If there is no particular limitation, the solid content concentration (concentration of components other than the organic solvent) derived from the thermosetting resin composition is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 40. It is made to become -70 mass%, Most preferably, it will be 50-70 mass%.

[Prepreg]
The prepreg of the present invention is obtained by impregnating or coating the thermosetting resin composition on a sheet-like reinforcing base material.
The prepreg of the present invention can be produced, for example, by impregnating or coating the thermosetting resin composition on a sheet-like reinforcing base material and semi-curing (B-stage) by heating or the like.
As the prepreg sheet-like reinforcing substrate, known materials used for various types of laminates for electrical insulating materials can be used. Examples of the material for the sheet-like reinforcing base include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like reinforcement base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, or a surfacing mat, for example. In addition, a material and a shape are selected by the use and performance of the target molding, and 1 type may be used independently and 2 or more types of materials and shapes can also be combined as needed.

As a method for impregnating or applying the thermosetting resin composition to the sheet-like reinforcing base material, the following hot melt method or solvent method is preferable.
The hot melt method is a method in which an organic solvent is not contained in a thermosetting resin composition, and (1) a coated paper having good peelability from the composition is once coated and laminated on a sheet-like reinforcing substrate. Or (2) A method of directly coating the sheet-like reinforcing substrate with a die coater.
On the other hand, in the solvent method, a varnish is prepared by adding an organic solvent to the thermosetting resin composition, a sheet-like reinforcing base material is immersed in the varnish, and the sheet-like reinforcing base material is impregnated, It is a method of drying.

The thickness of the sheet-like reinforcing base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface treatment with a silane coupling agent or the like or mechanical fiber opening treatment is performed. What has been applied is preferred from the viewpoints of heat resistance, moisture resistance and processability. The adhesion amount of the thermosetting resin composition to the substrate is such that the resin content of the prepreg after drying (that is, the solid content derived from the thermosetting resin composition) is 20 to 90% by mass. After impregnating or coating the material, it is usually heat-dried at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.
As the prepreg, one sheet is used, or preferably 2 to 20 sheets are overlapped.

[Laminated board]
The laminated board of this invention is a laminated board which has an insulating resin layer, Comprising: This insulating resin layer is a laminated board formed using the said thermosetting resin composition or the said prepreg.
For example, it can be manufactured by using one sheet of the prepreg, or stacking 2 to 20 sheets, and laminating and forming the metal foil on one or both sides thereof.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, preferably copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, Iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferable, copper and amylnium are more preferable, and copper is more preferable.
As the molding conditions of the laminated plate, a known molding method of a laminated plate for an electrical insulating material and a multilayer plate can be applied, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. It can be molded at 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
Moreover, the prepreg of the present invention and the printed wiring board for inner layer can be combined and laminated to produce a multilayer board.
There is no restriction | limiting in particular in the thickness of metal foil, According to the use of a printed wiring board, it can select suitably. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 10 to 50 μm, and particularly preferably 1 to 30 μm.

In addition, it is also preferable to form a plating layer by plating metal foil.
The metal of the plating layer is not particularly limited as long as it can be used for plating. The metal of the plating layer is selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. It is preferable.
There is no restriction | limiting in particular as a plating method, For example, a well-known method, for example, the electroplating method and the electroless-plating method, can be utilized.

The printed wiring board of the present invention is obtained using the laminate.
The printed wiring board of the present invention is, for example, a subtractive method, a full additive method, a semi-additive method (SAP) or a modified semi-additive method (m-SAP: modified Semi Additive Process). It can be manufactured by forming a wiring pattern by a known method. In other words, the metal foil of the laminated plate is processed by a known etching method, a plurality of laminated plates processed by wiring through the above-described prepreg are stacked, and multilayered by heating and pressing. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.
The semiconductor package of the present invention is obtained by mounting a semiconductor element on the printed wiring board. The semiconductor package of the present invention can be manufactured, for example, by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position of the printed wiring board of the present invention.

  Hereinafter, the present invention will be described by way of examples. In addition, this invention is not restrict | limited to these Examples.

[Evaluation / Measurement Method]
In each example and comparative example, each measurement was performed by the following method.
(1) Measurement of weight average molecular weight (Mw) The weight average molecular weight of the mixture containing the modified silicone compound is measured by gel permeation chromatography (GPC) using a solution after reaction for a predetermined time in each production example. Conversion was made from a calibration curve using polystyrene. A peak with a retention time of 5-11 minutes was utilized. The calibration curve was approximated by a cubic equation using a standard polystyrene kit (PStQuick Kit-L [trade name, manufactured by Tosoh Corporation]). The conditions of GPC are as follows.
Apparatus: HLC-8320GPC [manufactured by Tosoh Corporation]
Column: TSKgel SuperHZ2000 + TSKgel SuperHZ3000 (two in total) (trade name, manufactured by Tosoh Corporation)
Column size: 4.6 mm I.D. D x 150mm
Guard column: TSK guard column Super HZ-L
Guard column size: 4.6 mm I.D. D x 20mm
Eluent: Tetrahydrofuran Sample concentration: 10 mg / 1.3 mL
<Pump>
Sample side pump upper limit pressure: 70 MPa, Sample side pump lower limit pressure: 0.1 MPa, Sample side flow rate: 0.35 mL / min, Reference side pump upper limit pressure: 70 MPa, Reference side pump lower limit pressure: 0.1 MPa, Reference side flow rate ratio : Same size <sampler>
Tube volume: 112 μL, injection volume: 10 μL, pre-suction volume: 150 μL, sampling rate: 5 μL / sec, air volume: 1 μL, loop volume: 100 μL
<Oven>
Column oven control temperature: 40 ° C., column oven gas sensor level: 300 mV, pump oven control temperature: 40 ° C., pump oven gas sensor level: 300 mV
<Suggested refraction detector>
Balance value: 0.00 mV, Response: 0.50 sec, Temperature control temperature: 40 ° C., Polarity: +, Range: 256 μRIU / FS

(2) Measurement of glass transition temperature (Tg) The copper-clad laminate produced in each example was dissolved in copper etching solution (“Ammonium Persulfate” (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in hot water at 80 ° C. to make 500 g / l. 5 mm square evaluation board | substrate was cut out from the evaluation board | substrate which removed copper foil by immersing in a solution), and the thermomechanical analysis was performed by the compression method using the TMA test apparatus "TMA2940" (made by DuPont). After mounting the evaluation substrate on the apparatus in the X direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined.
(3) Evaluation of solder heat resistance Five test pieces obtained by cutting the copper clad laminates produced in each example into 25 mm squares were floated on a solder bath at 288 ° C., and the appearance was visually observed. It was judged whether there were any abnormalities. The results are shown by setting the number of test specimens that were not abnormal among the five to be the numerator and the denominator to be 5.

[Production Example 1] Production of Modified Silicone Compound 1 In a reaction vessel having a volume of 1 L, which can be heated and cooled, equipped with a thermometer, a stirrer and a reflux condenser, a siloxane diamine “X-22-161A as component (A)” was prepared. "(Shin-Etsu Chemical Co., Ltd.) 19.44g, (B) component bis (4-maleimidophenyl) methane (Keiai Kasei Co., Ltd.) 122.87g, (C) p-aminophenol (Ihara) (Manufactured by Chemical Industry Co., Ltd.) 4.68 g, as component (D) 3,3′-diethyl-4,4′-diaminodiphenylmethane “KAYAHARD A-A” (manufactured by Nippon Kayaku Co., Ltd.) 13.01 g, and organic solvent 240.0 g of propylene glycol monomethyl ether [total content of components (A) to (D): 40% by mass] was added. The mixture 1 was reacted at 115 ° C. for 1 hour to obtain a mixture 1 having a weight average molecular weight of 1139 containing a modified siloxane compound. After concentration to a solid content concentration of 60% under normal pressure, 53.33 g of cyclohexanone at 90 ° C. Was added and stirred for 30 minutes to obtain 300 g of a mixture 1-containing solution having a solid content concentration of 50% by mass.

[Production Examples 2-6] Production of Modified Silicone Compounds 2-6 In Production Example 1, the reaction time was 1.5 hours so that the weight average molecular weight of the mixture was 1211, 1296, 1386, 1482, 1530, respectively. The same operation was performed except that the time was adjusted to 2.0 hours, 2.5 hours, 3.0 hours, and 3.5 hours, and the mixture 2 containing solution, the mixture 3 containing solution having a solid content concentration of 50% by mass, A mixture 4 containing solution, a mixture 5 containing solution and a mixture 6 containing solution (all 300 g) were obtained.

[Production Comparative Examples 1 to 3] Production of Modified Silicone Compounds 7 to 9 In Production Example 1, the reaction times were 0.5 hours and 4.0 hours, respectively, so that the weight average molecular weights of the mixtures were 1070, 1595 and 1721, respectively. The mixture was operated in the same manner except that it was adjusted to 4.5 hours to obtain a mixture 7-containing solution, a mixture 8-containing solution, and a mixture 9-containing solution (both 300 g) having a solid content concentration of 50% by mass.

[Examples 1-6, Comparative Examples 1-3]
Using each component shown in Table 1 below, using methyl ethyl ketone as an organic solvent for dilution, mixing in the mixing ratio shown in Table 1 (however, the mixture-containing solution is a mixing ratio in terms of solid content) [unit: parts by mass] Then, a varnish having a solid content concentration (concentration of components other than the organic solvent) of 65% by mass derived from the thermosetting resin composition was obtained.
Next, the obtained varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm, and B-staged by heating and drying at 130 ° C. for 3 minutes, and the solid content derived from the thermosetting resin composition was A 48% by mass prepreg was obtained.
Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate. Using the obtained copper-clad laminate, heat resistance was evaluated according to the method described above. The results are shown in Table 1.

[Description of each component in Table 1]
* 1: “NC-7000L” (trade name), naphthol cresol novolac type epoxy resin (naphthalene type epoxy resin), manufactured by Nippon Kayaku Co., Ltd. * 2: “G-8809L” (trade name), isocyanate mask imidazole (hexa) Methylene diisocyanate resin and 2-ethyl-4-methylimidazole addition reaction product), manufactured by Daiichi Kogyo Seiyaku Co., Ltd. * 3: “SO-C2” (trade name), fused spherical silica, average particle size 0.5 μm, stock Made by company Admatex

From Table 1, in the Example, the prepreg and laminated board which were stable and excellent in heat resistance in any case are obtained.
On the other hand, in Comparative Example 1 using a mixture having a weight average molecular weight of less than 1100, the glass transition temperature is lowered, and in Comparative Examples 2 and 3 using a mixture having a weight average molecular weight exceeding 1550, solder heat resistance Sexually decreased.

  The laminate of the present invention is formed using a prepreg made of a thermosetting resin composition having a high glass transition temperature, excellent solder heat resistance, and a low coefficient of thermal expansion, and is highly integrated. It is useful as a printed circuit board for semiconductor packages and electronic devices.

Claims (13)

A siloxane compound (A) having a structural unit represented by the following general formula (1) and having an amino group at the molecular end,
A maleimide compound (B) having at least two N-substituted maleimide groups in one molecule;
An amine compound (C) having an acidic substituent represented by the following general formula (C-1), and an amine compound (D) having at least two primary amino groups in one molecule
A mixture having a weight-average molecular weight of 1100 to 1550, which contains a modified silicone compound obtained by reacting.

(In the formula, R ¹ and R ² each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.)

(In the formula, R ³ represents an acidic substituent selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. X represents 1 to 5) The integer and y are integers of 0 to 4 and satisfy 1 ≦ x + y ≦ 5, provided that when x is an integer of 2 to 5, a plurality of R ³ may be the same or different. In addition, when y is an integer of 2 to 4, a plurality of R ⁴ may be the same or different.   The mixture according to claim 1, wherein the siloxane compound (A) has one amino group at each of both ends of the molecule. The mixture according to claim 1 or 2, wherein both R ¹ and R ^{2 in the} general formula (1) are alkyl groups having 1 to 5 carbon atoms. The mixture according to claim 1 or 2, wherein the siloxane compound (A) is represented by the following general formula (A-1).

(In the formula, R ¹ and R ² are as defined above. N is an integer of 2 to 100. The plurality of R ¹ may be the same or different from each other. The plurality of R ² may be the same or different.
R ⁵ and R ⁶ are independently the same as defined for R ¹ and R ² .
X ¹ and X ² each independently represent a divalent organic group. ) In the general formula (A-1), R ¹ , R ² , R ⁵ and R ⁶ are all alkyl groups having 1 to 5 carbon atoms, and X ¹ and X ² are all having 1 to 5 carbon atoms. The mixture according to claim 4, which is a saturated hydrocarbon group. The mixture of any one of Claims 1-5 whose R < ³ > is a hydroxyl group in the said general formula (C-1).   The thermosetting resin composition containing the mixture of any one of Claims 1-6.   Furthermore, the thermosetting resin composition of Claim 7 containing an epoxy resin.   Furthermore, the thermosetting resin composition of Claim 7 or 8 containing an inorganic filler.   A prepreg obtained by impregnating or coating the sheet-shaped reinforcing base material with the thermosetting resin composition according to any one of claims 7 to 9.   A laminated board having an insulating resin layer, wherein the insulating resin layer is formed using the thermosetting resin composition according to any one of claims 7 to 9 or the prepreg according to claim 10. Board.   The printed wiring board obtained using the laminated board of Claim 11.   The semiconductor package which mounts a semiconductor element on the printed wiring board of Claim 12.