JP6848215B2 - Thermosetting resin composition, prepreg, laminated board and printed wiring board - Google Patents

Description

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

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, with the remarkable improvement in the amount of information communication and speed in network infrastructure equipment, large computers, etc., the semiconductor packages mounted on these electronic equipment need to be compatible with high frequencies, and low dielectric constants that enable reduction of transmission loss. A substrate material having a ratio and a low dielectric loss tangent is required.

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. Further, since the epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring and increasing the filling of an inorganic filler such as silica (see, for example, Patent Documents 1 and 2). .. However, it is known that increasing the filling amount of the inorganic filler causes deterioration of insulation reliability due to moisture absorption, insufficient adhesion between the resin and the wiring layer, poor press molding, etc., and the filling of the inorganic filler is increased. There was a limit to the low thermal expansion by chisel. Further, when an epoxy resin is used, it is difficult to obtain a cured resin product having a good relative permittivity and dielectric loss tangent, and improvement of the dielectric property has been required as a material for high-speed communication.

For the purpose of improving the dielectric properties, a laminated board to which a polybutadiene resin is added as a thermoplastic elastomer has been studied. The laminated board has excellent dielectric properties, but the prepreg has adhesiveness, compatibility with other thermosetting resins is low, the shrinkage rate at the time of curing is large, and copper foil. There are drawbacks such as poor adhesion to metal foils such as.
As a method for improving these, a method using a butadiene-vinyl aromatic compound copolymer has been proposed (see, for example, Patent Document 3), but vinyl is used in order to obtain sufficient compatibility with other thermosetting resins. It is necessary to increase the copolymerization ratio of the aromatic compound, and in that case, there arises a problem that the heat resistance is lowered.

On the other hand, a curable resin composition composed of a specific copolymer and a thermosetting resin and / or a vinyl monomer has been proposed as having excellent properties of a conventional thermosetting resin and a polybutadiene resin (for example). , Patent Documents 4, 5 and 6). However, there is a problem that the glass transition temperature of the laminated board obtained by using the curable resin composition is low. Further, the copolymer resin has a larger coefficient of thermal expansion than epoxy resins, polyimide resins, etc., which are generally used, and has a large shrinkage rate at the time of curing. Therefore, a semiconductor package particularly required to have heat resistance and low warpage. Is not preferable.
Further, a resin composition containing a polyphenylene ether and a thermosetting resin has been studied in order to exhibit good electrical characteristics (see, for example, Patent Document 7), but it is required as a material for semiconductor packaging in recent years. Properties that satisfy low thermal expansion rate, dielectric properties in the high frequency region, and moisture and heat resistance have not been obtained.

Further, in recent years, as a method for improving the difference in the coefficient of thermal expansion between a chip and a substrate and the warpage caused by the curing shrinkage of the substrate, which has been a problem in a semiconductor package substrate, a method of reducing the curing shrinkage rate of a resin is used. It is being considered. As one example thereof, a method of using a modified bismaleimide resin and a thermoplastic elastomer in combination has been proposed (see, for example, Patent Document 8). Thermoplastic elastomers are known to be effective in reducing the curing shrinkage rate of resins, and to exhibit low relative permittivity and low dielectric loss tangent because the polarity of the skeleton is very small. Therefore, by using the modified bismaleimide resin and the thermoplastic elastomer in combination, it is possible to achieve both low thermal expansion and excellent dielectric properties (low relative permittivity and low dielectric loss tangent).

Japanese Unexamined Patent Publication No. 5-148343 Japanese Unexamined Patent Publication No. 6-263843 Japanese Unexamined Patent Publication No. 61-23060 Japanese Unexamined Patent Publication No. 2-255855 Japanese Unexamined Patent Publication No. 3-269047 Japanese Unexamined Patent Publication No. 3-281650 Japanese Unexamined Patent Publication No. 58-69046 Japanese Unexamined Patent Publication No. 2014-24926

However, the resin composition in which the above-mentioned modified bismaleimide and the thermoplastic elastomer are used in combination has no problem in general heat resistance, but under severe conditions due to the recent high-density mounting of printed wiring boards and the high-multilayer configuration. There is a problem that the heat resistance, that is, the heat resistance after water absorption is inferior.

In view of the current situation, the subject of the present invention is to obtain a thermosetting resin composition having excellent heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent, and a prepreg, laminated board and printed wiring board using the same. To provide.

As a result of intensive research to achieve the above object, the present inventors can achieve the above object by using a modified polyimide compound having a specific structure, a thermoplastic elastomer, and a specific polyphenylene ether derivative. This has led to the completion of the present invention.
That is, the present invention provides the following thermosetting resin compositions, prepregs, laminated boards and printed wiring boards.
[1] (A) Addition of a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule. Reactant and
(B) Thermoplastic elastomer and
(C) A polyphenylene ether derivative having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (C-1) in one molecule.
Thermosetting resin composition containing.

（式中、Ｒ^Ｃ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は、０〜４の整数である。）
［２］前記Ｎ−置換マレイミド構造含有基が、下記一般式（Ｃ−２）で表される基である、上記［１］に記載の熱硬化性樹脂組成物。

(In the formula, ^RC is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively. X is an integer of 0 to 4.)
[2] The thermosetting resin composition according to the above [1], wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (C-2).

（式中、Ｒ^Ｃ０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は、０〜４の整数である。Ｘ^Ｃ１は、下記一般式（Ｃ−３）、（Ｃ−４）、（Ｃ−５）又は（Ｃ−６）で表される基である。）

(In the formula, ^RC0 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Y is an integer of 0 to 4. X ^C1 is the following general formula (C-). 3), (C-4), (C-5) or (C-6).)

（式中、Ｒ^Ｃ１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 formula, ^RC1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively. P is an integer of 0 to 4.)

（式中、Ｒ^Ｃ２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^Ｃ２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（Ｃ−４’）で表される基である。ｑは、各々独立に、０〜４の整数である。）

(In the formula, ^RC2 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X C2} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group, single bond or group represented by the following general formula (C-4'). Q is an integer of 0 to 4 independently. .)

（式中、Ｒ^Ｃ３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^Ｃ３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。ｒは、各々独立に、０〜４の整数である。）

(In the formula, ^RC3 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X C3} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond. R is an integer of 0 to 4 independently.)

（式中、ｎは、０〜１０の整数である。）

(In the formula, n is an integer from 0 to 10.)

（式中、Ｒ^Ｃ４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。）
［３］前記（Ｃ）成分の含有量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、２〜２０質量部である、上記［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］前記（ａ２）成分が、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］〜［３］のいずれかに記載の熱硬化性樹脂組成物。
［５］（Ｂ）熱可塑性エラストマーが、水添スチレン系熱可塑性エラストマーである、上記［１］〜［４］のいずれかに記載の熱硬化性樹脂組成物。
［６］（Ｂ）熱可塑性エラストマーの含有量が、熱硬化性樹脂組成物中の樹脂成分の固形分１００質量部に対して、４〜３０質量部である、上記［１］〜［５］のいずれかに記載の熱硬化性樹脂組成物。
［７］さらに、（Ｄ）硬化促進剤を含有する、上記［１］〜［６］のいずれかに記載の熱硬化性樹脂組成物。
［８］さらに、（Ｅ）無機充填材を含有する、上記［１］〜［７］のいずれかに記載の熱硬化性樹脂組成物。
［９］上記［１］〜［８］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。
［１０］上記［９］に記載のプリプレグを積層成形して得られる積層板。
［１１］上記［９］に記載のプリプレグ又は［１０］に記載の積層板を用いて製造されるプリント配線板。

(In the formula, ^RC4 is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U is an integer of 1 to 8.)
[3] In the above [1] or [2], the content of the component (C) is 2 to 20 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. The thermosetting resin composition according to the above.
[4] The thermosetting resin composition according to any one of [1] to [3] above, wherein the component (a2) contains a modified siloxane compound having an amino group at the terminal.
[5] The thermosetting resin composition according to any one of the above [1] to [4], wherein the (B) thermoplastic elastomer is a hydrogenated styrene-based thermoplastic elastomer.
[6] The above [1] to [5], wherein the content of the thermoplastic elastomer (B) is 4 to 30 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. The thermosetting resin composition according to any one of.
[7] The thermosetting resin composition according to any one of the above [1] to [6], which further contains (D) a curing accelerator.
[8] The thermosetting resin composition according to any one of the above [1] to [7], which further contains (E) an inorganic filler.
[9] A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of the above [1] to [8].
[10] A laminated board obtained by laminating and molding the prepreg according to the above [9].
[11] A printed wiring board manufactured by using the prepreg according to the above [9] or the laminated board according to the above [10].

According to the present invention, it is possible to provide a thermosetting resin composition having excellent heat resistance, low thermal expansion property, low relative permittivity and low dielectric loss tangent, and a prepreg, laminated board and printed wiring board using the same. ..

[Thermosetting resin composition]
The thermosetting resin composition of the present invention (A) has a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and at least two primary amino groups in one molecule. A polyphenylene ether derivative having an amine compound (a2), (B) a thermoplastic elastomer, (C) an N-substituted maleimide structure-containing group in the molecule, and a structural unit represented by the general formula (C-1) (hereinafter referred to as). , "(C) Polyphenylene ether derivative"), and a thermosetting resin composition containing.

<(A) Modified maleimide resin>
The modified maleimide resin (A) includes a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule. It is an addition reaction product of.

(Maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule)
A maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule (hereinafter, also referred to as “component (a1)”) is a maleimide compound having two N-substituted maleimide groups in one molecule. Is preferable, and the compound represented by the following general formula (a1-1) is more preferable.

（式中、Ｘ^Ａ１は、下記一般式（ａ１−２）、（ａ１−３）、（ａ１−４）又は（ａ１−５）で表される基である。）

^{(Wherein, X A1} is represented by the following general formula (a1-2), (a1-3), a group represented by (a1-4) or (a1-5).)

（式中、Ｒ^Ａ１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。ｐ１は、０〜４の整数である。）

^{(Wherein, R A1} are each independently, .P1 an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms is an integer of 0-4.)

（式中、Ｒ^Ａ２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^Ａ２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（ａ１−３’）で表される基である。ｑ１は、各々独立に、０〜４の整数である。）

(In the formula, ^RA2 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X A2} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group, single bond or group represented by the following general formula (a1-3'). Q1 is an integer of 0 to 4 independently. .)

（式中、Ｒ^Ａ３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^Ａ３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。ｒ１は、各々独立に、０〜４の整数である。）

(In the formula, ^RA3 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X A3} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond. R1 is independently an integer of 0 to 4).

（式中、ｎ１は、１〜１０の整数である。）

(In the formula, n1 is an integer of 1 to 10.)

（式中、Ｒ^Ａ４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。ｕ１は、１〜８の整数である。）

^{(Wherein, R A4} each independently, .U1 an aliphatic hydrocarbon group having a hydrogen atom or a C1-5 is an integer from 1 to 8.)

In the general formula ^(a1-2), examples of the aliphatic hydrocarbon group represented by ^{R A1,} a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl radical, n -Pentyl group and the like can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
p1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the general formula ^(a1-3), aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R A2} represents, as the halogen ^atom, include those similar to the case of ^{R A1.} 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.
As the alkylene group having 1 to 5 carbon atoms which X ^A2 represents, methylene group, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like Be done. Among these, from the viewpoints of heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.
The alkylidene group having 2 to 5 carbon atoms which X ^A2 represents, 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 heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent.
q1 is an integer of 0 to 4 independently, and is preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability.

In the general formula (a1-3 ^'), aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R A3} is represented, as the halogen ^atom, include those similar to the case of ^{R A2.}
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^A3 include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented ^{by X A2.} Be done.
Among the above options, X ^A3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
r1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the general formula (a1-4), n1 is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3 from the viewpoint of availability.
In the general formula ^(a1-5), aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R A4} is represented, as the halogen atom, the same ones mentioned in the case of ^{R A1} in the general formula (a1-2) Be done.
u1 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

As the component (a1), N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, 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-maleimidephenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidephenyl) ether, Bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ketone, bis (4-maleimidecyclohexyl) methane, 1,4-bis (4-maleimidephenyl) cyclohexane, 1 , 4-bis (maleimide methyl) cyclohexane, 1,4-bis (maleimide methyl) benzene, 1,3-bis (4-maleimide phenoxy) 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-hexafluoro Propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimide phenoxy) biphenyl, 4, 4-Bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] ketone, bis [4- (4-maleimide phenoxy) phenyl] ketone, 2,2' -Bis (4-maleimidephenyl) disulfide, bis (4-maleimidephenyl) disulfide, bis [4- (3-maleimidephenoxy) phenyl] sulfide, bis [4- (4-maleimidephenoxy) phenyl] sulfide, bis [4 -(3-Maleimide phenoxy) phenyl] sulfoxide, bis [4- (4-maleimide phenoxy) phenyl] sulfoxide, bis [4- (3-maleimide phenoxy) phenyl] sulfone, bis [4- (4-maleimide phenoxy) phenyl ] Sulfide, bis [4- (3-maleimide phenoxy) phenyl] ether, bis [4- (4-maleimide phenoxy) phenyl] ether and the like. The component (a1) may be used alone or in combination of two or more.
Among these, maleimide compounds having a phenoxy group are preferable from the viewpoint of excellent solubility in a solvent, and bis (4-maleimidephenyl) methane, 2,2- from the viewpoint of high reaction rate and higher heat resistance. Bis [4- (4-maleimide phenoxy) phenyl] propane is preferred.

(Amine compound (a2) having at least two primary amino groups in one molecule)
The amine compound (a2) having at least two primary amino groups in one molecule (hereinafter, also referred to as “component (a2)”) is preferably an amine compound having two primary amino groups in one molecule. , The compound represented by the following general formula (a2-1) is more preferable.

（式中、Ｙ^Ａ１は、下記一般式（ａ２−２）、（ａ２−３）又は（ａ２−４）で表される基である。）

^{(Wherein, Y A1} is represented by the following general formula (a2-2), a group represented by (a2-3) or (a2-4).)

（式中、Ｒ^Ａ５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。）

^{(Wherein, R A5} each independently, .P2 an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms is an integer of 0-4.)

（式中、Ｒ^Ａ６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^Ａ２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（ａ２−３’）で表される基である。ｑ２は、各々独立に、０〜４の整数である。）

^{(Wherein, R A6} are each independently, ^{.Y A2} is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms, alkylene group of 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group, single bond or group represented by the following general formula (a2-3'). Q2 is an integer of 0 to 4 independently. .)

（式中、Ｒ^Ａ７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^Ａ３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。ｓ１は、各々独立に、０〜４の整数である。）

^{(Wherein, R A7} each independently, ^{.Y A3} is an aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms, alkylene group of 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond. S1 is an integer of 0 to 4 independently.)

（式中、Ｒ^Ａ８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である。Ｒ^Ａ９は、各々独立に、２価の有機基である。ｍ２は、１〜１００の整数である。）

^{(Wherein, R A8} each independently represent an alkyl group having 1 to 5 carbon atoms, ^{.R A9} is phenyl or substituted phenyl are each independently a divalent organic group .m2 is 1 It is an integer of ~ 100.)

In the general formula ^(a2-2), examples of the aliphatic hydrocarbon group represented by ^{R A5,} methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl radical, n -Pentyl group and the like can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
p2 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 2 from the viewpoint of availability.

In the general formula ^(a2-3), aliphatic hydrocarbon group having 1 to 5 ^carbon atoms ^{R A6} represents, as the halogen atom ^include the same ones as for ^{R A5.} 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.
As the alkylene group having 1 to 5 carbon atoms which Y ^A2 represents, methylene group, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like Be done. Among these, from the viewpoints of heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.
The alkylidene group having 2 to 5 carbon atoms which Y ^A2 represents, 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 heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent.
q2 is an integer of 0 to 4 independently, and is preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability.

In the general formula (a2-3 ^'), aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R A7} represents, as the halogen atom ^include the same ones as for ^{R A6.}
Y ^A3 represents an alkylene group having 1 to 5 carbon atoms, alkylidene group having 2 to 5 carbon ^atoms, alkylene group having 1 to 5 carbon atoms represented by ^{Y A2,} include the same ones as the alkylidene group having 2 to 5 carbon atoms Be done.
The Y ^A3, among the above alternatives is preferably alkylidene group having 2 to 5 carbon atoms, more preferably an isopropylidene group.
s1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the general formula ^(a2-4), examples of the alkyl group having 1 to 5 carbon atoms ^{which R A8} is represented, more preferably an alkyl group having 1 to 3 carbon atoms. ^Examples of the alkyl group represented by RA8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group and the like. Group is preferred.
^{Examples of the substituent in the substituted phenyl group represented by RA8} include an alkyl group, an alkenyl group, an alkynyl group and the like, and among these, an alkyl group is preferable. Examples of the alkyl group include those similar to the alkyl group represented by ^{RA8.
Among the groups represented by RA8} , a phenyl group or a methyl group is preferable, and a methyl group is more preferable, from the viewpoint of solubility with other resins.
The divalent organic group R ^A9 represents an alkylene group, an alkylidene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or they can be cited and a divalent linking group in combination. Among these, an alkylene group and an arylene group are preferable. Examples of the alkylene group include a methylene group, an ethylene group and a propylene group. Examples of the arylene group include a phenylene group and a naphthylene group.
m2 is an integer of 1 to 100, and an integer of 2 to 50 is preferable from the viewpoint of compatibility and high elastic modulus.

As the component (a2), a modified siloxane having an amino group at the terminal, diaminobenzidine, diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, 3,3'-dichloro -4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4' -Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl-6,6'-disulfonic acid, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 4, 4'-methylene-bis (2-chloroaniline), 1,3'-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2'-bis [4- (4- (4- (4- (4-)4-)-bis] Aminophenoxy) phenyl] hexafluoropropane, 1,4'-bis (4-aminophenoxy) benzene, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4 Examples thereof include'-diamino-3,3'-biphenyldiol, 9,9'-bis (4-aminophenyl) fluorene, o-trizine sulfone and the like. The component (a2) may be used alone or in combination of two or more.

Among these, from the viewpoint of obtaining high elasticity and high heat resistance, 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane Is preferable.
Further, from the viewpoint of low thermal expansion, it is preferable to contain a modified siloxane having an amino group at the terminal. As the modified siloxane having an amino group at the terminal, a commercially available product may be used, and the commercially available products include "PAM-E" (functional group equivalent 130) and "KF-8010" (functional group) having amino groups at both ends. Equivalent 430), "X-22-161A" (functional group equivalent 800), "X-22-161B" (functional group equivalent 1,500), "KF-8012" (functional group equivalent 2,200), "KF" -8008 ”(functional group equivalent 5,700) [above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.],“ BY16-871 ”(functional group equivalent 130),“ BY16-853U ”(functional group equivalent 460) (above, Toredau) (Manufactured by Corning Co., Ltd.) and the like.

Further, the component (a2) contains a modified siloxane having an amino group at the terminal and an amine compound other than the modified siloxane having an amino group at the terminal from the viewpoint of achieving both low thermal expansion, high elasticity and high heat resistance. It is preferably composed of a modified siloxane having an amino group at the terminal, 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. It is more preferable to use in combination with one or more selected from the group.
When a modified siloxane having an amino group at the terminal and an amine compound other than the modified siloxane having an amino group at the terminal are used in combination as the component (a2), the mass ratio thereof [modified siloxane having an amino group at the terminal / terminal Amine compounds other than the modified siloxane having an amino group] are preferably 3/97 to 90/10, more preferably 10/90 to 80/20, and even more preferably 20/80 to 70/30.

The modified maleimide resin (A), which is an addition reaction product of the component (a1) and the component (a2), has, for example, a structural unit represented by the following general formula (A-1).

（式中、Ｘ^Ａ１は、前記一般式（ａ１−１）におけるＸ^Ａ１と同様であり、Ｙ^Ａ１は、前記一般式（ａ２−１）におけるＹ^Ａ１と同様である。）

^{(Wherein, X A1} is the same as ^{X A1} in the general formula ^{(a1-1), Y A1} is the same as ^{Y A1} in the general formula (a2-1).)

((A) Method for producing modified maleimide resin)
The modified maleimide resin (A) can be produced by subjecting the component (a1) and the component (a2) to an addition reaction.
As for the blending amount of the component (a1) and the component (a2) in the addition reaction, the equivalent of the maleimide group of the component (a1) is the equivalent of the primary amino group of the component (a2) from the viewpoint of preventing gelation and heat resistance. The ratio of the maleimide group equivalent of the component (a1) to the equivalent of the primary amino group of the component (a2) [(a1) component / (a2) component] is 2 to 15. It is preferably present, and more preferably 3 to 10.

The reaction temperature in the addition reaction 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 preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

The addition 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.
From the viewpoint of solubility and reaction rate, the amount of the organic solvent used is preferably 25 to 1,000 parts by mass, preferably 50 to 500 parts by mass, based on 100 parts by mass of the total of the components (a1) and (a2). More preferred.

The content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is preferably 50 to 95 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 90 parts by mass is more preferable, and 70 to 87 parts by mass is further preferable.
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 waxy ones. 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 an inorganic filler described later, and specifically, (A) a modified maleimide compound, (B) a thermoplastic elastomer, ( C) a polyphenylene ether derivative, (D) a curing accelerator and the like correspond to resin components.

The content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is the amount of the (A) modified maleimide resin in the thermosetting resin composition from the viewpoint of elasticity and low thermal expansion. The amount of the component (a1) of the raw material converted from is preferably 30 to 90 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and is preferably 50 to 85 parts by mass. Is more preferable.
Further, the content of the (A) modified maleimide resin in the thermosetting resin composition of the present invention is (A) modified in the thermosetting resin composition from the viewpoint of good low thermal expansion and copper foil adhesiveness. The amount of the component (a2) of the raw material converted from the amount of the maleimide resin is preferably 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. An amount of up to 40 parts by mass is more preferable.

<(B) Thermoplastic Elastomer>
Examples of the (B) thermoplastic elastomer (hereinafter, also referred to as “component (B)”) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. Examples thereof include derivatives of. The component (B) may be used alone or in combination of two or more.

Further, as the (B) thermoplastic elastomer, 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. 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)" (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.), "Diamid (registered trademark)" (manufactured by Daicel Evonik Industries, Ltd.), "PEBAX" (Registered trademark) ”(manufactured by Elastomer),“ Grillon (registered trademark) ELY ”(manufactured by MSM Japan Co., Ltd.),“ Novamid (registered trademark) ”(manufactured by Mitsubishi Chemical Industries, Ltd.) (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 (B) thermoplastic elastomers, 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 olefins are preferable from the viewpoint of dielectric properties. Elastomers are more preferred, and hydrogenated styrene thermoplastic elastomers are even more preferred.

The weight average molecular weight (Mw) of the thermoplastic elastomer (B) 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 (B) thermoplastic elastomer in the thermosetting resin composition is preferably 4 to 30 parts by mass, preferably 6 to 20 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 (B) the thermoplastic elastomer is 4 parts by mass or more, the effect of lowering the dielectric constant can be sufficiently obtained, and when it is 30 parts by mass or less, (B) the thermoplastic elastomer becomes compatible with the resin. It is sufficiently dispersed in and has excellent heat resistance and peel strength.

<(C) Polyphenylene ether derivative>
The (C) polyphenylene ether derivative is a polyphenylene ether derivative having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (C-1) in the molecule.

（式中、Ｒ^Ｃ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は、０〜４の整数である。）

(In the formula, ^RC is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively. X is an integer of 0 to 4.)

By containing the (C) polyphenylene ether derivative, the thermosetting resin composition of the present invention has an effect of being particularly excellent in heat resistance after water absorption. The reason for this effect is not clear, but it is thought to be as follows.
Conventionally, a method of adding a thermoplastic elastomer to a modified maleimide resin has been used for the purpose of improving the dielectric property, but the thermoplastic elastomer is compatible with each other because the structure of the modified maleimide resin and the skeleton are significantly different. It was in a difficult state. Therefore, if the modified maleimide resin and the thermoplastic elastomer are simply blended, there is a problem in heat resistance under severe conditions required in recent years (for example, after moisture absorption treatment with a pressure cooker).
The (C) polyphenylene ether derivative contained in the thermosetting resin composition of the present invention contains an N-substituted maleimide structure-containing group and a polyphenylene ether skeleton in the molecule, and the polyphenylene ether skeleton is a thermoplastic elastomer. The N-substituted maleimide structure-containing group is excellent in compatibility with the modified maleimide resin. Therefore, the (C) polyphenylene ether derivative functions as a compatibilizer between the (A) modified maleimide resin and the (B) thermoplastic elastomer, thereby forming the (A) modified maleimide resin and the (B) thermoplastic elastomer. It is considered that the compatibility with the resin has improved and the heat resistance has improved. Furthermore, since the (C) polyphenylene ether derivative itself also has excellent dielectric properties, it is considered that excellent heat resistance could be imparted without impairing the dielectric properties.

^{Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RC} in the general formula (C-1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Examples thereof include a t-butyl group and an n-pentyl group. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among the above, ^{as RC} , an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable.
x is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 2. When x is 1 or 2, it is preferable that ^RC is substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom).
The structural unit represented by the general formula (C-1) is preferably a structural unit represented by the following general formula (C-1').

As the N-substituted maleimide structure-containing group of the (C) polyphenylene ether derivative, the nitrogen atoms of the two maleimide groups are composed of two maleimide groups from the viewpoints of high frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature and thermal expansion coefficient. A group containing a bismaleimide structure bonded via an organic group is preferable, and a group represented by the following general formula (C-2) is more preferable.

（式中、Ｒ^Ｃ０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は、０〜４の整数である。Ｘ^Ｃ１は、下記一般式（Ｃ−３）、（Ｃ−４）、（Ｃ−５）又は（Ｃ−６）で表される基である。）

(In the formula, ^RC0 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Y is an integer of 0 to 4. X ^C1 is the following general formula (C-). 3), (C-4), (C-5) or (C-6).)

（式中、Ｒ^Ｃ１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 formula, ^RC1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively. P is an integer of 0 to 4.)

（式中、Ｒ^Ｃ２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^Ｃ２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（Ｃ−４’）で表される基である。ｑは、各々独立に、０〜４の整数である。）

(In the formula, ^RC2 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X C2} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group, single bond or group represented by the following general formula (C-4'). Q is an integer of 0 to 4 independently. .)

（式中、Ｒ^Ｃ３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^Ｃ３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。ｒは、各々独立に、０〜４の整数である。）

(In the formula, ^RC3 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X C3} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond. R is an integer of 0 to 4 independently.)

（式中、ｎは、０〜１０の整数である。）

(In the formula, n is an integer from 0 to 10.)

（式中、Ｒ^Ｃ４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 formula, ^RC4 is 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 (C-2), the ^{aliphatic hydrocarbon group represented by RC0} includes 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. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
y is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the above formula ^(C-3), an aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R C1} is represented, as the halogen atom ^include the same ones as for ^{R C0.}
p is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the general formula ^(C-4), aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R C2} is represented, as the halogen atom ^include the same ones as for ^{R C1.} 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 ^C2 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. Be done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group, from the viewpoints of heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^C2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoint of heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent.
q is an integer of 0 to 4 independently, and is preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability.

In the general formula (C-4 ^'), aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R C3} is represented, as the halogen atom ^include the same ones as for ^{R C2.}
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^C3 include the same alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented ^{by X C2.} Be done.
Among the above options, X ^C3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
r is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.
In the general formula (C-5), n is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3 from the viewpoint of availability.
In the general formula ^(C-6), aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^{R C4,} as the halogen atom, the same ones mentioned in the case of the formula (C-3) in the ^{R C1} And the preferred ones are the same.
u is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

^{X C1} among the groups represented by the general formula (C-2) is represented by any of the following formulas from the viewpoints of high frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature and coefficient of thermal expansion. The divalent group to be used is preferred.

The polyphenylene ether derivative (C) is preferably a polyphenylene ether derivative represented by the following general formula (C-7).

（式中、Ｘ^Ｃ１、Ｒ^Ｃ、Ｒ^Ｃ０、ｘ及びｙは前記定義のとおりである。ｍは、１以上の整数である。）

(In the formula, X ^C1 , ^{RC , RC0} , x and y are as defined above. M is an integer of 1 or more.)

m is preferably an integer of 1 to 300, more preferably an integer of 10 to 300, even more preferably an integer of 30 to 200, and particularly preferably an integer of 50 to 150.

The polyphenylene ether derivative (C) is preferably a polyphenylene ether derivative represented by any of the following general formulas (C-8) to (C-10).

（式中、ｍは前記一般式（Ｃ−７）中のｍと同じである。）

(In the formula, m is the same as m in the general formula (C-7).)

From the viewpoint of low cost of raw materials, the polyphenylene ether derivative represented by the general formula (C-8) is preferable, and from the viewpoint of excellent dielectric properties and low water absorption, the general formula (C-9) is used. The polyphenylene ether derivative represented by the above is preferable, and the polyphenylene ether derivative represented by the general formula (C-10) is preferable from the viewpoint of excellent adhesion to the conductor and mechanical properties (elongation, breaking strength, etc.). Therefore, it is preferable to use one or more of the polyphenylene ether derivatives represented by any of the general formulas (C-8) to (C-10) according to the desired characteristics.

The number average molecular weight of the polyphenylene ether derivative (C) is preferably 3,000 to 12,000, more preferably 5,000 to 12,000, even more preferably 7,000 to 12,000, and 7,000 to 10 000 is particularly preferred. When the number average molecular weight is 3,000 or more, a better glass transition temperature tends to be obtained in the resin composition of the present invention, the prepreg using the resin composition, and the laminated board. Further, when the number average molecular weight is 12,000 or less, better moldability tends to be obtained when the resin composition of the present invention is used for a laminated board.
In the present specification, the number average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, the measurement of the number average molecular weight described in Examples. It is a value obtained by the method.

((C) Method for producing polyphenylene ether derivative)
The polyphenylene ether derivative (C) can be obtained, for example, by the following production method.
First, an aminophenol compound represented by the following general formula (c1-1) (hereinafter, also referred to as “(c1) aminophenol compound”) and, for example, a polyphenylene ether having a number average molecular weight of 15,000 to 25,000 are organic. By carrying out a known redistribution reaction in a solvent, a polyphenylene ether compound having a primary amino group in the (C') molecule (hereinafter, simply, "(C')" is accompanied by a reduction in the molecular weight of the polyphenylene ether. ) Polyphenylene ether compound (also referred to as "polyphenylene ether compound"), and then (C') polyphenylene ether compound and a bismaleimide compound represented by the general formula (c2-1) (hereinafter, also referred to as "(c2) bismaleimide compound"). The (C) polyphenylene ether derivative can be produced by carrying out the Michael addition reaction.

（式中、Ｒ^Ｃ０及びｙは、前記一般式（Ｃ−２）中のものと同じである。）

(In the formula, ^RC0 and y are the same as those in the general formula (C-2).)

（式中、Ｘ^Ｃ１は、前記一般式（Ｃ−２）中のものと同じである。）

(In the formula, X ^C1 is the same as that in the general formula (C-2).)

Examples of the (c1) aminophenol compound include o-aminophenol, m-aminophenol, p-aminophenol and the like. Among these, m-aminophenol and p-aminophenol are preferable, and p-amino is preferable from the viewpoint of the reaction yield when producing the (C') polyphenylene ether compound and the heat resistance of the obtained thermosetting resin composition. Phenol is more preferred.

The molecular weight of the (C') polyphenylene ether compound can be controlled by the amount of the (c1) aminophenol compound used, and the larger the amount of the (c1) aminophenol compound used, the lower the molecular weight of the obtained (C') polyphenylene ether compound. Will be done. That is, the amount of the (c1) aminophenol compound used may be appropriately adjusted so that the number average molecular weight of the finally produced (C) polyphenylene ether derivative is in a suitable range.
The blending amount of the (c1) aminophenol compound is not particularly limited, but for example, if the number average molecular weight of the polyphenylene ether to be reacted with the (c1) aminophenol compound is 15,000 to 25,000. By using the polyphenylene ether in the range of 0.5 to 6 parts by mass with respect to 100 parts by mass, the (C) polyphenylene ether derivative having a number average molecular weight of 5,000 to 12,000 can be obtained.

Examples of the organic solvent used in the production process of the (C') polyphenylene ether compound include alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone, methyl ethyl ketone and methyl isobutyl ketone. Ketone solvents such as cyclohexanone; aromatic hydrocarbons such as toluene, xylene, mesitylen; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N- Examples thereof include nitrogen-containing compounds such as dimethylacetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, toluene, xylene, and mesitylene are preferable from the viewpoint of solubility.

Further, in the step of producing the (C') polyphenylene ether compound, a reaction catalyst can be used if necessary. As this reaction catalyst, a known reaction catalyst at the time of redistribution reaction can be applied. For example, from the viewpoint of obtaining a (C') polyphenylene ether compound having a stable number average molecular weight with good reproducibility, an organic peroxide such as t-butylperoxyisopropyl monocarbonate and a carboxylic acid metal salt such as manganese naphthenate are used. It may be used together. The amount of the reaction catalyst used is based on (c1) 100 parts by mass of the polyphenylene ether to be reacted with the aminophenol compound from the viewpoint of reaction rate and suppression of gelation when producing the (C') polyphenylene ether compound. 0.5 to 5 parts by mass of organic peroxide and 0.05 to 0.5 parts by mass of carboxylic acid metal salt may be used.

(C1) A (C') polyphenylene ether compound is obtained by charging an aminophenol compound, the polyphenylene ether, an organic solvent and, if necessary, a reaction catalyst in a predetermined amount into a reactor and reacting them with heating, heat retention and stirring. As the reaction temperature and reaction time in this step, the reaction conditions in the known redistribution reaction can be applied. From the viewpoint of workability and suppression of gelation, and from the viewpoint of controlling the molecular weight of the component (C), for example, the reaction may be carried out at a reaction temperature of 70 to 110 ° C. and a reaction time of 1 to 8 hours.

The solution of the (C') polyphenylene ether compound produced as described above may be continuously supplied as it is to the next step of producing the (C) polyphenylene ether derivative. At this time, the solution of the (C') polyphenylene ether compound may be cooled, or may be adjusted to the reaction temperature of the next step. Further, this solution may be concentrated as necessary to remove a part of the organic solvent as described later, or may be diluted by adding an organic solvent.

Examples of the (c2) bismaleimide compound used in producing the (C) polyphenylene ether derivative include the same as the maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule.
Among these, bis (4-maleimidephenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimide phenoxy) Phenyl] propane is preferred.
A polyphenylene ether derivative containing the polyphenylene ether derivative represented by the general formula (C-8) can be obtained, and bis (4-maleimidephenyl) methane is preferable from the viewpoint of low cost.
A polyphenylene ether derivative containing the polyphenylene ether derivative represented by the general formula (C-9) can be obtained, and from the viewpoint of excellent dielectric properties and low water absorption, 3,3'-dimethyl-5,5'- Dielectric-4,4'-diphenylmethane bismaleimide is preferred.
A polyphenylene ether derivative containing the polyphenylene ether derivative represented by the general formula (C-10) can be obtained, and from the viewpoint of excellent adhesion to a conductor and mechanical properties (elongation, breaking strength, etc.), 2,2- Bis [4- (4-maleimide phenoxy) phenyl] propane is preferred.

The amount of the (c2) bismaleimide compound used may be determined by the amount of the (c1) aminophenol compound used, and the -NH ₂ group equivalent (Ta1) of the (c1) aminophenol compound and the (c2) bismaleimide compound. The range in which the equivalent ratio (Tb1 / Ta1) with the maleimide group equivalent (Tb1) is 2 to 6 is preferable, and the range in which it is 2 to 4 is more preferable. By using the (c2) bismaleimide compound within the above equivalent ratio range, more excellent heat resistance and a high glass transition temperature tend to be obtained.

A reaction catalyst can also be used for the Michael addition reaction in producing the (C) polyphenylene ether derivative, if necessary. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. The blending amount of the reaction catalyst is, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the (C') polyphenylene ether compound.

A (C) polyphenylene ether derivative is obtained by charging (c2) a bismaleimide compound and, if necessary, a reaction catalyst or the like in a predetermined amount in a (C') polyphenylene ether compound solution, and causing a Michael addition reaction while heating, keeping warm, and stirring. .. The reaction conditions in this step may be, for example, a reaction temperature of 50 to 160 ° C. and a reaction time of 1 to 10 hours from the viewpoint of workability and suppression of gelation. Further, in this step, the reaction concentration (solid content concentration) and the solution viscosity can be adjusted by adding or concentrating the organic solvent as described above. As the organic solvent additionally used, the organic solvent exemplified in the production step of the (C') polyphenylene ether compound can be applied, and these may be used alone or in combination of two or more. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable from the viewpoint of solubility.

The content of the (C) polyphenylene ether derivative in the thermosetting resin composition is preferably 2 to 20 parts by mass and 3 to 17 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. By mass is more preferred, and 4 to 15 parts by mass is even more preferred. When the content of the (C) polyphenylene ether derivative is 2 parts by mass or more, the effect of reducing the dielectric constant is sufficiently obtained, and when it is 20 parts by mass or less, the dispersibility of the (C) polyphenylene ether derivative is excellent. Excellent heat resistance and peel strength.

<(D) Curing accelerator>
The thermosetting resin composition of the present invention may further contain (D) a curing accelerator from the viewpoint of accelerating the curing reaction.
(D) Organophosphorus compounds such as triphenylphosphine; imidazoles and derivatives thereof; nitrogen-containing compounds such as secondary amines, tertiary amines, and quaternary ammonium salts; 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 (D) may be used alone or in combination of two or more.
When the thermosetting resin composition of the present invention contains (D) a curing accelerator, the content thereof is 0.1 to 1 with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 5 parts by mass is preferable, and 0.3 to 2 parts by mass is more preferable.

<(E) Inorganic filler>
The thermosetting resin composition of the present invention may further contain (E) an inorganic filler.
(E) As the inorganic filler, silica, alumina, titanium oxide, mica, berylia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, 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 fiber, 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, 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 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 (E) inorganic filler before compounding by a dry method or a wet method, and the surface-untreated (E) inorganic filler may be treated with another method. A so-called integral 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 (E) an inorganic filler, 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, and 50 to 250 parts by mass are more preferable. When the content of the inorganic filler (E) is within the above range, the moldability and low thermal expansion property are good.

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

<Other ingredients>
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.

The prepreg of the present invention is, for example, a fiber base material so that the amount of the thermosetting resin composition adhered to the fiber base material (the content of the thermosetting resin composition in the prepreg) is 20 to 90% by mass. After impregnating with, it is usually obtained by heating and drying at a temperature of 100 to 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. 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 is manufactured by using 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.

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 compressed using a TMA test device (manufactured by TA Instruments, trade name: Q400). Thermomechanical analysis was performed by the method. 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 different tangents of the thermal expansion curves in the second measurement were obtained 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 a TMA test device (manufactured by TA Instruments Co., Ltd., product name: Thermomechanical analysis was performed by the compression method using Q400). 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 Electronics 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) Heat resistance of solder with copper A copper-clad laminate was cut out to a size of 25 mm square to prepare an evaluation substrate, and the evaluation substrate was floated in a solder bath at a temperature of 288 ° C for up to 60 minutes while observing the appearance. By doing so, the time until the swelling occurred was measured. The evaluation results are shown in Table 1 as ">60" in which no swelling was confirmed after floating for 60 minutes.

(5) Water-absorbing solder with half-copper Heat resistance Copper-clad laminate is cut to a size of 50 mm square, leaving half-sided copper on only one surface, and immersing the other surface in a copper etching solution to remove copper on the entire surface. As a result, a 50 mm square evaluation substrate with semi-copper was produced. The evaluation substrate with half-copper after being treated in a pressure cooker test (PCT) device (manufactured by Hirayama Seisakusho Co., Ltd.) (condition: 121 ° C., 2.2 atm) for 5 hours is placed in a solder bath at 288 ° C. for 20 seconds each. After immersion, the heat resistance of the solder with water-absorbing half-copper was evaluated by visually observing the appearance. The evaluation results are shown in Table 1 as "OK" when no swelling was confirmed and "swelling" when swelling was confirmed.

Production Example A-1: [Production of modified maleimide resin (A-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 Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161A) ) 15.9 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) AA) 28.6 g, and bis (4-maleimide) 280.5 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 at 126 ° C. for 5 hours to modify a modified maleimide resin (A). The solution of -1) was obtained.

Production Example A-2: [Production of Modified Maleimide Resin (A-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) ) 14.4 g and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 56.9 g and bis (4-maleimidephenyl) 253.7 g of methane (manufactured by Keiai Kasei Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether are added and reacted at 126 ° C. for 5 hours to modify a maleimide resin (A-2). ) Was obtained.

Production Example A-3: [Production of Modified Maleimide Resin (A-3)]
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 Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161B) ) 15.6 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) AA) 21.8 g, 2,2-bis [4- (4-Maleimidephenoxy) phenyl] Propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 274.2 g and propylene glycol monomethyl ether 200.0 g were added and reacted at 120 ° C. for 4 hours. A solution of the modified maleimide resin (A-3) was obtained.

Production Example A-4: [Production of Modified Maleimide Resin (A-4)]
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 Shin-Etsu Chemical Industry Co., Ltd., trade name: X-22-161A) ) 16.6 g and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP) 25.5 g and 2,2-bis [4 -(4-Maleimidephenoxy) phenyl] Propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) (292.6 g) and propylene glycol monomethyl ether (200.0 g) were added and reacted for 6 hours while refluxing. A solution of the modified maleimide resin (A-4) was obtained.

Production Example C-1: [Production of polyphenylene ether derivative (C-1)]
Toluene 950 g, polyphenylene ether (manufactured by SABIC Innovative Plastics, trade name: PPO640, number average molecular weight: approx. 16,000) 500 g and p-aminophenol (manufactured by Tokyo Kasei Co., Ltd.) were added, and the temperature inside the flask was set to 90 ° C., kept warm and dissolved with stirring. After confirming the dissolution, 10 g of t-butylperoxyisopropyl monocarbonate (manufactured by Alchema Yoshitomi Co., Ltd.) and 0.8 g of manganese naphthenate (manufactured by Tokyo Kasei Co., Ltd.) were added, and the mixture was reacted at a solution temperature of 90 ° C. for 4 hours. The mixture was cooled to 70 ° C. to obtain a (C') polyphenylene ether compound having a primary amino group at the molecular terminal. When a small amount of this reaction solution was taken out and measured by gel permeation chromatography (GPC), the peak derived from p-aminophenol disappeared, and the number average molecular weight of the polyphenylene ether compound was about 9,200. It was. Next, 22.5 g of bis (4-maleimidephenyl) methane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-1000) and 50 g of propylene glycol monomethyl ether are added to the above reaction solution, and the liquid temperature is raised while stirring. After warming and reacting at 120 ° C. for 4 hours, cooling and filtration through 200 mesh were performed to produce a polyphenylene ether derivative (C-1). The number average molecular weight of the polyphenylene ether derivative (C-1) was about 9,400.

Here, the number average molecular weight was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSKstandardPOLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) (manufactured by Tosoh Corporation, product) Name) was used for approximation by a cubic equation. The measurement conditions of GPC are shown below.
apparatus:
Pump: L-6200 type (manufactured by Hitachi High-Technologies Corporation)
Detector: L-3300 type RI (manufactured by Hitachi High-Technologies Corporation)
Column oven: L-655A-52 (manufactured by Hitachi High-Technologies Corporation)
Column: Guard column; TSK Guardcolum HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade name)
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C

Production Example C-2: [Production of Polyphenylene Ether Derivative (C-2)]
In Production Example C-1, instead of bis (4-maleimidephenyl) methane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) A polyphenylene ether derivative (C-2) was obtained in the same manner as in Production Example C-1 except that 36 g was used.

Examples 1-10 and Comparative Examples 1-5
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 the solution (excluding the organic solvent) or the dispersion liquid, the solid content conversion amount). A varnish having a solid content concentration of 65% by mass was prepared using methyl ethyl ketone as a solvent.
Next, this varnish was impregnated and coated on a low-dielectric glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 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 90 minutes to obtain a copper-clad laminate. Table 1 shows the evaluation results of the obtained copper-clad laminate.

Each component used in the formulation is shown below.

[(A) Modified maleimide resin]
-Modified maleimide resin (A-1): Modified maleimide resin (A-1) prepared in Production Example A-1.
-Modified maleimide resin (A-2): Modified maleimide resin (A-2) prepared in Production Example A-2.
-Modified maleimide resin (A-3): Modified maleimide resin (A-3) prepared in Production Example A-3.
-Modified maleimide resin (A-4): Modified maleimide resin (A-4) prepared in Production Example A-4.

[(B) Thermoplastic Elastomer]
-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.)
Septon 2063: Hydrogenated styrene-isoprene copolymer resin (manufactured by Kuraray Co., Ltd.)

[(C) Polyphenylene ether derivative]
-Polyphenylene ether derivative (C-1): The polyphenylene ether derivative (C-1) prepared in Production Example C-1.
-Polyphenylene ether derivative (C-2): The polyphenylene ether derivative (C-2) prepared in Production Example C-2.

[(D) Curing accelerator]
-TPP-MK: Tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical Industry Co., Ltd.)
-Perbutyl-P: α, α'-bis (t-butylperoxy) diisopropylbenzene (manufactured by NOF CORPORATION)
2E4MZ: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
2E4MZ-A: 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -ethyl-s-triazine (manufactured by Shikoku Chemicals Corporation)

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

As is clear from Table 1, the laminated plates obtained in Examples 1 to 10 are excellent in all of the glass transition temperature, the coefficient of thermal expansion, the dielectric property, the heat resistance of solder with copper, and the heat resistance of solder with water-absorbing semi-copper. There is. On the other hand, Comparative Examples 1 to 5 are inferior in either the dielectric property or the heat resistance of the solder with water-absorbing half-copper.

The printed wiring board obtained by using the thermosetting resin composition of the present invention has a high glass transition temperature, a low thermal expansion property, a low dielectric property, and a high heat resistance, so that it can be used for a highly integrated semiconductor package and high-speed communication. It is useful as a compatible printed wiring board for electronic devices.

Claims (11)

(A) An addition reaction product of a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having at least two primary amino groups in one molecule. ,
(B) Thermoplastic elastomer and
(C) A polyphenylene ether derivative having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (C-1) in one molecule.
Thermosetting resin composition containing.

(In the formula, ^RC is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively. X is an integer of 0 to 4.) The thermosetting resin composition according to claim 1, wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (C-2).

(In the formula, ^RC0 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Y is an integer of 0 to 4. X ^C1 is the following general formula (C-). 3), (C-4), (C-5) or (C-6).)

(In the formula, ^RC1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, respectively. P is an integer of 0 to 4.)

(In the formula, ^RC2 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X C2} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group, single bond or group represented by the following general formula (C-4'). Q is an integer of 0 to 4 independently. .)

(In the formula, ^RC3 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. X C3} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, carbooxy group, keto group or single bond. R is an integer of 0 to 4 independently.)

(In the formula, n is an integer from 0 to 10.)

(In the formula, ^RC4 is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U is an integer of 1 to 8.) The thermosetting resin according to claim 1 or 2, wherein the content of the component (C) is 2 to 20 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. Composition. The thermosetting resin composition according to any one of claims 1 to 3, wherein the component (a2) contains a modified siloxane compound having an amino group at the terminal. (B) The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermoplastic elastomer is a hydrogenated styrene-based thermoplastic elastomer. (B) The content of the thermoplastic elastomer is 4 to 30 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, according to any one of claims 1 to 5. The thermosetting resin composition according to the above. The thermosetting resin composition according to any one of claims 1 to 6, further comprising (D) a curing accelerator. The thermosetting resin composition according to any one of claims 1 to 7, further comprising (E) an inorganic filler. A prepreg obtained by impregnating a fiber base material with the thermosetting resin composition according to any one of claims 1 to 8. A laminated board obtained by laminating and molding the prepreg according to claim 9. A printed wiring board manufactured by using the prepreg according to claim 9 or the laminated board according to claim 10.