JP7124898B2 - Thermosetting resin compositions, prepregs, laminates, printed wiring boards and semiconductor packages - Google Patents

Description

The present invention relates to thermosetting resin compositions, prepregs, laminates, printed wiring boards and semiconductor packages.

Along with the trend toward smaller size and higher performance of electronic devices in recent years, printed wiring boards are progressing toward higher wiring density and higher integration. There is a growing demand for improved reliability due to improved heat resistance and the like. For such applications, particularly semiconductor package substrate applications, it is required to have both excellent heat resistance and low thermal expansion.
In addition, due to high-speed communication, there is a tendency for signals to be handled to be of higher frequency in order to process a large amount of data at high speed. Therefore, in order to suppress transmission loss due to higher frequencies, organic materials used in the high frequency range are required to have excellent dielectric properties (low dielectric constant and low dielectric loss tangent).

Laminates for printed wiring boards are generally produced by curing and integrally molding a prepreg containing a resin composition containing an epoxy resin as a main component and glass cloth.
Epoxy resin has an excellent balance of insulation, heat resistance, cost, etc., but further improvements are necessary to meet the demand for improved heat resistance that accompanies recent high-density mounting and multi-layer construction of printed wiring boards. becomes.

On the other hand, it is known that a modified maleimide resin obtained by modifying a maleimide compound with an amine compound has excellent heat resistance and low thermal expansion (see, for example, Patent Document 1). In addition, a thermosetting resin composition containing a modified maleimide resin obtained by modifying a maleimide compound with an amine compound, a thermosetting resin such as an epoxy resin, and a modified imidazole compound having a triazine ring can be used at high temperatures and long distances during prepreg lamination. It is known that it does not require time treatment, has good curability and storage stability of varnishes and prepregs, and is excellent in chemical resistance, heat resistance, adhesiveness and low warpage (for example, Patent Document 2).

WO2012/099133 JP 2011-157509 A

Polyimide resins such as the modified maleimide resin described in Patent Document 1 generally tend to have a higher glass transition temperature (Tg) than epoxy resins, and thus are excellent in heat resistance and low thermal expansion. In the case of epoxy resin, it is usually possible to cure at about 180 to 200°C, but in the case of polyimide resin such as modified maleimide resin, a high temperature of 220°C or higher and a long time curing treatment are required, and when prepreg is laminated. There was a problem that a high temperature and a long time were required, resulting in poor productivity. Therefore, there is a demand for a material that does not excessively raise the temperature during prepreg lamination, that is, the press temperature, has a high glass transition temperature after curing, and has excellent heat resistance and low thermal expansion.
In addition, the thermosetting resin composition described in Patent Document 2 has excellent heat resistance and low thermal expansion, but since the epoxy resin is inferior in dielectric properties, low relative dielectric constant and low dielectric loss tangent accompanying high-speed communication could not meet such demands. Resin compositions and prepregs for producing printed wiring boards must have storage stability. Since it uses a modified imidazole compound containing a triazine ring, which has high latency (that is, it does not promote the reaction unless under specific conditions), it is excellent in that it can be stored for a long time. However, a thermosetting resin composition essentially containing a modified imidazole compound containing a triazine ring has room for improvement in terms of low thermal expansion. Since dielectric properties are lowered when a resin is contained, it has been difficult to achieve both heat resistance and dielectric properties.

In view of the current situation, the present invention has a high glass transition temperature and low thermal expansion, excellent dielectric properties, solder heat resistance and storage stability, and requires a press temperature of 220 ° C. or higher during prepreg lamination. It is an object of the present invention to provide a thermosetting resin composition that does not have a high temperature, and a prepreg, a laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition.

The inventors of the present invention have made intensive studies to solve the above problems, and found that a thermosetting resin composition containing a specific modified maleimide resin and a specific imidazole compound does not contain an epoxy resin. , or a thermosetting resin composition having a content of not more than a predetermined amount, it was found that the above problems could be solved, and the present invention was completed.

（一般式（Ａ１）中、Ｒ^１は、水素原子、炭素数１～５の脂肪族炭化水素基、又は、炭素数６～２０の芳香族炭化水素基が置換した炭素数１～５の脂肪族炭化水素基を示す。Ｒ^２は、水素原子、炭素数１～２０の脂肪族炭化水素基又は炭素数６～２０の芳香族炭化水素基を示す。Ｒ^３及びＲ^４は各々独立に、水素原子又は炭素数１～５の脂肪族炭化水素基を示す。）
［２］１分子中に少なくとも２個の一級アミノ基を有するアミン化合物（ｂ－２）が、分子末端にアミノ基を有する変性シロキサン化合物を含有する、上記［１］に記載の熱硬化性樹脂組成物。
［３］さらに、硬化促進剤（Ｃ）、熱可塑性エラストマー（Ｄ）及び無機充填材（Ｅ）からなる群から選択される少なくとも１種を含有する、上記［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］上記［１］～［３］のいずれかに記載の熱硬化性樹脂組成物を繊維基材に含浸させてなるプリプレグ。
［５］上記［４］に記載のプリプレグを積層成形して得られる積層板。
［６］上記［４］に記載のプリプレグ又は上記［５］に記載の積層板を含有してなるプリント配線板。
［７］上記［６］に記載のプリント配線板を含有してなる半導体パッケージ。 That is, the present invention relates to the following [1] to [7].
[1] an imidazole compound (A) represented by the following general formula (A1);
A reaction product of a maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule and an amine compound (b-2) having at least two primary amino groups in one molecule. a modified maleimide resin (B);
A thermosetting resin composition containing
A thermosetting resin composition that does not contain an epoxy resin, or, if it contains an epoxy resin, the content thereof is 5% by mass or less relative to the thermosetting resin composition.

(In the general formula (A1), R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with an aromatic hydrocarbon group having 6 to 20 carbon atoms R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ³ and R ⁴ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.)
[2] The thermosetting resin according to [1] above, wherein the amine compound (b-2) having at least two primary amino groups in one molecule contains a modified siloxane compound having an amino group at the molecular end. Composition.
[3] The above [1] or [2], further comprising at least one selected from the group consisting of a curing accelerator (C), a thermoplastic elastomer (D) and an inorganic filler (E). A thermosetting resin composition.
[4] A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of [1] to [3] above.
[5] A laminate obtained by laminate-molding the prepreg according to [4] above.
[6] A printed wiring board comprising the prepreg according to [4] above or the laminate according to [5] above.
[7] A semiconductor package comprising the printed wiring board according to [6] above.

According to the present invention, it has a high glass transition temperature and low thermal expansion, is excellent in dielectric properties, solder heat resistance and storage stability, and is heat cured without requiring a press temperature of 220 ° C. or higher during prepreg lamination. A prepreg, a laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition can be provided.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention is
The imidazole compound (A) represented by the general formula (A1) described later [hereinafter sometimes referred to as "imidazole compound (A)". ]When,
A maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule [hereinafter sometimes referred to as "maleimide compound (b-1)". ] and an amine compound (b-2) having at least two primary amino groups in one molecule [hereinafter sometimes referred to as “amine compound (b-2)”. ] and the modified maleimide resin (B) [hereinafter, sometimes referred to as "modified maleimide resin (B)". ]When,
A thermosetting resin composition containing
The thermosetting resin composition does not contain an epoxy resin, or, if it contains an epoxy resin, the content thereof is 5% by mass or less relative to the thermosetting resin composition.
Each component will be described in order below.

<Imidazole compound (A)>
The thermosetting resin composition of the present invention contains the imidazole compound (A), but the imidazole compound (A) does not have sufficient latency for the reaction between the epoxy resin and the amine compound, making long-term storage difficult. is a compound. However, in the present invention, by using a modified maleimide resin instead of an epoxy resin as a thermosetting resin, long-term storage is possible in spite of containing the imidazole compound (A).
In addition, the imidazole compound (A), compared with the modified imidazole compound containing a triazine ring in the molecule as described in Patent Document 2, the modified maleimide resin (B) at a lower temperature (for example, about 200 ° C.). can be cured with Therefore, it is not necessary to set the pressing temperature to 220° C. or higher when laminating the prepregs, which will be described later, and the curing reaction proceeds sufficiently at a pressing temperature of about 200° C., resulting in a high glass transition temperature.

（一般式（Ａ１）中、Ｒ^１は、水素原子、炭素数１～５の脂肪族炭化水素基、又は、炭素数６～２０の芳香族炭化水素基が置換した炭素数１～５の脂肪族炭化水素基を示す。Ｒ^２は、水素原子、炭素数１～２０の脂肪族炭化水素基又は炭素数６～２０の芳香族炭化水素基を示す。Ｒ^３及びＲ^４は各々独立に、水素原子又は炭素数１～５の脂肪族炭化水素基を示す。） The imidazole compound (A) is represented by the following general formula (A1).

(In the general formula (A1), R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with an aromatic hydrocarbon group having 6 to 20 carbon atoms R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ³ and R ⁴ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.)

Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl. and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group.
The aliphatic hydrocarbon group having 1 to 5 carbon atoms in the aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ¹ is the same as those described above. and the preferred ones are also the same. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms as a substituent of the aliphatic hydrocarbon group include phenyl group, naphthyl group, anthryl group and biphenylyl group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and still more preferably a phenyl group.

Examples of aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl. group, n-octyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aliphatic hydrocarbon group having 8 to 12 carbon atoms, More preferred are methyl group, ethyl group and undecyl group.
Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ² include phenyl group, naphthyl group, anthryl group and biphenylyl group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and still more preferably a phenyl group.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ³ and R ⁴ include the same aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R ¹ , and the preferred ones are also the same. .
Each group of R ¹ to R ⁴ can be arbitrarily combined from the above options. In particular, R ¹ may be a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with an aromatic hydrocarbon group having 6 to 20 carbon atoms. Both are preferred, and R ² is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and each of R ³ and R ⁴ is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. is also preferred.

（一般式（Ａ１－１）～（Ａ１－３）中、Ｒ^２～Ｒ^４は、一般式（Ａ１）中のものと同じであり、好ましいものも同じである。） From the above, the imidazole compound (A) is preferably represented by any one of the following general formulas (A1-1) to (A1-3).

(In general formulas (A1-1) to (A1-3), R ² to R ⁴ are the same as in general formula (A1), and preferred ones are also the same.)

You may use a commercial item as an imidazole compound (A). Examples of the commercially available products include SIZ, 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ, 2PZ-PW, 2P4MZ, 1B2MZ, and 1B2PZ (manufactured by Shikoku Kasei Co., Ltd.).

(Content of imidazole compound (A))
The content of the imidazole compound (A) in the thermosetting resin composition of the present invention is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. , more preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and particularly preferably 0.2 to 2 parts by mass.
As used herein, the term "solid content" refers to non-volatile content excluding volatile substances such as solvents. Also includes liquid, starch syrup and wax. Here, room temperature indicates 25° C. in this specification.
In addition, the "resin component" is a resin or a component used in the production of a resin, excluding the inorganic filler (E) described later, and specifically includes an imidazole compound (A) and a modified maleimide resin (B). , curing accelerator (C), thermoplastic elastomer (D), etc. correspond to the resin component.

<Modified maleimide compound (B)>
The modified maleimide compound (B) includes a maleimide compound (b-1) having at least two N-substituted maleimide groups per molecule and an amine compound (b- 2).

(Maleimide compound (b-1))
The maleimide compound (b-1) is not particularly limited as long as it is a maleimide compound having at least two N-substituted maleimide groups in one molecule. A maleimide compound having an aliphatic hydrocarbon group between any two maleimide groups out of a plurality of maleimide groups [hereinafter referred to as an aliphatic hydrocarbon group-containing maleimide], and any of a plurality of maleimide groups and a maleimide compound containing an aromatic hydrocarbon group between two maleimide groups of (hereinafter referred to as an aromatic hydrocarbon group-containing maleimide). Among these, aromatic hydrocarbon group-containing maleimide is preferable from the viewpoint of glass transition temperature, coefficient of thermal expansion, dielectric properties, soldering heat resistance and storage stability. The aromatic hydrocarbon group-containing maleimide may contain an aromatic hydrocarbon group between any two arbitrarily selected combinations of maleimide groups.

As the maleimide compound (b-1), a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (b-1-1) is more preferable.

（一般式（ｂ－１－１）中、Ｘ^ｂ１は、下記一般式（ｂ１－１）、（ｂ１－２）、（ｂ１－３）又は（ｂ１－４）で表される基である。）

(In the general formula (b-1-1), X ^b1 is a group represented by the following general formula (b1-1), (b1-2), (b1-3) or (b1-4). )

（一般式（ｂ１－１）中、Ｒ^ｂ１は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｐは０～４の整数である。）

(In general formula (b1-1), each R ^b1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p is an integer of 0 to 4.)

（一般式（ｂ１－２）中、Ｒ^ｂ２及びＲ^ｂ３は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘ^ｂ２は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、単結合又は下記一般式（ｂ１－２－１）で表される基である。ｑ及びｒは各々独立に０～４の整数である。）

（一般式（ｂ１－２－１）中、Ｒ^ｂ４及びＲ^ｂ５は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘ^ｂ３は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ及びｔは各々独立に０～４の整数である。）

(In general formula (b1-2), R ^b2 and R ^b3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X ^b2 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carboxyl group, a keto group, a single bond, or a group represented by the following general formula (b1-2-1) of numbers 2 to 5. q and r are each independent; is an integer from 0 to 4.)

(In general formula (b1-2-1), R ^b4 and R ^b5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X ^b3 is an alkylene group having 1 to 5 carbon atoms; , an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carboxyl group, a keto group, or a single bond, and s and t are each independently an integer of 0 to 4.)

（一般式（ｂ１－３）中、ｎは１～１０の整数である。）

(In general formula (b1-3), n is an integer of 1 to 10.)

（一般式（ｂ１－４）中、Ｒ^ｂ６及びＲ^ｂ７は各々独立に、水素原子又は炭素数１～５の脂肪族炭化水素基である。ｕは１～８の整数である。）

(In general formula (b1-4), R ^b6 and R ^b7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer of 1 to 8.)

In the general formula (1), the aliphatic hydrocarbon group represented by R ^b1 includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group. Further, the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among them, R ^b1 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0 from the viewpoint of availability. When p is an integer of 2 or more, a plurality of R ^b1 may be the same or different.

In general formula (b1-2), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b2 and R ^b3 are the same as those for R ^b1 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably methyl group and ethyl group, still more preferably ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^b2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 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 glass transition temperature, coefficient of thermal expansion, dielectric properties, soldering heat resistance and storage stability.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^b2 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like. Among these, an isopropylidene group is preferable from the viewpoint of glass transition temperature, coefficient of thermal expansion, dielectric properties, soldering heat resistance, and storage stability.
Among the above options, X ^b2 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
q and r are each independently an integer of 0 to 4, and both are preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability. When q or r is an integer of 2 or more, a plurality of R ^b2 or R ^b3 may be the same or different.

（一般式（ｂ１－２－１’）中のＸ^ｂ３、Ｒ^ｂ４、Ｒ^ｂ５、ｓ及びｔは、一般式（ｂ１－２－１）中のものと同じであり、好ましいものも同じである。） In the general formula (b1-2-1), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b4 and R ^b5 are the same as in the case of R ^b2 and R ^b3 . , and the preferred ones are also the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^b3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^b2 . and the preferred ones are also the same.
Among the above options, X ^b3 is preferably an alkylidene group having 2 to 5 carbon atoms, more preferably as described above.
s and t are integers of 0 to 4, and both are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability. When s or t is an integer of 2 or more, a plurality of ^{Rb4's or Rb5 's} may be the same or different.
Further, the general formula (b1-2-1) is preferably represented by the following general formula (b1-2-1').

(X ^b3 , R ^b4 , R ^b5 , s and t in general formula (b1-2-1′) are the same as in general formula (b1-2-1), and preferred ones are also the same .)

In general formula (b1-3), n is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3, from the viewpoint of availability.
In general formula (b1-4), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b6 and R ^b7 are the same as in R ^b1 in general formula (b1-1). and the preferred ones are also the same. u is an integer of 1-8, preferably 1-3, more preferably 1;

（一般式（ｂ１－２’）中のＸ^ｂ２、Ｒ^ｂ２、Ｒ^ｂ３、ｑ及びｒは、一般式（ｂ１－２）中のものと同じであり、好ましいものも同じである。） In general formula (b-1-1), X ^b1 is represented by general formula (b1-2) from the viewpoint of glass transition temperature, coefficient of thermal expansion, dielectric properties, soldering heat resistance, and storage stability. A group represented by the following general formula (b1-2′) is more preferable.

(X ^b2 , R ^b2 , R ^b3 , q and r in general formula (b1-2′) are the same as in general formula (b1-2), and preferred ones are also the same.)

X ^b1 in the general formula (b-1-1) includes the following (b1-i) to (b1-iii) from the viewpoint of glass transition temperature, thermal expansion coefficient, dielectric properties, soldering heat resistance and storage stability. ), and more preferably a group represented by (b1-i) or (b1-ii) below.

Specific examples of the maleimide compound (b-1) include N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, bis(4-maleimidocyclohexyl)methane, and 1,4-bis(maleimide). Maleimides containing aliphatic hydrocarbon groups such as methyl)cyclohexane; 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′-diphenylmethanebismaleimide, 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)cyclohexane, 1,3-bis(4-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-maleimidophenoxy)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-hexafluoro Propane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]keto 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, 1,4 -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-maleimidophenoxy) )-3,5-dimethyl-α,α-dimethylbenzyl]benzene and aromatic hydrocarbon group-containing maleimides such as polyphenylmethane maleimide. These may be used alone or in combination of two or more.
Among these, a maleimide compound having a phenoxy group is preferable from the viewpoint of solubility in a solvent, and bis(4-maleimidophenyl)methane is preferable from the viewpoint of high reactivity and higher heat resistance. , 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane are more preferred.

（一般式（ｂ－２－１）中、Ｙ^ｂ１は、下記一般式（ｂ２－１）又は（ｂ２－２）で表される基である。） (Amine compound (b-2))
Amine compound (b-2) is not particularly limited as long as it is an amine compound having at least two primary amino groups in one molecule.
Amine compound (b-2) is preferably an amine compound having two primary amino groups in one molecule. A modified siloxane compound having

(In the general formula (b-2-1), ^Yb1 is a group represented by the following general formula (b2-1) or (b2-2).)

（一般式（ｂ２－１）中、Ｒ^ｂ’１は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｐ２は０～４の整数である。）

(In general formula (b2-1), each R ^b′1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p2 is an integer of 0 to 4.)

（一般式（ｂ２－２）中、Ｒ^ｂ’２及びＲ^ｂ’３は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｙ^ｂ２は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基、単結合又は下記一般式（ｂ２－２－１）で表される基である。ｑ２及びｒ２は各々独立に０～４の整数である。）

（一般式（ｂ２－２－１）中、Ｒ^ｂ’４及びＲ^ｂ’５は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｙ^ｂ３は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボオキシ基、ケト基又は単結合である。ｓ２及びｔ２は各々独立に０～４の整数である。）

(In general formula (b2-2), R ^b′2 and R ^b′3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y ^b2 is a an alkylene group, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carboxyl group, a keto group, a single bond, or a group represented by the following general formula (b2-2-1): q2 and Each r2 is independently an integer of 0 to 4.)

(In general formula (b2-2-1), R ^b′4 and R ^b′5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y ^b3 has 1 to an alkylene group having 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carboxyl group, a keto group, or a single bond, and s2 and t2 are each independently an integer of 0 to 4.)

In the general formula (b2-1), examples of the aliphatic hydrocarbon group represented by R ^b′1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t- butyl group, n-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group. Further, the halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among them, R ^b′1 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 2 from the viewpoint of availability. When p2 is an integer of 2 or more, a plurality of R ^b'1 may be the same or different.

In the general formula (b2-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b′2 and R ^b′3 are the same as in the case of R ^b′1 . be done. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably methyl group and ethyl group, still more preferably ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by Y ^b2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 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 glass transition temperature, coefficient of thermal expansion, dielectric properties, soldering heat resistance and storage stability.
The alkylidene group having 2 to 5 carbon atoms represented by ^Yb2 includes, for example, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group and the like. Among these, an isopropylidene group is preferable from the viewpoint of glass transition temperature, coefficient of thermal expansion, dielectric properties, soldering heat resistance, and storage stability.
Among the above options, ^Yb2 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. More preferred are as described above.
q2 and r2 are each independently an integer of 0 to 4, and both are preferably integers of 0 to 2, more preferably 0 or 2 from the viewpoint of availability. When q2 or r2 is an integer of 2 or more, a plurality of R ^b'2 or R ^b'3 may be the same or different.

（一般式（ｂ２－２－１’）中のＹ^ｂ３、Ｒ^ｂ’４、Ｒ^ｂ’５、ｓ２及びｔ２は、一般式（ｂ２－２－１）中のものと同じであり、好ましいものも同じである。） In general formula (b2-2-1), the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^b′4 and R ^b′5 are R ^b′2 and R ^b′3 The same ones as in the case of are mentioned, and preferable ones are also the same.
The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by Y ^b3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by Y ^b2 . and the preferred ones are also the same.
Among the above options, Y ^b3 is preferably an alkylidene group having 2 to 5 carbon atoms, more preferably as described above.
s2 and t2 are integers of 0 to 4, and both are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0 from the viewpoint of availability. When s2 or t2 is an integer of 2 or more, a plurality of R ^b'4 or R ^b'5 may be the same or different.
The general formula (b2-2-1) is preferably represented by the following general formula (b2-2-1').

(Y ^b3 , R ^b′4 , R ^b′5 , s2 and t2 in general formula (b2-2-1′) are the same as in general formula (b2-2-1), and are preferred is the same.)

（一般式（ｂ２－２’）中のＹ^ｂ２、Ｒ^ｂ’２、Ｒ^ｂ’３、ｑ２及びｒ２は、一般式（ｂ２－２）中のものと同じであり、好ましいものも同じである。） In the general formula (b-2-1), Y ^b1 is represented by the general formula (b2-2) from the glass transition temperature, thermal expansion coefficient, dielectric properties, soldering heat resistance and storage stability. and more preferably a group represented by the following general formula (b2-2′).

(Y ^b2 , R ^b′2 , R ^b′3 , q2 and r2 in general formula (b2-2′) are the same as in general formula (b2-2), and preferred ones are also the same .)

Y ^b1 in the general formula (b-2-1) is represented by the following formulas (b2-i) to (b2-iii) from the viewpoint of glass transition temperature, thermal expansion coefficient, dielectric properties, soldering heat resistance and storage stability. ), and more preferably a group represented by the following formula (b2-ii) or (b2-iii).

Specific examples of the diamine represented by the general formula (b-2-1) include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, 2,5- Dimethyl-1,4-diaminobenzene, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4 '-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 , 2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3′-dimethyl-5,5′ -diethyl-4,4'-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3- aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-( 4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene and the like. These may be used alone or in combination of two or more.

Among these, for example, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-diethyl-4,4'-diaminodiphenylmethane, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane is preferred.

（一般式（ｂ－２－２）中、Ｒ^ｂ’７及びＲ^ｂ’８は各々独立に、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表す。）
Ｒ^ｂ’７及びＲ^ｂ’８が表す炭素数１～５のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。該アルキル基としては、炭素数１～３のアルキル基が好ましく、メチル基がより好ましい。
置換フェニル基におけるフェニル基が有する置換基としては、例えば、炭素数１～５のアルキル基、炭素数２～５のアルケニル基、炭素数２～５のアルキニル基が挙げられる。該炭素数１～５のアルキル基としては、前記したものと同じものが挙げられる。該炭素数２～５のアルケニル基としては、ビニル基、アリル基等が挙げられる。炭素数２～５のアルキニル基としては、エチニル基、プロパルギル基等が挙げられる。
Ｒ^ｂ’７及びＲ^ｂ’８は、いずれも炭素数１～５のアルキル基であることが好ましく、メチル基であることがより好ましい。 Further, the above-mentioned modified siloxane compound having an amino group at the molecular end preferably contains a structural unit represented by the following general formula (b-2-2).

(In general formula (b-2-2), R ^b'7 and R ^b'8 each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group.)
Examples of alkyl groups having 1 to 5 carbon atoms represented by R ^b'7 and R ^b'8 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. , n-pentyl group and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
Examples of substituents of the phenyl group in the substituted phenyl group include alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, and alkynyl groups having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms are the same as those described above. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. The alkynyl group having 2 to 5 carbon atoms includes ethynyl group, propargyl group and the like.
Each of R ^b'7 and R ^b'8 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group.

（一般式（ｂ－２－３）中、Ｒ^ｂ’７及びＲ^ｂ’８は、一般式（ｂ－２－２）中のものと同じである。Ｒ^ｂ’９及びＲ^ｂ’１０は各々独立に、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表す。Ｒ^ｂ’１１及びＲ^ｂ’１２は各々独立に、２価の有機基を表し、ｍは２～１００の整数である。） A siloxane diamine represented by the following general formula (b-2-3) is more preferable as the modified siloxane compound having an amino group at the molecular terminal.

(In general formula (b-2-3), R ^b'7 and R ^b'8 are the same as in general formula (b-2-2). R ^b'9 and R ^b'10 are each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group, each of R ^b′11 and R ^b′12 independently represents a divalent organic group, m is 2 to 100; is an integer.)

The alkyl group having 1 to 5 carbon atoms, the phenyl group and the substituted phenyl group represented by R ^b'9 and R ^b'10 are explained in the same manner as for R ^b'7 and R ^b'8 . R ^b'9 and R ^b'10 are preferably methyl groups.
Examples of the divalent organic group represented by R ^b'11 and R ^b'12 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, and a divalent linking group in which these are combined. be done. The alkylene group includes an alkylene group having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group. The alkenylene group includes alkenylene groups having 2 to 10 carbon atoms. The alkynylene group includes an alkynylene group having 2 to 10 carbon atoms. The arylene group includes arylene groups having 6 to 20 carbon atoms such as phenylene group and naphthylene group.
Among these, R ^b'11 and R ^b'12 are preferably alkylene groups and arylene groups.

Although there are no particular restrictions on the functional group equivalent weight of the modified siloxane compound, it is preferably 300 to 3,000 g/mol, more preferably 400 to 2,000 g/mol, still more preferably 600 to 2,000 g/mol.

A commercially available product can be used as the modified siloxane compound. Commercially available products include, for example, "KF-8010" (functional group equivalent of amino group: 430 g/mol), "X-22-161A" (functional group equivalent of amino group: 800 g/mol), "X-22- 161B" (functional group equivalent of amino group: 1,500 g / mol), "KF-8012" (functional group equivalent of amino group: 2,200 g / mol), "KF-8008" (functional group equivalent of amino group: 5,700 g/mol), "X-22-9409" (functional group equivalent of amino group: 700 g/mol), "X-22-1660B-3" (functional group equivalent of amino group: 2,200 g/mol) (manufactured by Shin-Etsu Chemical Co., Ltd.), "BY-16-853U" (functional group equivalent of amino group: 460 g / mol), "BY-16-853" (functional group equivalent of amino group: 650 g / mol) , "BY-16-853B" (functional group equivalent of amino group: 2,200 g / mol) (manufactured by Dow Corning Toray Co., Ltd.), "XF42-C5742" (functional group equivalent of amino group: 1,280 g / mol), "XF42-C6252" (functional group equivalent of amino group: 1,255 g / mol), "XF42-C5379" (functional group equivalent of amino group: 745 g / mol) (above, Momentive Performance Materials・Manufactured by Japan LLC), etc. These may be used alone or in combination of two or more.
Among these, for example, "X-22-161A", "X-22-161B", "KF-8012", "X-22-1660B- 3”, “XF42-C5379”, “XF42-C6252”, and “XF42-C5742” are preferred, and from the viewpoint of excellent compatibility and high elastic modulus, “X-22-161A” and “X-22-161B ”, “XF42-C6252”, and “XF42-C5742” are more preferred.

The modified maleimide resin (B) contained in the thermosetting resin composition of the present invention is the maleimide compound (b-1) and a siloxane diamine containing a structural unit represented by the general formula (b-2-2). It is preferably a reactant with. Furthermore, the modified maleimide resin (B) comprises the maleimide compound (b-1), the diamine represented by the general formula (b-2-1), and the structure represented by the general formula (b-2-2). More preferably, it is a reactant with a siloxane diamine containing unit. In the latter case, the usage ratio of the diamine represented by the general formula (b-2-1) and the siloxane diamine containing the structural unit represented by the general formula (b-2-2) [siloxane diamine/general formula The diamine represented by (b-2-1)] is preferably 3/97 to 90/10, more preferably 10/90 to 80/20, and still more preferably 20/80 to 70/30 in mass ratio. , particularly preferably 30/70 to 70/30.

一般式（Ｂ１）中、Ｘ^ｂ１は、前記一般式（ｂ－１－１）中のものと同じであり、好ましいものも同じである。
Ｙは、前記一般式（ｂ－２－１）中のＹ^ｂ１であるか、又は下記一般式（ｂ－２－３’）で表される２価の基である。

（一般式（ｂ－２－３’）中、Ｒ^ｂ’７～Ｒ^ｂ’１２及びｍは、前記一般式（ｂ－２－３）中のものと同じであり、好ましいものも同じである。） The modified maleimide resin (B) has a structural unit represented by the following general formula (B1).

In general formula (B1), X ^b1 is the same as in general formula (b-1-1) above, and preferred ones are also the same.
Y is Y ^b1 in general formula (b-2-1) above, or a divalent group represented by general formula (b-2-3′) below.

(In the general formula (b-2-3′), R ^b′7 to R ^b′12 and m are the same as in the general formula (b-2-3), and the preferred ones are also the same .)

The modified maleimide resin (B) may be a modified maleimide resin represented by the following general formula (B1-1).

In general formula (B1-1), ^Xb1 and Y are the same as in general formula (B1), and preferred ones are also the same.
w is preferably an integer of 1-30, more preferably an integer of 1-20. However, when w is an integer of 2 or more, a plurality of Y's may be the same or different. That is, when w is an integer of 2 or more, Y which is Y ^b1 and Y which is a divalent group represented by the general formula (b-2-3′) may coexist, and , preferably coexist.

(Method for producing modified maleimide resin (B))
The modified maleimide resin (B) can be produced by reacting the maleimide compound (b-1) with the amine compound (b-2).
In the reaction, the ratio of the maleimide compound (b-1) and the amine compound (b-2) to be used is such that the equivalent of the maleimide group of the maleimide compound (b-1) is the same as the amine, from the viewpoint of gelation prevention and heat resistance. The ratio of the equivalent weight of the maleimide group of the maleimide compound (b-1) to the equivalent weight of the primary amino group of the amine compound (b-2) [(b -1)/(b-2)] is preferably 2 to 15, more preferably 3 to 10.

The reaction temperature is preferably 70 to 150°C, more preferably 100 to 130°C, from the viewpoint of productivity and uniform progress of the reaction. The reaction time is not particularly limited, but preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

The reaction can use a reaction catalyst, if necessary. Although the reaction catalyst is not particularly limited, examples thereof include amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine. These can be used individually by 1 type or in mixture of 2 or more types.

The reaction is preferably carried out in an organic solvent. Examples of organic solvents include 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; ester solvents; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide, etc. mentioned. The organic solvent may be used alone or in combination of two or more.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are preferable from the viewpoint of low toxicity, high volatility, and little residual solvent. , dimethylacetamide is preferred.
From the viewpoint of solubility and reaction rate, the amount of the organic solvent used is preferably 25 to 1,000 parts by mass with respect to the total of 100 parts by mass of the maleimide compound (b-1) and the amine compound (b-2). 50 to 500 parts by mass is more preferable.

(Content of modified maleimide resin (B))
The content of the modified maleimide resin (B) in the thermosetting resin composition of the present invention is preferably 50 to 99 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 60 to 95 parts by mass is more preferable, 70 to 95 parts by mass is more preferable, and 80 to 95 parts by mass is particularly preferable.
In addition, from the viewpoint of elastic modulus and low thermal expansion, the content of the modified maleimide resin (B) is the amount of the raw material maleimide compound (b-1) converted from the amount of the modified maleimide resin (B). The amount is preferably 20 to 95 parts by mass, more preferably 40 to 90 parts by mass, based on 100 parts by mass of the solid content of the resin component in the curable resin composition.
In addition, the content of the modified maleimide resin (B) in the thermosetting resin composition of the present invention is the modified maleimide resin ( The amount of the raw material amine compound (b-2) converted from the amount of B) is 3 to 50 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. Preferably, the amount of 5 to 40 parts by mass is more preferable.

<Curing accelerator (C)>
The thermosetting resin composition of the present invention containing the imidazole compound (A) and the modified maleimide resin (B) has good thermosetting reactivity. C) may be contained. Inclusion of the curing accelerator (C) tends to improve heat resistance, copper foil adhesion and mechanical strength.
As the curing accelerator (C), organic phosphorus compounds such as triphenylphosphine; imidazoles and their derivatives; nitrogen-containing compounds such as secondary amines, tertiary amines, and quaternary ammonium salts; dicumyl Peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, α,α'- organic peroxides such as bis(t-butylperoxy)diisopropylbenzene; and organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. The curing accelerator (C) may be used alone or in combination of two or more.
When the thermosetting resin composition of the present invention contains a curing accelerator (C), its content is 0.01 to 0.01 parts per 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 10 parts by weight is preferred, 0.1 to 5 parts by weight is more preferred, 0.2 to 2 parts by weight is even more preferred, and 0.2 to 2 parts by weight is particularly preferred.

<Thermoplastic elastomer (D)>
The thermoplastic elastomer (D) includes styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, silicone-based elastomers, and derivatives thereof. The thermoplastic elastomer (D) may be used alone or in combination of two or more.

As the thermoplastic elastomer (D), one having a reactive functional group at the molecular end or in the molecular chain can be used. Examples of reactive functional groups include epoxy group, hydroxyl group, carboxy group, amino group, amide group, isocyanate group, acrylic group, methacrylic group, vinyl group and the like. By having these reactive functional groups in the molecular terminal or in the molecular chain, the compatibility is improved, the internal stress generated during curing of the thermosetting resin composition can be more effectively reduced, and the substrate Warping can be reduced.
Among these reactive functional groups, it is preferable to have an epoxy group, a hydroxyl group, a carboxyl group, an amino group, or an amide group from the viewpoint of adhesion to the metal foil, and an epoxy group from the viewpoint of heat resistance and insulation reliability. , a hydroxyl group, and an amino group.

Styrene-based elastomers include styrene-butadiene copolymers such as styrene-butadiene-styrene block copolymers; styrene-isoprene copolymers such as styrene-isoprene-styrene block copolymers; styrene-ethylene-butylene-styrene block copolymers; Examples include ethylene-propylene-styrene block copolymers. Styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used as raw material monomers for styrene-based elastomers in addition to styrene. Among these, styrene-butadiene copolymers and styrene-isoprene copolymers are preferred, and hydrogenated styrene-butadiene copolymer resins and hydrogenated styrene-isoprene copolymers obtained by hydrogenating the double bond portions of these copolymers. Hydrogenated styrene thermoplastic elastomers such as resins are more preferred.
As the styrene-based elastomer, a commercially available product may be used, and commercially available products include "Tufprene (registered trademark)", "Asaprene (registered trademark) T", "Tuftec (registered trademark) H1043", and "Tuftec (registered trademark)". ) MP10”, “Tuftec (registered trademark) M1911”, “Tuftec (registered trademark) M1913” (manufactured by Asahi Kasei Chemicals Corporation), “Epofriend (registered trademark) AT501”, “Epofriend (registered trademark) CT310” (manufactured by Daicel Corporation), "Septon (registered trademark) 2063" (manufactured by Kuraray Co., Ltd.), and the like.

Examples of olefinic elastomers include copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene; , 1,4-hexadiene, cyclooctandiene, methylenenorbornene, ethylidenenorbornene, butadiene, isoprene and other non-conjugated dienes having 2 to 20 carbon atoms; carboxy-modified butadiene-acrylonitrile rubber and the like.
Copolymers of α-olefins include ethylene-propylene copolymers (EPR) and ethylene-propylene-diene copolymers (EPDM).
Commercially available products may be used as the olefinic elastomer, and commercially available products include “PB3600”, “PB4700” (manufactured by Daicel Corporation), “G-1000”, “G-2000”, “G- 3000", "JP-100", "JP-200", "BN-1015", "TP-1001", "TEA-1000", "EA-3000", "TE-2000", "EMA-3000" (manufactured by Nippon Soda Co., Ltd.), "Denarex (registered trademark) R45" (manufactured by Nagase ChemteX Corporation), and the like.

Urethane-based elastomers include those having a hard segment composed of a low-molecular-weight (short-chain) diol and diisocyanate and a soft segment composed of a high-molecular-weight (long-chain) diol and diisocyanate.
Low molecular weight (short chain) diols include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A and the like. The low-molecular-weight (short-chain) diol preferably has a number average molecular weight of 48-500.
Polymeric (long-chain) diols include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene/1,4-butylene adipate), polycaprolactone, poly(1,6-heptylene adipate), xylene carbonate), poly(1,6-hexylene/neopentylene adipate), and the like. The number average molecular weight of the high molecular weight (long chain) diol is preferably 500 to 10,000.
As the urethane-based elastomer, a commercially available product may be used, and commercially available products include "PANDEX (registered trademark) T-2185" and "PANDEX (registered trademark) T-2983N" (manufactured by DIC Corporation). mentioned.

Polyester-based elastomers include those obtained by polycondensation of a dicarboxylic acid or its derivative and a diol compound or its derivative.
Dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; acids; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Dicarboxylic acids may be used alone or in combination of two or more.
Diol compounds include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,10-decanediol; Cyclic diols; aromatic diols such as bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane and resorcinol. The diol compounds may be used alone or in combination of two or more.
Also, a multi-block copolymer may be used in which an aromatic polyester (eg, polybutylene terephthalate) portion is used as a hard segment component and an aliphatic polyester (eg, polytetramethylene glycol) portion is used as a soft segment component. As the multi-block copolymer, there are various grades of commercial products depending on the type, ratio, and molecular weight of the hard segment and the soft segment. ), “Pelprene (registered trademark)” (manufactured by Toyobo Co., Ltd.), “Espel (registered trademark)” (manufactured by Hitachi Chemical Co., Ltd.), and the like.

Polyamide-based elastomers include polyamide as a hard segment component, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene-propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate, poly Examples include block copolymers having soft segment components such as methacrylate, polyurethane, and silicone rubber.
As the polyamide-based elastomer, a commercially available product may be used, and commercially available products include "UBE polyamide elastomer" (manufactured by Ube Industries, Ltd.), "DAIAMID (registered trademark)" (manufactured by Daicel-Evonik Co., Ltd.), "PEBAX (registered trademark)” (manufactured by Arkema), “Grillon (registered trademark) ELY” (manufactured by M Chemie Japan Co., Ltd.), “Novamid (registered trademark)” (manufactured by Mitsubishi Chemical Corporation), “Grelix (registered trademark)” ” (manufactured by DIC Corporation), “BPAM-01”, “BPAM-155” (manufactured by Nippon Kayaku Co., Ltd.) and the like.

Examples of acrylic elastomers include polymers obtained by polymerizing raw material monomers containing acrylic acid ester as a main component. Acrylic acid esters include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and the like. Moreover, as a cross-linking monomer, glycidyl methacrylate, allyl glycidyl ether, or the like may be used as a raw material, and acrylonitrile, ethylene, or the like may be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer and the like.

Silicone-based elastomers are mainly composed of organopolysiloxane, and are classified into polydimethylsiloxane-based, polymethylphenylsiloxane-based, polydiphenylsiloxane-based, and the like according to the structure of the skeleton.
As the silicone-based elastomer, a commercially available product may be used. Co., Ltd.), core-shell type silicone rubber "SY series" (manufactured by Wacker), "SE series", "CY series", "SH series" (manufactured by Dow Corning Toray Co., Ltd.). .

Among these, styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers, and silicone-based elastomers are preferable from the viewpoint of heat resistance and insulation reliability, and styrene-based elastomers and olefin-based elastomers are more preferable from the viewpoint of dielectric properties. A styrene-based thermoplastic elastomer is more preferred.

The weight average molecular weight (Mw) of the thermoplastic elastomer (D) is preferably 1,000 to 300,000, more preferably 2,000 to 150,000. When the weight average molecular weight (Mw) is at least the lower limit, the low thermal expansion property is excellent, and when it is at most the upper limit, the compatibility is excellent.
The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene.

The content of the thermoplastic elastomer (D) in the thermosetting resin composition is preferably 4 to 20 parts by mass, preferably 6 to 15 parts by mass, per 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. Parts by mass are more preferred. When the content of the thermoplastic elastomer (D) is 4 parts by mass or more, a sufficient effect of lowering the dielectric constant can be obtained. It is well dispersed inside and has excellent heat resistance and peel strength.

<Inorganic filler (E)>
The thermosetting resin composition of the present invention may further contain an inorganic filler (E).
Inorganic fillers (E) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, and aluminum silicate. , calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, silicon carbide, quartz powder, glass short fiber, fine glass powder, hollow glass, etc. . As the glass, E glass, T glass, D glass and the like are preferably used. The inorganic filler (E) may be used alone or in combination of two or more.
Among these, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. Examples of silica include precipitated silica, which is produced by a wet method and has a high water content, and dry-process silica, which is produced by a dry method and contains almost no bound water. , crushed silica, fumed silica, fused spherical silica, etc. Among these, fused spherical silica is preferable from the viewpoint of low thermal expansion and fluidity when filled in a resin.

The average particle size of the inorganic filler (E) is preferably 0.1-10 μm, more preferably 0.3-8 μm. When the average particle diameter is 0.1 μm or more, good fluidity can be maintained when the resin is highly filled. occurrence can be suppressed. Here, the average particle size is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve by 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 a particle size distribution measuring device or the like.
The inorganic filler (E) may be surface-treated with a coupling agent. The method of surface treatment with a coupling agent may be a method of performing a dry or wet surface treatment on the inorganic filler (E) before blending. A so-called integral blend treatment method may be employed in which a silane coupling agent is added to the composition after blending it with the components to form a composition.
Examples of coupling agents include silane-based coupling agents, titanate-based coupling agents, and silicone oligomers.

When the thermosetting resin composition of the present invention contains an inorganic filler (E), its content is 10 to 300 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. parts, more preferably 50 to 250 parts by mass, and even more preferably 70 to 180 parts by mass. When the content of the inorganic filler (E) is within the above range, good moldability and low thermal expansion properties are obtained.

When the thermosetting resin composition of the present invention contains an inorganic filler (E), it is optionally treated with a dispersing machine such as a triple roll, a bead mill, or a nanomizer to remove the inorganic filler (E). Improved dispersibility is preferred.

<Other ingredients>
As described above, the thermosetting resin composition of the present invention does not contain an epoxy resin, or even if it contains an epoxy resin, the content is 5% by mass or less with respect to the thermosetting resin composition. is. By setting the content of the epoxy resin to 5% by mass or less based on the thermosetting resin composition, excellent dielectric properties and storage stability can be obtained. When an epoxy resin is contained, the content thereof is preferably 2% by mass or less, more preferably 1% by mass or less, relative to the thermosetting resin composition from the same viewpoint. Moreover, it is more preferable that the thermosetting resin composition of the present invention does not substantially contain an epoxy resin.
The thermosetting resin composition of the present invention optionally contains known organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, adhesion improvers, and the like. good too.
Examples of organic fillers include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., and resin fillers having a core-shell structure.
Flame retardants include aromatic phosphate ester compounds, phosphazene compounds, phosphinate esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its phosphorus-based flame retardants such as derivatives; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; halogen-containing flame retardants containing bromine, chlorine, etc.; inorganic flame retardants such as antimony trioxide A fuel and the like can be mentioned.
Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers.
Antioxidants include hindered phenol antioxidants, hindered amine antioxidants, and the like.
Photopolymerization initiators include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
Examples of fluorescent brightening agents include fluorescent brightening agents of stilbene derivatives.
Examples of the adhesion improver include urea compounds such as urea silane and the above coupling agents.

The thermosetting resin composition of the present invention may be in the form of a varnish in which each component is dissolved or dispersed in an organic solvent for use in the production of prepregs and the like.

Organic solvents used for varnish include alcohol solvents such as methanol, 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; butyl acetate, propylene. ester solvents such as glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Sulfur atom-containing solvents and the like are included. These organic solvents may be used alone or in combination of two or more.
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferred from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferred from the viewpoint of low toxicity.
The solid content concentration of the varnish is preferably 40-90% by mass, more preferably 50-80% by mass. When the solid content concentration of the varnish is within the above range, good coatability can be maintained, and a prepreg having an appropriate resin composition adhesion amount can be obtained.

[Prepreg]
The prepreg of the present invention is obtained by impregnating a fiber base material with the thermosetting resin composition of the present invention.
The prepreg of the present invention can be produced by impregnating a fiber base material with the thermosetting resin composition of the present invention and semi-curing it by heating or the like (to B-stage).
As the fiber base material, well-known ones used for various laminates for electrical insulating materials can be used. Examples of materials thereof include inorganic fibers such as E glass, S glass, low dielectric glass and Q glass; organic fibers such as low dielectric glass polyimide, polyester and tetrafluoroethylene; and mixtures thereof. In particular, low dielectric glass and Q glass are preferable from the viewpoint of obtaining a substrate having excellent dielectric properties.

These fiber base materials have shapes such as woven fabrics, non-woven fabrics, roving, chopped strand mats, and surfacing mats. Therefore, it is possible to combine one or two or more types of materials and shapes. The thickness of the fiber base material can be, for example, about 0.03 to 0.5 mm. These fiber substrates are preferably surface-treated with a silane coupling agent or the like or mechanically fiber-opened from the standpoint of heat resistance, moisture resistance, processability, and the like.

In the prepreg of the present invention, for example, the amount of solids adhering to the base material of the thermosetting resin composition is preferably 20 to 90% by mass in terms of the content of the thermosetting resin composition relative to the prepreg after drying.
The prepreg of the present invention is, for example, such that the solid content adhesion amount of the thermosetting resin composition in the prepreg is within the above range, and after impregnating the base material with the thermosetting resin composition of the present invention, 100 to 100 It can be manufactured by heating and drying at a temperature of 200° C. for 1 to 30 minutes to semi-harden (to B stage).

[Laminate]
The laminate of the present invention is obtained by laminate-molding the prepreg of the present invention.
The laminate of the present invention can be produced by stacking, for example, 1 to 20 sheets of the prepreg of the present invention, and laminating a metal foil such as copper or aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used as an electrical insulating material.
As for the molding conditions for producing the laminate, for example, the technique of laminates for electrical insulating materials and multilayer boards can be applied, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc., at a temperature of 100 to 250. C., pressure 0.2 to 10 MPa, and heating time 0.1 to 5 hours. A laminate can also be produced by combining the prepreg of the present invention and an inner-layer wiring board and performing lamination molding.

[Printed wiring board]
The printed wiring board of the present invention contains the prepreg or laminate of the present invention.
The printed wiring board of the present invention can be produced, for example, by forming a circuit on the surface of the laminate of the present invention. Alternatively, the conductor layer of the laminate of the present invention may be subjected to wiring processing by an ordinary etching method, a plurality of laminates subjected to wiring processing via the prepreg of the present invention may be laminated, and the laminate may be multi-layered at once by hot pressing. can also Thereafter, a multilayer printed wiring board can be manufactured through the formation of through holes or blind via holes by drilling or laser processing and the formation of interlayer wiring by plating or conductive paste.

[Semiconductor package]
The semiconductor package of the present invention is obtained by mounting a semiconductor on the printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor chip, a memory, etc. at predetermined positions on the printed wiring board of the present invention.

The invention will now be described in more detail with reference to the following examples, but these examples are not intended to limit the invention.
The thermosetting resin composition and copper-clad laminate obtained in each example were evaluated as follows.

(1) Glass transition temperature (Tg)
A copper clad laminate was immersed in a copper etchant to prepare a 5 mm square evaluation board from which the copper foil was removed. A thermomechanical analysis was performed. After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was continuously performed twice under the measurement conditions of a load of 5 g and a temperature increase rate of 10° C./min. A point indicated by the intersection of different tangents of the thermal expansion curve in the second measurement was determined and taken as the glass transition temperature (Tg).

(2) Coefficient of thermal expansion A copper clad laminate was immersed in a copper etchant to remove the copper foil to prepare a 5 mm square evaluation board, and a TMA test device "Q400" (manufactured by TA Instruments) was prepared. Thermomechanical analysis was performed by the compression method using After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was continuously performed twice under the measurement conditions of a load of 5 g and a temperature increase rate of 10° C./min. The average coefficient of thermal expansion from 30° C. to 100° C. in the second measurement was calculated and used as the coefficient of thermal expansion.

(3) Dielectric properties (relative permittivity and dielectric loss tangent)
A 100 mm × 2 mm evaluation board was prepared by removing the copper foil by immersing the copper clad laminate in a copper etching solution, and using a cavity resonator device (manufactured by Kanto Denshi Applied Development Co., Ltd.), the ratio at a frequency of 10 GHz was measured. Permittivity and dissipation factor were measured.

(4) Solder heat resistance (solder heat resistance with copper)
An evaluation board is prepared by cutting a copper-clad laminate into a size of 25 mm square, and the evaluation board is floated in a solder bath at a temperature of 288 ° C. for up to 60 minutes, and the appearance is observed to generate blisters. The time (unit: minutes) was measured. In addition, ">60" was given when no swelling was observed after 60 minutes of floating.

(5) Evaluation of varnish storage stability Curability (time until gelation) was measured using a gel timer manufactured by Nisshin Kagaku Co., Ltd. using 0.5 ml of the varnish obtained in each example as a sample and set to 160 ° C. , the time (T0 (seconds)) from when the sample was added until gelation was measured.
After storing the varnish obtained in each example at 40 ° C. for 3 days, the time until gelation (T1 (seconds)) was measured in the same manner as in the above "curing property" test. (%) was determined and used as an index of storage stability. The higher the value, the better the storage stability.
Storage stability rate (%) = (T1/T0) x 100

The method for producing the modified maleimide resin (B) used in each example is shown below.
[Production of modified maleimide resin (B)]
Production Example 1: [Production of modified maleimide resin (B-1)]
A thermometer, a stirrer, a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a water meter with a reflux condenser, was charged with diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A). ) 33.3 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) AA) 33.3 g, and bis(4-maleimide Phenyl)methane (manufactured by K.I. Kasei Co., Ltd., trade name: BMI) 233.3 g and propylene glycol monomethyl ether: 200.0 g were added and reacted for 5 hours while refluxing to obtain a solution of modified maleimide resin (B-1). got

Production Example 2: [Production of modified maleimide resin (B-2)]
A thermometer, a stirrer, a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a water meter with a reflux condenser, was charged with diamine-modified siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B). ) 28.6 g, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 14.3 g, 2,2-bis[4 -(4-Maleimidophenoxy)phenyl]propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 257.2 g and propylene glycol monomethyl ether: 200.0 g are added and reacted for 5 hours while refluxing to modify maleimide. A solution of resin (B-2) was obtained.

Production Example 3: [Production of modified maleimide resin (B-3)]
A thermometer, a stirrer, a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a water meter with a reflux condenser, was charged with diamine-modified siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B). ) 50.4 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) AA) 28.7 g, and 2,2-bis 220.9 g of [4-(4-maleimidophenoxy)phenyl]propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) and 200.0 g of propylene glycol monomethyl ether are added and reacted at 120° C. for 6 hours for modification. A solution of maleimide resin (B-3) was obtained.

Examples 1-10, Comparative Examples 1-6
The composition is blended and mixed according to the blending ratio shown in Table 1 (the numerical values in the table are parts by mass of solid content, and in the case of solutions (excluding organic solvents) or dispersions, the amount is converted to solid content), Using methyl ethyl ketone as a solvent, a varnish having a solid content concentration of the resin component of 65% by mass was produced.
Next, a 0.1 mm thick low dielectric glass cloth was impregnated with this varnish and dried by heating at 160° C. for 5 minutes to obtain a prepreg having a thermosetting resin composition content of 47 mass %.
Four sheets of this prepreg were stacked, 12 μm electrolytic copper foils were placed on top and bottom, and pressed at a pressure of 2.5 MPa and a temperature of 200° C. for 60 minutes to obtain a copper-clad laminate. Using the obtained copper-clad laminate, each physical property was evaluated according to the methods described above. Table 1 shows the results.

The raw materials used in each example are as follows.

[Imidazole compound (A)]
・ 2MZ-H: 2-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)
・ C11Z: 2-undecylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)
・ 1,2DMZ: 1,2-dimethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)
・ 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)
・ 1B2MZ: 1-benzyl-2-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)
[Imidazole compound for comparison]
・ G-8009L: isocyanate mask imidazole (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
・ C11Z-A: 2,4′-diamino-6-[2′-undecylimidazolyl-(1′)-]-ethyl-s-triazine (manufactured by Shikoku Chemical Industry Co., Ltd.)
・ 2MZ-CN: 1-cyanoethyl-2-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)

[Modified maleimide resin (B)]
Modified Maleimide Resin (B-1): Modified Maleimide Resin (B-1) Prepared in Production Example 1
Modified Maleimide Resin (B-2): Modified Maleimide Resin (B-2) Prepared in Production Example 2
Modified Maleimide Resin (B-3): Modified Maleimide Resin (B-3) Prepared in Production Example 3

[Epoxy resin]
・ NC-3000H: Biphenyl aralkyl type epoxy resin, epoxy equivalent: 280 to 300 g / eq (manufactured by Nippon Kayaku Co., Ltd.)
・EXA-4710: “EPICLON EXA-4710”, tetrafunctional naphthalene type epoxy resin, epoxy equivalent: 170 g / eq (manufactured by DIC Corporation)

[Curing accelerator (C)]
・TPP-MK: Tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokko Chemical Industry Co., Ltd.)
・ TPP: Triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd.)
・ Perbutyl-P: α, α'-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF Corporation)

[Thermoplastic elastomer (D)]
・ Tuftec H1043: Hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Co., Ltd.)
・ Tuftec M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Co., Ltd.)

[(E) inorganic filler]
・SC2050-KNK: Spherical fused silica surface-treated with phenylaminosilane (manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm)

From Table 1, all the examples have a high glass transition temperature, a low coefficient of thermal expansion, excellent dielectric properties, and excellent solder heat resistance and varnish storage stability.
On the other hand, when an imidazole compound that does not correspond to the component (A) of the present invention is used (Comparative Examples 1 and 2), the glass transition temperature is lower and the heat resistance is inferior to those of the examples. Further, when an imidazole compound that does not correspond to the component (A) of the present invention is used, and an epoxy resin is used in combination with a modified maleimide resin (Comparative Examples 3 and 4), the glass transition temperature and heat resistance can be improved. However, the dielectric properties are inferior to those of the examples. Further, when an epoxy resin is used together with the imidazole compound (A) and the modified maleimide resin (B) of the present invention (Comparative Examples 5 and 6), the dielectric properties and varnish storage stability are poor.

The thermosetting resin composition of the present invention has a high glass transition temperature and low thermal expansion, and is excellent in dielectric properties, solder heat resistance and storage stability. The resulting prepreg and laminate are useful as a printed wiring board for electronic equipment that supports highly integrated semiconductor packages and high-speed communication.

Claims (7)

an imidazole compound (A) represented by the following general formula (A1);
A reaction product of a maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule and an amine compound (b-2) having at least two primary amino groups in one molecule. a modified maleimide resin (B);
A thermosetting resin composition containing
The amine compound (b-2) contains a modified siloxane compound having an amino group at the molecular terminal, and the amine compound (b-2) is further represented by the following general formula (b-2-1). containing a diamine,
The content of the modified maleimide resin (B) is 50 to 99 parts by mass with respect to 100 parts by mass of the resin component in the thermosetting resin composition,
A thermosetting resin composition that does not contain an epoxy resin, or, if it contains an epoxy resin, the content thereof is 5% by mass or less relative to the thermosetting resin composition.

(In the general formula (A1), R ¹ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with an aromatic hydrocarbon group having 6 to 20 carbon atoms R ² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ³ and R ⁴ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.)

(In the general formula (b-2-1), ^Yb1 is a group represented by the following general formula (b2-1) or (b2-2).)

(In general formula (b2-1), each R ^b′1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p2 is an integer of 0 to 4.)

(In general formula (b2-2), R ^b′2 and R ^b′3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y ^b2 is a an alkylene group, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a group represented by the following general formula (b2-2-1): q2 and r2 are each independently an integer of 0 to 4.)

(In general formula (b2-2-1), R ^b′4 and R ^b′5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y ^b3 has 1 to 5 alkylene group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group or single bond, s2 and t2 are each independently an integer of 0 to 4; ) 2. The thermosetting resin composition according to claim 1, wherein the modified siloxane compound having an amino group at the molecular terminal is a siloxane diamine represented by the following general formula (b-2-3).

(In general formula (b-2-3), R ^b′7 , R ^b′8 , R ^b′9 and R ^b′10 are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl R ^b′11 and R ^b′12 each independently represent a divalent organic group, and m is an integer of 2 to 100.) The thermosetting resin composition according to claim 1 or 2 , further comprising at least one selected from the group consisting of a curing accelerator (C), a thermoplastic elastomer (D) and an inorganic filler (E). . A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of claims 1 to 3 . A laminate obtained by laminate-molding the prepreg according to claim 4 . A printed wiring board comprising the prepreg according to claim 4 or the laminate according to claim 5 . A semiconductor package comprising the printed wiring board according to claim 6 .