JP6874281B2 - Thermosetting resin compositions, prepregs, laminates, printed wiring boards and semiconductor packages - Google Patents

Description

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

With the recent trend toward miniaturization and higher performance of electronic devices, the wiring density of printed wiring boards has become more sophisticated and highly integrated, and along with this, laminated boards for printed wiring boards have become more popular. There is an increasing demand for improved reliability by improving heat resistance. In 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, the signals to be handled tend to have high frequencies in order to process a large amount of data at high speed. Therefore, in order to suppress transmission loss due to high frequency, the organic material used in the high frequency region is required to have excellent dielectric properties (low relative permittivity and low dielectric loss tangent).

As a laminated board for a printed wiring board, a prepreg containing a resin composition containing an epoxy resin as a main component and a glass cloth is generally cured and integrally molded.
Epoxy resin has an excellent balance of insulation, heat resistance, cost, etc., but further improvement is required to meet the recent demand for improved heat resistance due to high-density mounting of printed wiring boards and high-multilayer configurations. It 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). Further, 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 has a high temperature and a long length during prepreg lamination. It is known that varnishes and prepregs do not require time treatment, have good curability and storage stability, and are excellent in chemical resistance, heat resistance, adhesiveness, and low warpage (for example, Patent Documents). 2).

International Publication No. 2012/099133 Japanese Unexamined Patent Publication No. 2011-157509

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 are therefore excellent in heat resistance and low thermal expansion. Epoxy resins can usually be cured at about 180 to 200 ° C., but polyimide resins such as modified maleimide resins require a high temperature of 220 ° C. or higher and a long-term curing treatment during prepreg lamination. There is a problem that high temperature and long time are required and productivity is poor. Therefore, there is a demand for a material that does not raise the temperature at the time of prepreg lamination, that is, the press temperature too much, has a high glass transition temperature after curing, and is excellent in heat resistance and low thermal expansion.
Further, the thermosetting resin composition described in Patent Document 2 has excellent heat resistance and low thermal expansion property, but since the epoxy resin is inferior in dielectric properties, it has a low relative permittivity and a low dielectric loss tangent due to high-speed communication. I couldn't meet the demand. The resin composition and prepreg for producing a printed wiring board require storage stability, and the thermosetting resin composition described in Patent Document 2 is used as a curing accelerator for the reaction of an epoxy resin and an amine compound. On the other hand, since a modified imidazole compound containing a triazine ring having high potential (that is, the reaction is not promoted unless specific conditions are used) is used, it is excellent in that long-term storage is possible. However, there is room for improvement in low thermal expansion in a thermosetting resin composition that requires a modified imidazole compound containing a triazine ring, and heat resistance becomes insufficient unless an epoxy resin is contained. On the other hand, epoxy Since the dielectric property deteriorates when the resin is contained, it is difficult to achieve both heat resistance and dielectric property at the same time.

In view of these circumstances, the present invention needs to have a high glass transition temperature and a low thermal expansion property, excellent dielectric properties, solder heat resistance and storage stability, and a press temperature of 220 ° C. or higher during prepreg lamination. It is an object of the present invention to provide a non-thermosetting resin composition, a prepreg using the thermosetting resin composition, a laminated board, a printed wiring board, and a semiconductor package.

As a result of intensive studies to solve the above problems, the present inventors have found that the 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 less than or equal to a predetermined amount has been found to be able to solve the above problems, and the present invention has been 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] The imidazole compound (A) represented by the following general formula (A1) and
It is 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. Modified maleimide resin (B) and
A thermosetting resin composition containing
A thermosetting resin composition that does not contain an epoxy resin, or even if it contains an epoxy resin, its content is 5% by mass or less with respect to the thermosetting resin composition.

(In the general formula (A1), R ¹ is a fat having 1 to 5 carbon atoms substituted with a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Group hydrocarbon groups 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. R ³ and R ⁴ are independent of each other. Indicates a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.)
[2] The thermosetting resin according to the above [1], 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 terminal. Composition.
[3] The above-mentioned [1] or [2], which further contains at least one selected from the group consisting of a curing accelerator (C), a thermoplastic elastomer (D) and an inorganic filler (E). Thermosetting resin composition.
[4] A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of the above [1] to [3].
[5] A laminated board obtained by laminating and molding the prepreg according to the above [4].
[6] A printed wiring board containing the prepreg according to the above [4] or the laminated plate according to the above [5].
[7] A semiconductor package including the printed wiring board according to the above [6].

According to the present invention, it has a high glass transition temperature and a low thermal expansion property, is excellent in dielectric properties, solder heat resistance and storage stability, and is thermosetting without the need for a press temperature of 220 ° C. or higher during prepreg lamination. It is possible to provide a sex resin composition, a prepreg using the thermosetting resin composition, a laminated board, a printed wiring board, and a semiconductor package.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention
The imidazole compound (A) represented by the general formula (A1) described later [hereinafter, may be referred to as "imidazole compound (A)". ]When,
Maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule [hereinafter, may be referred to as “maleimide compound (b-1)”. ], And an amine compound (b-2) having at least two primary amino groups in one molecule [hereinafter, may be referred to as "amine compound (b-2)". ], Which is a reaction product of the modified maleimide resin (B) [hereinafter, may be referred to as "modified maleimide resin (B)". ]When,
A thermosetting resin composition containing
It is a thermosetting resin composition that does not contain an epoxy resin, or even if it contains an epoxy resin, its content is 5% by mass or less with respect to the thermosetting resin composition.
Hereinafter, each component will be described in order.

<Imidazole compound (A)>
The thermosetting resin composition of the present invention contains the imidazole compound (A), but the imidazole compound (A) has insufficient potential for the reaction between the epoxy resin and the amine compound, which makes long-term storage difficult. It is a compound. However, in the present invention, by using a modified maleimide resin instead of an epoxy resin as the thermosetting resin, long-term storage is possible even though the imidazole compound (A) is contained.
Further, the imidazole compound (A) has a lower temperature (for example, about 200 ° C.) of the modified maleimide resin (B) than the modified imidazole compound containing a triazine ring in the molecule as described in Patent Document 2. Can be cured with. Therefore, it is not necessary to set the press temperature at the time of laminating the prepreg, which will be described later, to 220 ° C. or higher, and the curing reaction proceeds sufficiently at a press temperature of about 200 ° C., and therefore the glass transition temperature becomes high.

（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 fat having 1 to 5 carbon atoms substituted with a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Group hydrocarbon groups 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. R ³ and R ⁴ are independent of each other. Indicates a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.)

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms indicated by R ¹ 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. Group etc. can be mentioned. 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 further preferably a methyl group.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms in the aliphatic hydrocarbon group having 1 to 5 carbon atoms in which an aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ¹ is substituted, the same as those described above And the preferred ones are the same. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms, which is a substituent of the aliphatic hydrocarbon group, include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group and the like. 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 further preferably a phenyl group.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by 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. Examples thereof include a group, an n-octyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and an icosyl group. 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 preferably, it is a methyl group, an ethyl group, or an undecyl group.
Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms indicated by R ² include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group and the like. 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 further preferably a phenyl group.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms indicated by R ³ and R ⁴ include the same aliphatic hydrocarbon group having 1 to 5 carbon atoms indicated by ^{R 1, and the preferred one is also the same.} ..
Each group of R ^{1 to} R ⁴ can be arbitrarily combined from the above options. In particular, R ¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. both preferably, the R ^2, preferably aliphatic hydrocarbon group having 1 to 20 carbon atoms, each independently as R ³ and R ^4, a hydrogen atom, one of the aliphatic hydrocarbon group having 1 to 5 carbon atoms Is also preferable.

（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 of the following general formulas (A1-1) to (A1-3).

(In the general formula ^{(A1-1) ~ (A1-3),} R 2 ~R 4 are the same as those in the general formula (A1), it is preferable also the same.)

A commercially available product may be used as the imidazole compound (A). Examples of the commercially available products include SIZ, 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ (all manufactured by Shikoku Chemicals Corporation) and the like.

(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. , 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.
In the present specification, the "solid content" is a non-volatile component excluding a volatile substance such as a solvent, and indicates a component that remains without volatilization when the resin composition is dried, and at room temperature. Includes liquid, starch syrup and wax. Here, the room temperature is 25 ° C. in the present specification.
The "resin component" is a component used in the production of a resin or a resin, excluding the inorganic filler (E) described later, and specifically, an imidazole compound (A) and a modified maleimide resin (B). , Curing accelerator (C), thermoplastic elastomer (D) and the like 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 in one molecule and an amine compound (b-) having at least two primary amino groups in one molecule. It is a reaction product with 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 among a plurality of maleimide groups [hereinafter referred to as an aliphatic hydrocarbon group-containing maleimide], and any of a plurality of maleimide groups. A maleimide compound containing an aromatic hydrocarbon group between the two maleimide groups [hereinafter referred to as an aromatic hydrocarbon group-containing maleimide] can be mentioned. Among these, maleimide containing an aromatic hydrocarbon group is preferable from the viewpoint of glass transition temperature, coefficient of thermal expansion, dielectric property, solder heat resistance and storage stability. The aromatic hydrocarbon group-containing maleimide may contain an aromatic hydrocarbon group between any combination of two optionally selected 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 formulas (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 the general formula (b1-1), R ^b1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. 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 the general formula (b1-2), R ^b2 and R ^b3 are independently aliphatic hydrocarbon groups or halogen atoms ^{having 1 to 5 carbon atoms. X b2} is an alkylene group having 1 to 5 carbon atoms and carbon. The number 2 to 5 is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (b1-2-1). Q and r are independent of each other. Is an integer from 0 to 4.)

(In the general formula (b1-2-1), R ^b4 and R ^b5 are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms or halogen atoms. X ^b3 is an alkylene group having 1 to 5 carbon atoms. , Alkylidene group, ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond having 2 to 5 carbon atoms. S and t are independently integers of 0 to 4).

（一般式（ｂ１−３）中、ｎは１〜１０の整数である。）

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

In the general formula (1) ^{, examples of the aliphatic hydrocarbon group represented by R b1} 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 n. -Pentyl group and the like can be mentioned. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the above, an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable as ^{R b1.}
p is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of availability. When p is an integer of 2 or more, the plurality of R ^b1s may be the same or different.

In the general formula (b1-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented ^{by R b2} and R ^b3 and the halogen atom are the same as those in the case of ^{R b1.} The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^b2 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. Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group, from the viewpoints of glass transition temperature, coefficient of thermal expansion, dielectric properties, solder heat resistance and storage stability.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^b2 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 glass transition temperature, coefficient of thermal expansion, dielectric property, solder heat resistance and storage stability.
Among the above options, X ^b2 is preferably an alkylene group having 1 to 5 carbon atoms and 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 from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 2. When q or r is an integer of 2 or more, the plurality of R ^b2s or R ^b3s may be the same or different from each other.

（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), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented ^{by R b4} and R ^b5 and the halogen atom are the same as those in the cases of ^{R b2} and R ^b3. , The preferred ones are 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.} The same is true for the preferred ones.
Among the above options, X ^b3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferable one is as described above.
s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s or t is an integer of 2 or more, the plurality of R ^b4s or R ^b5s may be the same or different from each other.
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 the general formula (b1-2-1') are the same as those in the general formula (b1-2-1), and the preferred ones are also the same. .)

In the general formula (b1-3), n is an integer of 1 to 10, preferably 1 to 5, and more preferably 1 to 3 from the viewpoint of availability.
In the general formula (b1-4), the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented ^{by R b6} and R ^b7 and the halogen atom are the same as in the case ^{of R b1 in the general formula (b1-1).} The same is true for the preferred ones. u is an integer of 1 to 8, preferably 1 to 3, and 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 the general formula (b-1-1), X ^b1 is the general formula (b1-2) from the viewpoints of glass transition temperature, coefficient of thermal expansion, dielectric property, solder heat resistance and storage stability. It is preferably a group represented by the following, and more preferably a group represented by the following general formula (b1-2').

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

^{The X b1} in the general formula (b-1-1) includes the following (b1-i) to (b1-iii) from the viewpoints of glass transition temperature, coefficient of thermal expansion, dielectric properties, solder heat resistance and storage stability. ) Is preferable, and the group represented by (b1-i) or (b1-ii) below is more preferable.

Specific examples of the maleimide compound (b-1) include, for example, N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, bis (4-maleimide cyclohexyl) methane, and 1,4-bis (maleimide). Maleimide containing an aliphatic hydrocarbon group 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-maleimidephenyl) methane, bis (3-methyl-4- Maleimide phenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, bis (4-) Maleimide phenyl) sulfide, bis (4-maleimide phenyl) ketone, 1,4-bis (4-maleimidephenyl) cyclohexane, 1,4-bis (maleimidemethyl) cyclohexane, 1,3-bis (4-maleimidephenoxy) benzene , 1,3-bis (3-maleimide phenoxy) benzene, bis [4- (3-maleimide phenoxy) phenyl] methane, bis [4- (4-maleimide phenoxy) phenyl] methane, 1,1-bis [4- (3-Maleimide phenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,2- Bis [4- (4-maleimide phenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (3-maleimide phenoxy)) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 4,4-bis (3-maleimide phenoxy) biphenyl, 4,4-bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] keto Benzene, bis [4- (4-maleimidephenoxy) phenyl] ketone, 2,2'-bis (4-maleimidephenyl) disulfide, bis (4-maleimidephenyl) disulfide, bis [4- (3-maleimidephenoxy) phenyl ] Sulfate, bis [4- (4-maleimide phenoxy) phenyl] sulfide, bis [4- (3-maleimide phenoxy) phenyl] sulfoxide, bis [4- (4-maleimide phenoxy) phenyl] sulfoxide, bis [4- 3-Maleimide Phenoxy) Benzene] Benzene, Bis [4- (4-Maleimide Phenoxy) phenyl] , 1,4-bis [4- (4-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1, , 4-bis [4- (3-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,4 -Bis [4- (4-maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide phenoxy) -3,5-dimethyl-α, α-Dimethylbenzyl] Benzene, 1,4-bis [4- (3-maleimidephenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidephenoxy) ) -3,5-dimethyl-α, α-dimethylbenzyl] Examples thereof include aromatic hydrocarbon group-containing maleimides such as benzene and 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-maleimidephenyl) methane is preferable from the viewpoint of high reactivity and higher heat resistance. , 2,2-Bis [4- (4-maleimidephenoxy) phenyl] propane is 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))
The 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.
The amine compound (b-2) is preferably an amine compound having two primary amino groups in one molecule, a diamine represented by the following general formula (b-2-1), and an amino group at the molecular terminal described later. A modified siloxane compound having the above is more preferable.

(In the general formula (b-2-1), Y ^b1 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 the general formula (b2-1), R ^b'1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. 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 the general formula (b2-2), R ^b'2 and R ^b'3 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. ^{Y b2 has 1 to 5 carbon atoms.} An alkylene group, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (b2-2-1). r2 is an independently integer from 0 to 4).

(In the general formula (b2-2-1), R ^b'4 and R ^b'5 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms. Y ^b3 has 1 to 5 carbon atoms. It is an alkylene group of 5, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group or a single bond. S2 and t2 are independently integers of 0 to 4).

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

In the general formula (b2-2), an aliphatic hydrocarbon group having 1 to 5 ^carbon atoms ^{R b'2} and ^{R b'3} represented, as the halogen atom, the same ones mentioned in the case of the ^{R b'1} Be done. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by Y ^b2 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. Can be mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group, from the viewpoints of glass transition temperature, coefficient of thermal expansion, dielectric properties, solder heat resistance and storage stability.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by Y ^b2 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 glass transition temperature, coefficient of thermal expansion, dielectric property, solder heat resistance and storage stability.
Among the above options, Y ^b2 is preferably an alkylene group having 1 to 5 carbon atoms and 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 from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 2. When q2 or r2 is an integer of 2 or more, the plurality of R ^b'2 or R ^b'3 may be the same or different from each other.

（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 the general formula (b2-2-1), aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^{R B'4} and ^{R B'5,} as the halogen atom, the ^{R b'2} and ^{R b'3} The same as in the case of, and the preferable one is 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.} The same is true for the preferred ones.
Among the above options, Y ^b3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferable one is as described above.
s2 and t2 are integers of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s2 or t2 is an integer of 2 or more, the plurality of R ^b'4s or R ^b'5s may be the same or different from each other.
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 the general formula (b2-2-1') are the same as those in the general formula (b2-2-1') and are preferable. 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 (b2-1), Y ^b1 is represented by the general formula (b2-2) from the viewpoint of glass transition temperature, coefficient of thermal expansion, dielectric property, solder heat resistance and storage stability. It is preferably a group represented by the following general formula (b2-2'), 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 the general formula (b2-2') are the same as those in the general formula (b2-2), and the preferable ones are also the same. .)

^{Y b1} in the general formula (b-2-1) has the following formulas (b2-i) to (b2-iii) from the viewpoints of glass transition temperature, coefficient of thermal expansion, dielectric properties, solder heat resistance and storage stability. ) Is preferable, and the group represented by the following formula (b2-ii) or (b2-iii) is more preferable.

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'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylketone, benzene, 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- (4-aminophenoxy) Examples thereof include 4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and 9,9-bis (4-aminophenyl) fluorene. These may be used alone or in combination of two or more.

Among these, for example, from the viewpoint of high reactivity and higher heat resistance, and from the viewpoint of low thermal expansion and dielectric properties, 3,3'-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 terminal preferably contains a structural unit represented by the following general formula (b-2-2).

(In the general formula (b-2-2), R ^b'7 and R ^b'8 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 b'7 and R ^b'8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. , N-pentyl group and the like. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
Examples of the substituent contained in the phenyl group in the substituted phenyl group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include 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. Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group and a propargyl group.
Both R ^b'7 and R ^b'8 are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably methyl groups.

（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。） As the modified siloxane compound having an amino group at the molecular terminal, a siloxane diamine represented by the following general formula (b-2-3) is more preferable.

(In the general formula (b-2-3), R ^b'7 and R ^b'8 are the same as those in the 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. R ^b'11 and R ^b'12 each independently represent a divalent organic group, and m is 2 to 100. It is an integer.)

Alkyl group having 1 to 5 carbon atoms R ^B'9 and ^{R b'10} represented, phenyl group and substituted phenyl groups are described as well as described in ^{R B'7} and ^{R b'8.} As R ^b'9 and R ^b'10 , a methyl group is preferable.
^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-, or a divalent linking group in which these are combined. Be done. Examples of the alkylene group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group. Examples of the alkenylene group include an alkenylene group having 2 to 10 carbon atoms. Examples of the alkynylene group include an alkynylene group having 2 to 10 carbon atoms. Examples of the arylene group include an arylene group having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group.
Among these, as R ^b'11 and R ^b'12 , an alkylene group and an arylene group are preferable.

The functional group equivalent of the modified siloxane compound is not particularly limited, but is preferably 300 to 3,000 g / mol, more preferably 400 to 2,000 g / mol, and even more preferably 600 to 2,000 g / mol.

As the modified siloxane compound, a commercially available product can be used. Examples of commercially available products include "KF-8010" (functional group equivalent of amino group: 430 g / mol), "X-22-161A" (functional group equivalent of amino group: 800 g / mol), and "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) (The above is manufactured by Shin-Etsu Chemical Industry 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) (all manufactured by Toray Dow Corning 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)・ Made by Japan GK), 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-" because of their high reactivity during synthesis and low thermal expansion. "3", "XF42-C5379", "XF42-C6252", "XF42-C5742" are preferable, and "X-22-161A", "X-22-161B" are excellent in compatibility and high elastic modulus. , "XF42-C6252", "XF42-C5742" are more preferable.

The modified maleimide resin (B) contained in the thermosetting resin composition of the present invention is a siloxane diamine containing the maleimide compound (b-1) and a structural unit represented by the general formula (b-2-2). It is preferably a reaction product with. Further, the modified maleimide resin (B) contains the maleimide compound (b-1), a diamine represented by the general formula (b-2-1), and a structure represented by the general formula (b-2-2). More preferably, it is a reaction product with a siloxane diamine containing a unit. In the latter case, the ratio of the diamine represented by the general formula (b-2-1) to 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 even more preferably 20/80 to 70/30 in terms of 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 the general formula (B1), X ^b1 is the same as that in the general formula (b-1-1), and the preferred one is also the same.
^{Y is Y b1} in the general formula (b-2-1), or is a divalent group represented by the following general formula (b-2-3').

(In the general formula (b-2-3'), R ^{b'7 to} R ^b'12 and m are the same as those 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 the general formula (B1-1), X ^b1 and Y are the same as those in the general formula (B1), and the preferable ones are also the same.
w is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. However, when w is an integer of 2 or more, the plurality of Ys existing 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. , It is preferable that they coexist.

(Manufacturing method of 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).
As for the ratio of the maleimide compound (b-1) and the amine compound (b-2) used in the reaction, the equivalent of the maleimide group of the maleimide compound (b-1) is determined from the viewpoint of gelation prevention and heat resistance. It is preferable to exceed the equivalent of the primary amino group of the compound (b-2), and the ratio of the equivalent of the maleimide group of the maleimide compound (b-1) to the equivalent of the primary amino group of the amine compound (b-2) [(b). -1) / (b-2)] is preferably 2 to 15, and 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 reaction progress. The reaction time is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

A reaction catalyst can be used for the reaction, if necessary. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. These can be used alone or in admixture of two or more.

The reaction is preferably carried out in an organic solvent. Examples of the organic solvent 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; acetate, γ-butyrolactone, and the like. Ester-based solvent; Ether-based solvent such as tetrahydrofuran; Aromatic solvent such as toluene, xylene, mesitylene; Nitrogen atom-containing solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Sulfur atom-containing solvent such as dimethylsulfoxide, etc. Can be 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 highly volatile and hardly remain as a residual solvent. , Dimethylacetamide is preferred.
The amount of the organic solvent used is preferably 25 to 1,000 parts by mass with respect to 100 parts by mass in total of the maleimide compound (b-1) and the amine compound (b-2) from the viewpoint of solubility and reaction rate. More preferably, 50 to 500 parts by mass.

(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 further preferable, and 80 to 95 parts by mass is particularly preferable.
Further, the content of the modified maleimide resin (B) is such that the amount of the raw material maleimide compound (b-1) converted from the amount of the modified maleimide resin (B) is heat from the viewpoint of elasticity and low thermal expansion. The amount of the resin component in the curable resin composition is preferably 20 to 95 parts by mass, more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the solid content.
The content of the modified maleimide resin (B) in the thermosetting resin composition of the present invention is the modified maleimide resin (B) in the thermosetting resin composition from the viewpoint of good low thermal expansion and copper foil adhesiveness. 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. The amount is preferably 5 to 40 parts by mass, more preferably.

<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, but from the viewpoint of further promoting the curing reaction, a curing accelerator ( C) may be contained. By containing the curing accelerator (C), heat resistance, copper foil adhesiveness and mechanical strength tend to be improved.
Examples of the curing accelerator (C) include organophosphorus compounds such as triphenylphosphine; imidazoles and derivatives thereof; nitrogen-containing compounds such as secondary amines, tertiary amines and quaternary ammonium salts; dicumyl. Peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α'- Organic peroxides such as bis (t-butylperoxy) diisopropylbenzene; organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate and the like can be mentioned. 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), the content thereof is 0.01 to 100 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 10 parts by mass is preferable, 0.1 to 5 parts by mass is more preferable, 0.2 to 2 parts by mass is further preferable, and 0.2 to 2 parts by mass is particularly preferable.

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

Further, 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 the reactive functional group include an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amide group, an isocyanato group, an acrylic group, a methacryl group and a vinyl group. By having these reactive functional groups at the molecular ends or in the molecular chain, the compatibility is improved, the internal stress generated at the time of curing of the thermosetting resin composition can be more effectively reduced, and the substrate can be used. It is possible to reduce the warp.
Among these reactive functional groups, it is preferable to have an epoxy group, a hydroxyl group, a carboxy group, an amino group and an amide group from the viewpoint of adhesion to a metal foil, and an epoxy group from the viewpoint of heat resistance and insulation reliability. It is more preferable to have a hydroxyl group and an amino group.

Examples of 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, and styrene-. Examples include ethylene-propylene-styrene block copolymers. As the raw material monomer for the styrene-based elastomer, in addition to styrene, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used. Among these, styrene-butadiene copolymers and styrene-isoprene copolymers are preferable, and hydrogenated styrene-butadiene copolymer resins and hydrogenated styrene-isoprene copolymers in which the double bond portion of these copolymers is hydrogenated are preferable. A hydrogenated styrene-based thermoplastic elastomer such as a resin is more preferable.
As the styrene-based elastomer, a commercially available product may be used, and the commercially available products include "Toughprene (registered trademark)", "Asaprene (registered trademark) T", "Toughtech (registered trademark) H1043", and "Toughtech (registered trademark)". ) MP10 ”,“ Tough Tech (registered trademark) M1911 ”,“ Tough Tech (registered trademark) M1913 ”(above, manufactured by Asahi Kasei Chemicals Co., Ltd.),“ Epofriend (registered trademark) AT501 ”,“ Epofriend (registered trademark) CT310 ” (The above is manufactured by Daicel Co., Ltd.), "Septon (registered trademark) 2063" (manufactured by Kuraray Co., Ltd.) and the like.

Examples of the olefin-based elastomer include copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butylene, 1-hexene and 4-methyl-1-pentene; the α-olefin and dicyclopentadiene. , 1,4-Hexadiene, cyclooctanediene, methylenenorbornene, etilidennorbornene, butadiene, isoprene and other copolymers with non-conjugated diene having 2 to 20 carbon atoms; Examples thereof include carboxy-modified butadiene-acnillonitrile rubber.
Examples of the α-olefin copolymer include ethylene-propylene copolymer (EPR) and ethylene-propylene-diene copolymer (EPDM).
As the olefin-based elastomer, a commercially available product may be used, and the commercially available products include "PB3600", "PB4700" (all manufactured by Daicel Corporation), "G-1000", "G-2000", and "G-". 3000 ”,“ JP-100 ”,“ JP-100 ”,“ BN-1015 ”,“ TP-1001 ”,“ TEA-1000 ”,“ EA-3000 ”,“ TE-2000 ”,“ EMA-3000 ” (The above is manufactured by Nippon Soda Co., Ltd.), "Denalex (registered trademark) R45" (manufactured by Nagase ChemteX Corporation), and the like.

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

Examples of the polyester-based elastomer include those obtained by polycondensing a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; aromatic dicarboxylic acids in which the hydrogen atom of the aromatic nucleus of these aromatic dicarboxylic acids is substituted with a methyl group, an ethyl group, a phenyl group, or the like. Acids; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and the like can be mentioned. The dicarboxylic acid may be used alone or in combination of two or more.
Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,10-decanediol; and fats such as 1,4-cyclohexanediol. Cyclic diols; examples thereof include aromatic diols such as bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, and resorcin. The diol compound may be used alone or in combination of two or more.
Further, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) moiety as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) moiety as a soft segment component may be used. As the multi-block copolymer, there are various grades of commercially available products depending on the type, ratio, and molecular weight of the hard segment and the soft segment. Specifically, "Hytrel (registered trademark)" (Toray DuPont Co., Ltd.) ), "Perprene (registered trademark)" (manufactured by Toyobo Co., Ltd.), "Esper (registered trademark)" (manufactured by Hitachi Kasei Co., Ltd.), etc.

As the polyamide-based elastomer, polyamide is a hard segment component, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylenepropylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate, poly. Examples thereof include block copolymers containing methacrylate, polyurethane, silicone rubber and the like as soft segment components.
As the polyamide-based elastomer, a commercially available product may be used, and as the commercially available product, "UBE Polyamide Elastoma" (manufactured by Ube Industries, Ltd.), "Dyamide (registered trademark)" (manufactured by Daicel Evonik Co., Ltd.), "PEBAX" (Registered trademark) ”(Arkema),“ Grillon (registered trademark) ELY ”(Mschemy Japan Co., Ltd.),“ Novamid (registered trademark) ”(Mitsubishi Chemical Co., Ltd.),“ Grelax (registered trademark) (Made by DIC Co., Ltd.), "BPAM-01", "BPAM-155" (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

Examples of the acrylic elastomer include a polymer obtained by polymerizing a raw material monomer containing an acrylic acid ester as a main component. Examples of the acrylic acid ester include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate. Further, as the cross-linking point monomer, glycidyl methacrylate, allyl glycidyl ether or the like may be used as a raw material, or acrylonitrile, ethylene or the like may be copolymerized. Specific examples thereof include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

Silicone-based elastomers contain organopolysiloxane as a main component, 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, and the commercially available products include "X22-163B", "X22-163C", "X22-1821", and "X-22-162C" (above, Shin-Etsu Chemical Co., Ltd.). (Manufactured by Co., Ltd.), core-shell type silicone rubber "SY series" (manufactured by Wacker), "SE series", "CY series", "SH series" (manufactured by Toray Dow Corning Co., Ltd.), etc. ..

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, and water. A styrene-based thermoplastic elastomer is more preferable.

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 value, the low thermal expansion property is excellent, and when the weight average molecular weight (Mw) is at least the upper limit value, 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, based on 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, the effect of lowering the dielectric constant can be sufficiently obtained, and when it is 20 parts by mass or less, the resin (B) is compatible with the thermoplastic elastomer. It is sufficiently dispersed in 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).
Examples of the inorganic filler (E) include silica, alumina, titanium oxide, mica, beryria, 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, short glass fibers, fine glass powder, hollow glass and the like. .. As the glass, E glass, T glass, D glass and the like are preferably mentioned. 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 manufactured by a wet method and having a high water content, and dry silica manufactured by a dry method and containing almost no bound water, etc. Further, the dry silica further depends on the difference in the manufacturing method. , Crushed silica, fumed silica, fused spherical silica and the like. Among these, molten 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 to 10 μm, more preferably 0.3 to 8 μm. When the average particle size is 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and when the average particle size is 10 μm or less, the mixing probability of coarse particles is reduced, and defects caused by coarse particles are deteriorated. Occurrence can be suppressed. Here, the average particle size is the particle size of a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with the 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 surface-treating the inorganic filler (E) before compounding by a dry method or a wet method, and the surface-untreated inorganic filler (E) may be treated with another inorganic filler (E). A so-called inorganic blend treatment method may be used in which a silane coupling agent is added to the composition after blending with the components to obtain a composition.
Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, a silicone oligomer and the like.

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

When the thermosetting resin composition of the present invention contains the inorganic filler (E), it is treated with a disperser such as a three-roll roll, a bead mill, or a nanomizer, if necessary, to obtain the inorganic filler (E). It is preferable to improve the dispersibility.

<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, its 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 with respect to the thermosetting resin composition, the dielectric properties and storage stability can be improved. When the epoxy resin is contained, the content thereof is preferably 2% by mass or less, more preferably 1% by mass or less, based on the thermosetting resin composition, from the same viewpoint. Further, 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 a known organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, adhesiveness improver and the like. May be good.
Examples of the organic filler include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin and the like, resin fillers having a core-shell structure, and the like.
Flame retardants include aromatic phosphoric acid ester compounds, phosphazene compounds, phosphinic acid esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itss. Phosphazene flame retardants such as derivatives; Nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate; Halogen-containing flame retardants containing bromine, chlorine, etc .; Inorganic flame retardants such as antimony trioxide Examples include flame retardants.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.
Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant and the like.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative.
Examples of the adhesiveness improving agent include urea compounds such as ureasilane and the coupling agent.

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

Examples of the organic solvent used for the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; butyl acetate and propylene. Ester-based solvents such as glycol monomethyl ether acetate; Ether-based solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene and mesitylene; Nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Examples include a sulfur atom-containing solvent. 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 preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, the coatability can be kept good and a prepreg having an appropriate amount of the resin composition adhered 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 (B-stage) by heating or the like.
As the fiber base material, well-known materials used for various laminated boards for electrical insulating materials can be used. Examples of the material 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 base material having excellent dielectric properties.

These fiber base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats, but the materials and shapes are selected and required according to the intended use and performance of the molded product. Can be used alone or in combination of two or more materials and shapes. As the thickness of the fiber base material, for example, one having a thickness of about 0.03 to 0.5 mm can be used. As these fiber base materials, those surface-treated with a silane coupling agent or the like or those subjected to mechanical opening treatment are suitable from the viewpoints of heat resistance, moisture resistance, processability and the like.

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

[Laminated board]
The laminated board of the present invention is obtained by laminating and molding the prepreg of the present invention.
The laminated board of the present invention can be manufactured by laminating and molding, for example, 1 to 20 prepregs of the present invention in a configuration in which metal foils such as copper and aluminum are arranged on one side or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating material.
For the molding conditions when manufacturing the laminated board, for example, the method of the laminated board for electric insulating material and the multi-layer board can be applied, and a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and the temperature is 100 to 250. It can be molded in the range of ° C., pressure 0.2 to 10 MPa, and heating time 0.1 to 5 hours. Further, the prepreg of the present invention and the wiring board for the inner layer can be combined and laminated to produce a laminated plate.

[Printed circuit board]
The printed wiring board of the present invention comprises the prepreg or laminated board of the present invention.
The printed wiring board of the present invention can be manufactured, for example, by forming a circuit on the surface of the laminated board of the present invention. Further, the conductor layer of the laminated plate of the present invention is wired by an ordinary etching method, and a plurality of laminated plates wired via the prepreg of the present invention are laminated and heat-pressed to collectively form multiple layers. You can also. After that, a multi-layer 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 comprises 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, or the like at a predetermined position on the printed wiring board of the present invention.

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

(1) Glass transition temperature (Tg)
A 5 mm square evaluation substrate from which the copper foil was removed was prepared by immersing the copper-clad laminate in a copper etching solution, and a compression method was used using the TMA test device "Q400" (manufactured by TA Instruments). Thermomechanical analysis was performed. After the evaluation substrate was mounted on the apparatus in the X direction, the measurement was carried out twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The points indicated by the intersections of the tangents of the different thermal expansion curves in the second measurement were determined and used as the glass transition temperature (Tg).

(2) Coefficient of thermal expansion A 5 mm square evaluation substrate from which the copper foil was removed was produced by immersing the copper-clad laminate in a copper etching solution, and the TMA test device "Q400" (manufactured by TA Instruments) was produced. 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 carried out twice in succession under the measurement conditions of a load of 5 g and a heating 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 value of the coefficient of thermal expansion.

(3) Dielectric properties (relative permittivity and dielectric loss tangent)
A 100 mm × 2 mm evaluation substrate from which the copper foil was removed was prepared by immersing the copper-clad laminate in a copper etching solution, and a cavity resonator device (manufactured by Kanto Denshi Applied Development Co., Ltd.) was used to produce a ratio at a frequency of 10 GHz. The permittivity and dielectric loss tangent were measured.

(4) Solder heat resistance (solder heat resistance with copper)
An evaluation substrate is prepared by cutting a copper-clad laminate into a size of 25 mm square, and the evaluation substrate is floated in a solder bath at a temperature of 288 ° C. for a maximum of 60 minutes while observing the appearance to cause swelling. Time to time (unit: minutes) was measured. If no swelling was confirmed after floating for 60 minutes, the value was set to ">60".

(5) Evaluation of storage stability of varnish For the curability (time until gelation), 0.5 ml of the varnish obtained in each example was used as a sample, and a gel timer manufactured by Nissin Kagaku Co., Ltd. was set at 160 ° C. , The time (T0 (seconds)) from the time of sample injection to 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-mentioned "curability" test, and the storage stability rate was measured by the following formula. (%) Was calculated and used as an index of storage stability. The larger the value, the better the storage stability.
Storage stability (%) = (T1 / T0) x 100

The method for producing the modified maleimide resin (B) used in each example is shown below.
[Manufacturing of modified maleimide resin (B)]
Production Example 1: [Production of Modified Maleimide Resin (B-1)]
A reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser, and a diamine-modified siloxane at both ends (manufactured by Shinetsu Chemical Industry 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) 233.3 g of phenyl) methane (manufactured by Keiai Kasei Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether are added and reacted for 5 hours while refluxing to prepare a solution of modified maleimide resin (B-1). Got

Production Example 2: [Production of modified maleimide resin (B-2)]
In a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser, both terminal diamine-modified siloxanes (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name: X-22-161B) ) 28.6 g and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 14.3 g and 2,2-bis [4 -(4-Maleimide phenoxy) 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)]
Both-terminal diamine-modified siloxane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161B) is placed in a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. ) 50.4 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) AA) 28.7 g, 2,2-bis [4- (4-maleimide phenoxy) phenyl] Propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) (220.9 g) and propylene glycol monomethyl ether (200.0 g) were 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 was blended and mixed according to the blending ratio shown in Table 1 (the numerical value in the table is the mass part of the solid content, and in the case of a solution (excluding the organic solvent) or the dispersion liquid, the solid content conversion amount). Using methyl ethyl ketone as a solvent, a varnish having a solid content concentration of 65% by mass as a resin component was prepared.
Next, this varnish was impregnated into a low-dielectric glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a thermosetting resin composition content of 47% by mass.
Four of these 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 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 above method. The results are shown in Table 1.

The raw materials used in each example are as follows.

[Imidazole compound (A)]
・ 2MZ-H: 2-methylimidazole (manufactured by Shikoku Chemicals Corporation)
・ C11Z: 2-Undecylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
・ 1,2DMZ: 1,2-dimethylimidazole (manufactured by Shikoku Chemicals Corporation)
2E4MZ: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
1B2MZ: 1-benzyl-2-methylimidazole (manufactured by Shikoku Chemicals Corporation)
[Comparative imidazole compound]
G-8009L: Isocyanate mask imidazole (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
C11Z-A: 2,4'-diamino-6- [2'-undecyl imidazolyl- (1')-]-ethyl-s-triazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
2MZ-CN: 1-cyanoethyl-2-methylimidazole (manufactured by Shikoku Chemicals Corporation)

[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: 280-300 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 Hokuko Chemical Industry Co., Ltd.)
・ TPP: Triphenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd.)
-Perbutyl-P: α, α'-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF CORPORATION)

[Thermoplastic Elastomer (D)]
-Tough Tech H1043: Hydrogenated styrene-butadiene copolymer resin (manufactured by Asahi Kasei Chemicals Co., Ltd.)
-Tough Tech 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 Admatex Co., Ltd., average particle size: 0.5 μm)

From Table 1, in each of the examples, the glass transition temperature is high, the coefficient of thermal expansion is low, the dielectric properties are excellent, and the solder heat resistance and the varnish storage stability are excellent.
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 as compared with Examples. Further, when the epoxy resin was used in combination with the modified maleimide resin while using the imidazole compound which does not correspond to the component (A) of the present invention (Comparative Examples 3 and 4), the glass transition temperature and heat resistance could be improved. However, the dielectric properties are inferior to those of the examples. Further, when the epoxy resin is used in combination with the imidazole compound (A) and the modified maleimide resin (B) of the present invention (Comparative Examples 5 and 6), the dielectric properties and the varnish storage stability are inferior.

The thermosetting resin composition of the present invention contains the thermosetting resin composition because it has a high glass transition temperature and a low thermal expansion property, and is excellent in dielectric properties, solder heat resistance, and storage stability. The prepreg and the laminated board are useful as a highly integrated semiconductor package, a printed wiring board for electronic devices compatible with high-speed communication, and the like.

Claims (7)

The imidazole compound (A) represented by the following general formula (A1) and
It is 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. Modified maleimide resin (B) and
Thermoplastic elastomer (D) and
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) contains a modified siloxane compound.
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 even if it contains an epoxy resin, its content is 5% by mass or less with respect to the thermosetting resin composition.

(In the general formula (A1), R ¹ is a fat having 1 to 5 carbon atoms substituted with a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Group hydrocarbon groups 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. R ³ and R ⁴ are independent of each other. Indicates a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.) The thermosetting resin composition according to claim 1, wherein the maleimide compound (b-1) is an aromatic hydrocarbon group-containing maleimide. Further comprises at least one member selected from the group consisting of curing accelerator (C)及beauty inorganic filler (E), the thermosetting resin composition according to claim 1 or 2. A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of claims 1 to 3. A laminated board obtained by laminating and molding the prepreg according to claim 4. A printed wiring board comprising the prepreg according to claim 4 or the laminated board according to claim 5. A semiconductor package comprising the printed wiring board according to claim 6.