JP7100799B2 - Thermosetting resin composition, prepreg, laminated board, printed wiring board and high-speed communication compatible module - Google Patents

Description

The present invention relates to a thermosetting resin composition, a prepreg, a laminated board, a printed wiring board, and a module compatible with high-speed communication.

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 and the like. 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 and speed of information communication in network infrastructure equipment, large computers, etc., the semiconductor packages mounted on these electronic equipment need to support higher frequencies, and low dielectric constants that enable reduction of transmission loss. There is a demand for a substrate material having a ratio and a low dielectric loss tangent.

As a laminated board for a printed wiring board, a prepreg containing a resin composition containing an epoxy resin as a main component and a glass cloth is generally cured and integrally molded.
Epoxy resins have an excellent balance of insulation, heat resistance, cost, and the like, but further improvements are required to meet the excellent heat resistance and low thermal expansion required for recent semiconductor package substrate applications. 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 Document 1). 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.

It is known that a modified maleimide resin in which a siloxane skeleton is introduced into a bismaleimide resin has excellent heat resistance and low thermal expansion without excessively increasing the content of an inorganic filler (see, for example, Patent Document 2). ). Further, the modified maleimide resin has a low relative permittivity and a low dielectric loss tangent as compared with the epoxy resin, but has not yet achieved the relative permittivity and the dielectric loss tangent required in recent years.

For the purpose of improving the dielectric property, 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, the compatibility with other thermosetting resins is low, the shrinkage rate at the time of curing is large, copper foil, etc. Has drawbacks such as poor adhesion to metal foil.
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, which causes a problem that the heat resistance is lowered.

Further, in recent years, in a semiconductor package substrate, the difference in the coefficient of thermal expansion between the chip and the substrate and the warp caused by the curing shrinkage of the substrate have been problems. As a method for improving the warp, a method of reducing the coefficient of thermal expansion of the base material and the rate of curing shrinkage of the resin have been studied. As an example of the approach, a method of using a modified maleimide resin and a thermoplastic elastomer in combination has been proposed (see, for example, Patent Document 4). In Patent Document 4, the thermoplastic elastomer is applied for the purpose of reducing the curing shrinkage rate of the resin. Here, when a hydrogenated styrene-based elastomer is used as the thermoplastic elastomer, the polarity of the skeleton is very small, so that it exhibits a low relative permittivity and a low dielectric loss tangent. Therefore, by using the modified maleimide resin and the hydrogenated styrene-based elastomer in combination, it is possible to achieve both low thermal expansion and excellent dielectric properties (low relative permittivity and low dielectric loss tangent).

Further, a laminated board for a printed wiring board is required to be environmentally friendly, halogen-free, and flame-retardant. However, although the flame retardant can be ensured by adding a phosphorus-based or inorganic flame retardant as the flame retardant, if the type and amount of the flame retardant are not properly mixed, the heat resistance is lowered and the dielectric property is deteriorated. Will occur. For example, a phosphorus-based flame retardant does not contribute to curing and acts as a plasticizer, so that heat resistance deteriorates due to insufficient curing. Further, the inorganic flame retardant increases the water absorption rate of the resin composition and causes deterioration of the dielectric property.

Japanese Unexamined Patent Publication No. 5-148343 International Publication No. 2012-099133 Japanese Unexamined Patent Publication No. 61-23060 Japanese Unexamined Patent Publication No. 2014-24926

The resin composition in which the above-mentioned modified maleimide resin and the thermoplastic elastomer are used in combination has no problem in general heat resistance, but has heat resistance under severe conditions due to the recent high-density mounting of printed wiring boards and the high-multilayer configuration. That is, there is a problem that the heat resistance after water absorption is inferior. It is considered that this is because the compatibility between the modified maleimide resin and the thermoplastic elastomer was insufficient according to the study by the present inventors.

In view of the current situation, the subject of the present invention is halogen-free, has flame retardancy while suppressing deterioration of heat resistance and dielectric properties, and has excellent heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent. It is an object of the present invention to provide a thermosetting resin composition having the above, a prepreg using the same, a laminated board, a printed wiring board, and a high-speed communication compatible module.

As a result of diligent research to achieve the above object, the present inventors have made a modified maleimide resin having a specific structure, a thermoplastic elastomer, an aromatic vinyl compound, and a copolymer resin using a carboxylic acid anhydride as a raw material monomer. It was found that the above object could be achieved by using the above-mentioned material, and the present invention was completed. Furthermore, by selecting a phosphorus-based flame retardant as the flame retardant, sufficient flame retardancy could be imparted without deteriorating the characteristics.
That is, the present invention provides the following thermosetting resin composition, prepreg, laminated board, printed wiring board, and high-speed communication compatible module.
[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. Reactants and
(B) Thermoplastic elastomer and
(C) A copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride,
(D) Phosphorus-based flame retardants as flame retardants,
A thermosetting resin composition containing
The thermoplastic elastomer of the component (B) is a hydrogenated styrene-based thermoplastic elastomer, and the content of styrene-derived structural units in the hydrogenated styrene-based thermoplastic elastomer is 20 to 60% by mass. Sex resin composition.
[2] The structural unit derived from the aromatic vinyl compound of the component (C) is represented by the following general formula (C-1), and the structural unit derived from the carboxylic acid anhydride is represented by the following general formula (C-2). The thermosetting resin composition according to the above item [1], which is a structural unit derived from maleic anhydride represented by.

（一般式（Ｃ-１）中、Ｒ^Ｃ１は、水素原子又は炭素数１～５の脂肪族炭化水素基を示し、Ｒ^Ｃ２は、各々独立に、炭素数１～５の脂肪族炭化水素基又は炭素数６～２０の芳香族炭化水素基を示し、ｘは、０～３の整数を示す。）

(In the general formula ( ^C -1), RC1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and ^RC2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Alternatively, it indicates an aromatic hydrocarbon group having 6 to 20 carbon atoms, and x indicates an integer of 0 to 3).

[3] As the component (C), the structural unit represented by the general formula (C-1) in which RC1 in the general formula ( ^C -1) is a hydrogen atom and x is 0, and the general formula (C-1) are used. The above [2] , which contains a copolymer resin having a content ratio [(C-1) / (C-2)] (molar ratio) of 5 to 10 with the structural unit represented by the formula (C-2). The thermosetting resin composition according to the section .
[4] The content of the component (B) is 4 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, and the content of the component (C) is The thermosetting resin composition according to any one of the above [1] to [3], which 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. thing.
[5] The thermosetting resin composition according to any one of the above [1] to [4], wherein the component (a2) contains a modified siloxane having an amino group at the terminal.
[6] When the amount of the phosphorus-based flame retardant of the component (D) is 100 parts by mass when the total mass of the components (A), (B) and (C) is 100 parts by mass, the content of the phosphorus atom is 1. The thermosetting resin composition according to any one of the above [1] to [5], which is 0.0 to 4.0 parts by mass.
[7] The thermosetting resin composition according to any one of the above [1] to [6], which further contains (E) a curing accelerator.
[8] The thermosetting resin composition according to any one of the above [1] to [7], which further contains (F) 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 item [9].
[11] A printed wiring board manufactured by using the prepreg according to the above item [9] or the laminated board according to the above item [10].
[12] A high-speed communication compatible module manufactured by using the printed wiring board according to the above item [11].

According to the present invention, it is halogen-free, has flame retardancy while suppressing deterioration of heat resistance and deterioration of dielectric properties, and has excellent heat resistance, low thermal expansion, low relative permittivity and low dielectric loss tangent. It is possible to provide a resin composition, a prepreg using the resin composition, a laminated board, a printed wiring board, and a high-speed communication compatible module.

[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. Additive reaction product with amine compound (a2) (hereinafter, also referred to as "(A) modified maleimide resin"), (B) thermoplastic elastomer, (C) structural unit derived from aromatic vinyl compound, and carboxylic acid anhydride. A thermosetting resin composition containing a copolymer resin containing a structural unit of origin (hereinafter, also referred to as “(C) copolymer resin”) and (D) a phosphorus-based flame retardant as a flame retardant. ..

<(A) Modified maleimide resin>
(A) The modified maleimide resin 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)
The maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule (hereinafter, also referred to as “component (a1)”) has at least two N-substituted maleimide groups in one molecule. The structure is not particularly limited, but a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (a1-1) is more preferable.

（一般式（ａ１－１）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。）

(In the general formula (a1-1), XA1 is a group represented by the following general formulas (a1-2), (a1-3), (a1-4) or ( ^a1-5 )).

（一般式（ａ１－２）中、Ｒ^Ａ１は、各々独立に、炭素数１～５の脂肪族炭化水素基である。ｐ１は、０～４の整数である。）

(In the general formula (a1-2), ^RA1 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms independently. P1 is an integer of 0 to 4).

（一般式（ａ１－３）中、Ｒ^Ａ２は、各々独立に、炭素数１～５の脂肪族炭化水素基ある。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、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 general formula (a1-3), RA2 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms independently, and ^XA2 is an alkylene group having 1 to 5 carbon atoms and ² to 5 carbon atoms. It is an alkylidene group, an ether group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (a1-3'). Q1 is an independently integer of 0 to 4).

（一般式（ａ１－３’）中、Ｒ^Ａ３は、各々独立に、炭素数１～５の脂肪族炭化水素基である。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、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 general formula (a1-3'), ^{RA3 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms independently, and X A3 is} an alkylene group having 1 to 5 carbon atoms and 2 to 2 carbon atoms. 5 is an alkylidene group, an ether group, a carbooxy group, a keto group or a single bond. R1 is independently an integer of 0 to 4).

（一般式（ａ１－４）中、ｎ１は、１～１０の整数である。）

(In the general formula (a1-4), n1 is an integer of 1 to 10.)

（一般式（ａ１－５）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。）

(In the general formula (a1-5), ^RA4 is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U1 is an integer of 1 to 8).

In the general formula ( ^a1-2 ), the aliphatic hydrocarbon group represented by RA1 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. -Examples include an alkyl group having 1 to 5 carbon atoms such as a pentyl group.

In the general formula (a1-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^RA2 are the same as in the case of ^RA1 .
Examples of the alkylene group having 1 to 5 carbon atoms represented by ^XA2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Be done.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by ^XA2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.

In the general formula ( ^a1-3 '), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RA3 include the same as in the case of ^RA2 .
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.

In the general formula ( ^a1-5 ), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^RA4 are the same as those in the case of RA1 in the general formula (a1-2).

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) ketone, bis (4-maleimidecyclohexyl) methane, 1,4-bis (4-maleimidephenyl) cyclohexane, 1,4-bis (maleimidemethyl) cyclohexane, 1,4-bis (maleimidemethyl) ) Benzene, 1,3-bis (4-maleimidephenoxy) benzene, 1,3-bis (3-maleimidephenoxy) benzene, bis [4- (3-maleimidephenoxy) phenyl] methane, bis [4- (4- (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-Maleimidephenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidephenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidephenoxy) 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 , 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, bis [4- (3-maleimidephenoxy) phenyl] ether, bis [4- (4-maleimidephenoxy) 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-maleimidephenoxy) 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.

（一般式（ａ２－１）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。）

(In the general formula (a2-1), YA1 is a group represented by the following general formula ( ^a2-2 ), (a2-3) or (a2-4).)

（一般式（ａ２－２）中、Ｒ^Ａ５は、各々独立に、炭素数１～５の脂肪族炭化水素基である。ｐ２は、０～４の整数である。）

(In the general formula (a2-2), ^RA5 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms independently. P2 is an integer of 0 to 4).

（一般式（ａ２－３）中、Ｒ^Ａ６は、各々独立に、炭素数１～５の脂肪族炭化水素基である。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、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。）

(In the general formula ( ^a2-3 ), RA6 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms independently, and YA2 is an alkylene group having 1 to 5 carbon atoms and ² to 5 carbon atoms. Alkylidene group, ether group, carooxy group, keto group, single bond or group represented by the following general formula (a2-3'). Q2 is an independently integer of 0 to 4).

（一般式（ａ２－３’）中、Ｒ^Ａ７は、各々独立に、炭素数１～５の脂肪族炭化水素基である。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。）

(In the general formula (a2-3'), ^RA7 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms independently, and ^YA3 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. 5 is an alkylidene group, an ether group carbooxy group, a keto group or a single bond. S1 is an independently integer of 0 to 4).

（一般式（ａ２－４）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。）

(In the general formula (a2-4), ^RA8 is an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group, respectively. ^RA9 is an independently divalent organic group. Yes, m2 is an integer from 1 to 100.)

In the general formula (a2-2), the aliphatic hydrocarbon group represented by ^RA5 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. -Examples include an alkyl group having 1 to 5 carbon atoms such as a pentyl group.

In the general formula ( ^a2-3 ), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by RA6 are the same as those in the case of ^RA5 .
Examples of the alkylene group having 1 to 5 carbon atoms represented by ^YA2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Be done.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by YA2 include an ethylidene group, a ^propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.

In the general formula (a2-3'), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^RA7 are the same as in the case of ^RA6 .
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by ^YA3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by ^YA2 . Be done.

In the general formula (a2-4), as the alkyl group having 1 to 5 carbon atoms represented by ^RA8 , an alkyl group having 1 to 3 carbon atoms is more preferable. 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, and among these, methyl. Groups are 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 the same as the alkyl group represented by ^RA8 .
Examples of the divalent organic group represented by ^RA9 include an alkylene group, an alkylidene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined. 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.

The components (a2) include modified siloxane having an amino group at the terminal, diaminobenzidine, diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether, 3,3'-dimethoxy-4,4. ´-Diaminobiphenyl, 3,3 ′-dimethyl-4,4 ′-diaminobiphenyl, 1,3 ′-bis (4-aminophenoxy) benzene, 2,2 ′-bis [4- (4-aminophenoxy) phenyl ] Propane ,, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4'-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4 ′ -Diamino-3,3′-biphenyldiol and the like can be mentioned.
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, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane Is preferable.
Further, from the viewpoint of low thermal expansion, a modified siloxane having an amino group at the terminal is preferable. As the modified siloxane having an amino group at the terminal, a commercially available product may be used, and the commercially available product includes "X-22-161A" (functional group equivalent 800 g / mol) and "X-" having amino groups at both ends. 22-161B ”(functional group equivalent 1,500 g / mol) (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.),“ BY16-853U ”(functional group equivalent 460 g / mol) (above, manufactured by Toray Dow Corning Co., Ltd.), Examples thereof include "XF42-C5379" (functional group equivalent 750 g / mol) (all manufactured by Momentive Performance Materials Japan GK).

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 one or more kinds selected from the group in combination.
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 modified siloxanes 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 (A) modified maleimide resin, 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).

（一般式（Ａ－１）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。）

(In the general formula (A-1), X ^A1 is the same as X ^A1 in the general formula (a1-1), and Y ^A1 is the same as Y ^A1 in the general formula (a2-1). )

((A) Method for producing modified maleimide resin)
The (A) modified maleimide resin 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 equivalent of the maleimide group 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 and propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as acetate ethyl ester; aromatic solvents such as toluene; dimethyl. Examples thereof include nitrogen atom-containing solvents such as acetamide and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are preferable from the viewpoint of low toxicity and high volatility and less likely to remain as a residual solvent. Is preferable.
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 content excluding volatile substances such as a solvent, and indicates a component that remains unvolatile when the resin composition is dried, and at room temperature. Includes liquid, candy-like and wax-like substances. Here, the room temperature is 25 ° C. in the present specification.
The "resin component" is a component used in the production of a resin or a resin, excluding the inorganic filler described later, and specifically, (A) a modified maleimide resin, (B) a thermoplastic elastomer, ( C) Copolymerized resin or the like corresponds to the resin component.

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, 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>
The (B) thermoplastic elastomer (hereinafter, also referred to as “component (B)”) is not particularly limited, and can be appropriately selected from conventionally known thermoplastic elastomers. However, in the present invention, the (B) thermoplastic elastomer is defined as not containing a copolymer resin containing (C) a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride, which will be described later. Ru.
Examples of the thermoplastic elastomer (B) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and derivatives thereof. The 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, a vinyl group and the like. By having these reactive functional groups at the molecular end or in the molecular chain, the compatibility is improved and the heat resistance of the substrate can be improved.
Among these reactive functional groups, it is more preferable to have a carboxy group, an amino group and a hydroxyl group from the viewpoint of adhesion to the metal foil and from the viewpoint of heat resistance and insulation reliability.

Further, from the viewpoint of compatibility with the modified polyimide resin, the (B) thermoplastic elastomer is preferably a styrene-butadiene copolymer or a styrene-isoprene copolymer, and from the viewpoint of dielectric properties, these copolymers are two. A hydrogenated styrene-based thermoplastic elastomer such as a hydrogenated styrene-butadiene copolymer resin and a hydrogenated styrene-isoprene copolymer resin to which a double-bonded portion is hydrogenated is more preferable.
Further, the content of the structural unit derived from styrene (hereinafter, also referred to as “styrene amount”) in the hydrogenated styrene-based thermoplastic elastomer is preferably 20 to 60% by mass, preferably 25 to 55% by mass. Is more preferable. (B) Moisture absorption is achieved by using a hydrogenated styrene-based thermoplastic elastomer such as a hydrogenated styrene-butadiene copolymer resin or a hydrogenated styrene-isoprene copolymer resin having a styrene content of 20 to 60% by mass as the thermoplastic elastomer. In addition to being excellent in heat resistance, the appearance of the prepreg after coating is excellent, and it is possible to achieve a resin in which the amount of prepreg powder falling off is small. When the amount of styrene is 60% by mass or less, the base material properties (thermal expansion rate, dielectric properties, heat resistance) are good, and the appearance of the prepreg after coating tends to be less likely to be cracked. It is considered that this is because the stacking aggregation of styrene is suppressed and the flexibility of the resin is excellent. When the amount of styrene is 20% by mass or more, the substrate properties (coefficient of thermal expansion, dielectric properties, heat resistance) are good, and in addition, the compatibility between (A) modified maleimide resin and (B) thermoplastic elastomer It is excellent, the amount of resin powder falling off is small, and it tends to be easy to handle. This is because (A) the maleimide group contained in the modified maleimide resin has a structure similar to that of styrene as compared with butadiene, isoprene, etc., and therefore (B) when the amount of styrene in the thermoplastic elastomer is 20% by mass or more. (A) It is considered to be derived from the excellent compatibility between the modified maleimide resin and the styrene-based skeleton.
As the styrene-based elastomer, a commercially available product may be used, and the commercially available products include "Tough Tech (registered trademark) H1051", "Tough Tech H1053", "Tough Tech M1911", and "Tough Tech M1913" (all manufactured by Asahi Kasei Chemicals Co., Ltd.). ), "Septon (registered trademark) 2002", "Septon HG252" (manufactured by Kuraray Co., Ltd.) and the like.

The content of the (B) thermoplastic elastomer in the thermosetting resin composition is preferably 4 to 20 parts by mass, preferably 6 to 15 parts by mass with respect to 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 is sufficiently obtained, and when it is 20 parts by mass or less, (B) the thermoplastic elastomer is compatible with each other in the resin. It disperses sufficiently and has excellent heat resistance and peel strength.

<(C) Copolymer resin>
The (C) copolymer resin is a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride.
By containing (C) the copolymerized resin, 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. However, since the thermoplastic elastomer has a significantly different skeleton structure from the modified maleimide resin, they are compatible with each other. 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) copolymer resin contained in the thermosetting resin composition of the present invention contains a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride, and is derived from an aromatic vinyl compound. The structural unit has excellent compatibility with thermoplastic elastomers (particularly styrene-containing elastomers), and the structural unit derived from carboxylic acid anhydride has excellent compatibility with modified maleimide resins. Therefore, the (C) copolymer resin functions as a compatibilizer between the (A) modified maleimide resin and the (B) thermoplastic elastomer, whereby the (A) modified maleimide resin and the (B) thermoplastic elastomer can be combined. It is considered that the compatibility was improved and the heat resistance was improved. Furthermore, since the (C) copolymer resin itself also has excellent dielectric properties, it is considered that excellent heat resistance could be imparted without impairing the dielectric properties.

As the structural unit derived from the aromatic vinyl compound of the (C) copolymer resin, the structural unit represented by the following general formula (C-1) is preferable. Examples of the structural unit derived from the carboxylic acid anhydride of the component (C) include a structural unit derived from maleic anhydride, a structural unit derived from phthalic anhydride, a structural unit derived from succinic anhydride, and the like. A) From the viewpoint of compatibility with the modified maleimide resin, a structural unit derived from maleic anhydride represented by the following general formula (C-2) having a structure close to that of a maleimide group is preferable.

（一般式（Ｃ－１）中、Ｒ^Ｃ１は、水素原子又は炭素数１～５の脂肪族炭化水素基を示し、Ｒ^Ｃ２は、各々独立に、炭素数１～５の脂肪族炭化水素基又は炭素数６～２０の芳香族炭化水素基を示し、ｘは、０～３の整数を示す。）

(In the general formula ( ^C -1), RC1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and ^RC2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Alternatively, it indicates an aromatic hydrocarbon group having 6 to 20 carbon atoms, and x indicates an integer of 0 to 3).

The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^RC1 and ^RC2 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 an n-. Examples include a pentyl group. Among these, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable, from the viewpoint of adhesion to a copper foil and dielectric properties.
Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms indicated by ^RC2 include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group and the like.
In the structural unit represented by the general formula (C-1), the structural unit represented by the following formula ( ^C -1') in which RC1 is a hydrogen atom and x is 0 is preferable.

(C) Content ratio of the structural unit represented by the general formula (C-1) and the structural unit represented by the general formula (C-2) in the copolymer resin [(C-1) / (C). -2)] (molar ratio) is preferably 2 to 12, more preferably 5 to 10. When the content ratio is 2 or more, the effect of improving the dielectric property and the heat resistance tends to be sufficient, and when the content ratio is 12 or less, the compatibility tends to be good. Further, when [(C-1) / (C-2)] (molar ratio) is 5 to 10, in addition to having good substrate characteristics, (B) is excellent in compatibility with the thermoplastic elastomer. Since the content of the structural unit derived from styrene is in a preferable range, the compatibility between (A) the modified maleimide resin and (B) the thermoplastic elastomer is further improved, and the powder removal property of the prepreg is also improved.
The total content of the structural unit represented by the general formula (C-1) and the structural unit represented by the general formula (C-2) in the (C) copolymer resin is preferably 50% by mass or more. 70% by mass or more is more preferable, 90% by mass or more is further preferable, and substantially 100% by mass is particularly preferable.

(C) The copolymerized resin can be produced by copolymerizing an aromatic vinyl compound with maleic anhydride.
Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene and the like. These may be used alone or in combination of two or more.
Further, in addition to the aromatic vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. Examples of various polymerizable components include vinyl compounds such as ethylene, propylene and butadiene.

(C) As the copolymerized resin, a commercially available product can also be used, and as the commercially available product, "SMA (registered trademark) EF30" (styrene / maleic anhydride = 3, Mw = 9,500), "SMAEF40" ( Styrene / maleic anhydride = 4, Mw = 11,000), "SMAEF60" (styrene / maleic anhydride = 6, Mw = 11,500), "SMAEF80" (styrene / maleic anhydride = 8, Mw = 14, 400) (above, manufactured by Styrene) and the like. Among these, "SMAEF60" and "SMA-EF80" are preferable.

The content of the (C) copolymer resin in the thermosetting resin composition is preferably 2 to 20 parts by mass, preferably 3 to 15 parts by mass, based on 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. Parts by mass are more preferable, and parts by mass of 4 to 13 are even more preferable. When the content of the (C) copolymer resin is 2 parts by mass or more, the effect of lowering the dielectric constant is sufficiently obtained, and when it is 20 parts by mass or less, the dispersibility of the (C) copolymer resin is excellent. Excellent heat resistance and peel strength.

<(D) Phosphorus flame retardant>
Examples of the flame retardant that imparts flame retardancy to the resin composition used for the laminated board include halogen-based flame retardants, phosphorus-based flame retardants, and inorganic flame retardants. In recent years, due to the demand for environmental friendliness, it has been required not to use halogen-based flame retardants. Examples of the inorganic flame retardant include antimony trioxide and aluminum hydroxide, but these materials increase the water absorption rate of the resin composition and deteriorate the dielectric properties. Therefore, it is difficult to apply it to a resin composition having excellent dielectric properties required in recent years.
The phosphorus-based flame retardant is halogen-free and can impart flame retardancy without deteriorating the dielectric properties.

Examples of the organic phosphorus-based flame retardant include aromatic phosphoric acid esters, mono-substituted phosphonic acid diesters, 2-substituted phosphinic acid esters, metal salts of 2-substituted phosphinic acid, organic nitrogen-containing phosphorus compounds, and cyclic organic phosphorus compounds. Phosphorus-containing phenolic resin and the like can be mentioned. Among these, aromatic phosphate ester compounds, metal salts of disubstituted phosphinic acid, and cyclic organic phosphorus compounds are preferable. Here, the metal salt is preferably any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt and a zinc salt, and preferably an aluminum salt. Further, among the organic phosphorus-based flame retardants, aromatic phosphoric acid esters are more preferable.

Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyldi-2,6-xylenyl phosphate, resorcinolbis (diphenyl phosphate), 1,3. -Phenylene bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate) and the like can be mentioned.
Examples of the mono-substituted phosphonic acid diester include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphine acid and methyl diphenylphosphine acid.
Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, and a metal salt of diarylphosphinic acid. As described above, these metal salts are preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt.

Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.
As the cyclic organic phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Examples thereof include phosphaphenanthrene-10-oxide.
Among these, at least one selected from aromatic phosphate ester, metal salt of disubstituted phosphinic acid and cyclic organic phosphorus compound is preferable, and aromatic phosphoric acid ester and metal salt of disubstituted phosphinic acid are more preferable. preferable.

The aromatic phosphoric acid ester is preferably an aromatic phosphoric acid ester represented by the following general formula (D-1) or (D-2), and the metal salt of the disubstituted phosphinic acid is described below. It is preferably a metal salt of disubstituted phosphinic acid represented by the general formula (D-3).

(In the general formulas (D-1) to (D-3), R ^E1 to R ^E5 are independent, and each is an aliphatic hydrocarbon group or a hydrogen atom having 1 to 5 carbon atoms. E and f are independent of each other. It is an integer of 0 to 5, g, h and i are independently integers of 0 to 4. R ^E6 and R ^E7 are independently each of an aliphatic hydrocarbon group having 1 to 5 carbon atoms or 6 carbon atoms. 14 aromatic hydrocarbon groups. M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, and a zinc atom.)
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the hydrogen atom represented by ^{RE1 to RE5 include} a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group, as in the above general formulas. Examples thereof include an isobutyl group, a t-butyl group and an n-pentyl group. e and f are preferably integers of 0 to 2, and preferably 2. g, h and i are preferably integers of 0 to 2, preferably 0 or 1, and preferably 0.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by ^RE6 and ^RE7 include the same groups as those of ^RE1 to ^RE5 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and preferably an ethyl group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by ^RE6 and ^RE7 include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group and the like. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.
j represents the valence of the metal ion, that is, it changes in the range of 1 to 4 according to the type of M. As M, it is preferable that it is an aluminum atom. When M is an aluminum atom, j is 3.

The above-mentioned phosphorus-based flame retardant may be used alone or in a plurality of types.
Regarding the blending amount of the phosphorus-based flame retardant of the component (D), the content of the phosphorus atom is 1.0 when the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass. It is preferably about 4.0 parts by mass, and more preferably 1.2 parts by mass to 3.5 parts by mass. If the content of the phosphorus atom is less than 1.0 part by mass, sufficient flame retardancy cannot be imparted. If the content of the phosphorus atom exceeds 4.0 parts by mass, the phosphorus-based flame retardant acts as a plasticizer, resulting in deterioration of heat resistance.

<(E) Curing accelerator>
The thermosetting resin composition of the present invention may further contain (E) a curing accelerator from the viewpoint of accelerating the curing reaction.
(E) Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine; imidazoles and derivatives thereof; nitrogen-containing compounds such as secondary amines, tertiary amines and quaternary ammonium salts; dicumyl. Peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α'- Organic peroxides such as bis (t-butylperoxy) diisopropylbenzene; organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate and the like can be mentioned. (E) The curing accelerator may be used alone or in combination of two or more.
When the thermosetting resin composition of the present invention contains (E) a curing accelerator, the content thereof is 0.1 to 100 parts by mass with respect to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 5 parts by mass is preferable, and 0.3 to 2 parts by mass is more preferable.

<(F) Inorganic filler>
The thermosetting resin composition of the present invention may further contain (F) an inorganic filler.
(F) Examples of the inorganic filler include silica, alumina, titanium oxide, mica, barium titanate, strontium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, calcium carbonate, silicon nitride, boron nitride, talc, and 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.
(F) The inorganic filler 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 or the like. , 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 the resin.

(F) The average particle size of the inorganic filler 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 caused. The 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.
(F) The inorganic filler 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 (F) inorganic filler before compounding by a dry method or a wet method, and the surface-untreated (F) inorganic filler may be treated with another method. A so-called inorganic blend treatment method may be used in which a silane coupling agent is added to the composition after blending with the components to form 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 (F) an inorganic filler, the content thereof is 10 to 300% 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. (F) When the content of the inorganic filler is within the above range, the moldability and the low thermal expansion property are good.

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

<Other ingredients>
The (A) modified maleimide resin of the present invention is a thermosetting resin and has good thermosetting properties by itself. However, if necessary, it can be used in combination with other thermosetting resins to provide adhesiveness, mechanical strength, etc. Can be improved.
The thermosetting resin to be used in combination is not particularly limited, and examples thereof include epoxy resin, phenol resin, cyanate resin, isocyanate resin, benzoxazine resin, allyl resin, dicyclopentadiene resin, silicone resin, and triazine resin. May be used alone or in combination of two or more. Among these, cyanate resin and benzoxazine resin are preferable from the viewpoint of moldability and electrical insulation.
Further, although good adhesiveness can be obtained by containing an epoxy resin, the content thereof is preferably 2% by mass or less in the solid content of the thermosetting resin composition. By setting the content of the epoxy resin to 2% by mass or less, the dielectric properties and storage stability can be improved.

The thermosetting resin composition of the present invention may optionally contain a known organic filler, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent whitening agent, adhesiveness improver and the like.
Examples of the organic filler include a resin filler made of polyethylene, polypropylene resin and the like, a resin filler having a core-shell structure, and the like.
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.

The organic solvent used for the varnish includes alcohol solvents such as ethanol, propanol and propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as acetate ethyl ester; aromatics such as toluene and xylene. Group solvents: Nitrogen atom-containing solvents such as dimethylacetamide and N-methylpyrrolidone can be mentioned. These organic solvents may be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and toluene are preferable from the viewpoint of solubility, and propylene glycol monomethyl ether, methyl isobutyl ketone, cyclohexanone, and toluene 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-staged) by heating or the like.
As the fiber base material, well-known materials used for various laminated plates 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.

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 according to the intended use, performance, etc. of the molded product, and if necessary. It 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 can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

[Laminate 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.
As the forming conditions when manufacturing the laminated plate, for example, the method of the laminated plate for electric insulating material and the multilayer plate can be applied, and a multi-stage press, a multi-stage vacuum press, continuous forming, an autoclave forming machine, etc. are used, and the temperature is 100 to 250. It can be molded in the range of ° C., pressure 0.2 to 10 MPa, and heating time 0.1 to 5 hours. Further, the prepreg of the present invention and the wiring board for the inner layer can be combined and laminated to produce a laminated board.

[Printed wiring board]
The printed wiring board of the present invention is manufactured by using the prepreg or the 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 board of the present invention is wired by an ordinary etching method, and a plurality of laminated boards wire-processed via the prepreg of the present invention are laminated and heat-pressed to form a plurality of layers at once. 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.

[High-speed communication compatible module]
The high-speed communication compatible module of the present invention is a high-speed communication compatible module manufactured by using the printed wiring board of the present invention.
The high-speed communication compatible module of the present invention is, for example, a communication module or the like in which a semiconductor chip or the like is mounted on the printed wiring board of the present invention, and particularly uses signals in a high frequency range of wireless communication equipment, network infrastructure equipment, and the like. , Suitable for applications with high information communication volume and speed.

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 heat was applied by a compression method using a TMA test device (manufactured by TA Instruments, trade name: Q400). A machine analysis was performed. 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 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 prepared by immersing the copper-clad laminate in a copper etching solution, and a TMA test device (manufactured by TA Instruments, trade name: Q400) was used. Thermomechanical analysis was performed using the compression method. 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 x 2 mm (length x width) evaluation board 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. Relative permittivity and dielectric etching were measured at a frequency of 10 GHz.

(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 board, and the evaluation board 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 semi-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 board 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.

(6) A flame-retardant copper-clad laminate was immersed in a copper etching solution to remove the copper foil, and an evaluation substrate with a length of 125 mm and a width of 12.5 mm was prepared, and conformed to the UL-94 vertical test method. It was measured.

Production Example 1: [Production of Modified Maleimide Resin (A-1)]
A reaction vessel with a volume of 2 liters that can be heated and cooled equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser, and a double-ended diamine-modified siloxane (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). A modified maleimide resin (A) was prepared by adding 280.5 g of phenyl) methane (manufactured by Keiai Kasei Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether and allowing them to react for 5 hours while refluxing at 126 ° C. The solution of -1) was obtained.

Production Example 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 water meter with a reflux cooling tube, both-ended diamine-modified siloxane (manufactured by Shin-Etsu 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 form a modified maleimide resin (A-2). ) Was obtained.

Production Example 3: [Production of Modified Maleimide Resin (A-3)]
A reaction vessel with a volume of 2 liters capable of heating and cooling equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser, and a double-ended diamine-modified siloxane (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: KAYAHARDA-A) 21.8 g, 2,2-bis [4- (4) -Maleimide phenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 274.2 g and propylene glycol monomethyl ether: 200.0 g are added and reacted at 120 ° C. for 4 hours to modify maleimide. A solution of the resin (A-3) was obtained.

Production Example 4: [Production of Modified Maleimide Resin (A-4)]
A reaction vessel with a volume of 2 liters that can be heated and cooled equipped with a thermometer, a stirrer and a water content meter with a reflux cooling tube, and a double-ended diamine-modified siloxane (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-Maleimide phenoxy) phenyl] Propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 292.6 g and propylene glycol monomethyl ether 200.0 g are added and refluxed at 126 ° C for 6 hours. The reaction was carried out to obtain a solution of modified maleimide resin (A-4).

Examples 1 to 8 and Comparative Examples 1 to 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, which is the solid content conversion amount in the case of a solution (excluding the organic solvent) or the dispersion liquid). A varnish having a solid content concentration of 65% by mass was prepared by using methyl ethyl ketone and toluene as a solvent.
Next, this varnish was impregnated and coated on an E glass cloth (manufactured by Nitto Spinning Co., Ltd.) having a thickness of 0.1 mm and dried by heating at 160 ° C. for 5 minutes, and the content of the thermosetting resin composition was 46% by mass. I got the prepreg of.
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 ingredient 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 1.
Modified maleimide resin (A-2): Modified maleimide resin (A-2) prepared in Production Example 2.
Modified Maleimide Resin (A-3): Modified Maleimide Resin (A-3) Prepared in Production Example 3
Modified Maleimide Resin (A-4): Modified Maleimide Resin (A-4) Prepared in Production Example 4

[(B) Thermoplastic Elastomer]
Tough Tech H1051: Hydrogenated Styrene-butadiene copolymer resin (styrene amount: 42% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
-Tough Tech H1053: Hydrogenated styrene-butadiene copolymer resin (styrene amount: 29% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
Tough Tech M1913: Carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin (styrene amount: 30% by mass) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
Septon 2002: Hydrogenated styrene-isoprene copolymer resin (styrene amount: 30% by mass) (manufactured by Kuraray Co., Ltd.)

[(C) Copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride]
SMA-EF80 (styrene / maleic anhydride molar ratio = 8) (manufactured by Sartmer)

[(D) Phosphorus flame retardant]
PX-200: Aromatic phosphate ester (see structural formula below, 1,3-phenylene-bis- (di-2,6-xylenyl phosphate)) Phosphorus content 9% by mass (Daihachi Chemical Industry Co., Ltd.) Made)

・ＯＰ－９３５：ホスフィン酸アルミニウム、リン含有量２３質量％（クラリアントジャパン株式会社製）
・ＳＰＢ－１００：シクロホスファゼン、リン含有量１３質量％（大塚化学株式会社製）
・ＨＣＡ－ＨＱ－ＨＳ：１０－（２，５－ジヒドロキシフェニル）－９,１０－ジヒドロ－９－オキサ－１０－フォスファフェナントレン－１０－オキサイドの微粉砕品、リン含有量９．６質量％（三光株式会社製、平均粒子径１．５μｍ）

OP-935: Aluminum phosphinate, phosphorus content 23% by mass (manufactured by Clariant Japan Co., Ltd.)
-SPB-100: Cyclophosphazene, phosphorus content 13% by mass (manufactured by Otsuka Chemical Co., Ltd.)
HCA-HQ-HS: 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide finely pulverized product, phosphorus content 9.6% by mass (Made by Sanko Co., Ltd., average particle diameter 1.5 μm)

[(E) 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 Chemicals Corporation)
2E4MZ-A: 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -ethyl-s-triazine (manufactured by Shikoku Chemicals Corporation)

[(F) Inorganic filler]
・ Spherical fused silica (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 8 have glass transition temperature, coefficient of thermal expansion, dielectric properties, heat resistance to solder with copper, heat resistance to solder with water-absorbing semi-copper, and flame retardancy. Excellent in everything.
On the other hand, Comparative Examples 1 to 5 are inferior in any of the dielectric properties, the heat resistance of the solder with water-absorbing half-copper, and the flame retardancy.

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

Claims (12)

(A) 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 copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride,
(D) Phosphorus-based flame retardants as flame retardants,
A thermosetting resin composition containing
The thermoplastic elastomer of the component (B) is a hydrogenated styrene-based thermoplastic elastomer, and the content of styrene-derived structural units in the hydrogenated styrene-based thermoplastic elastomer is 20 to 60% by mass. Sex resin composition. The structural unit derived from the aromatic vinyl compound of the component (C) is represented by the following general formula (C-1), and the structural unit derived from the carboxylic acid anhydride is represented by the following general formula (C-2). The thermosetting resin composition according to claim 1, which is a structural unit derived from maleic anhydride.

(In the general formula ( ^C -1), RC1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and ^RC2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Alternatively, it indicates an aromatic hydrocarbon group having 6 to 20 carbon atoms, and x indicates an integer of 0 to 3). As the component (C), RC1 in the general formula ( ^C -1) is a hydrogen atom, x is 0, and the structural unit represented by the general formula (C-1) and the general formula (C). The heat according to claim 2 , which contains a copolymer resin having a content ratio [(C-1) / (C-2)] (molar ratio) of 5 to 10 with the structural unit represented by -2). Curable resin composition. The content of the component (B) is 4 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, and the content of the component (C) is heat-cured. The thermosetting resin composition according to any one of claims 1 to 3, wherein the solid content of the resin component in the sex resin composition is 2 to 20 parts by mass with respect to 100 parts by mass. The thermosetting resin composition according to any one of claims 1 to 4, wherein the component (a2) contains a modified siloxane having an amino group at the terminal. When the amount of the phosphorus-based flame retardant of the component (D) is 100 parts by mass when the total mass of the component (A), the component (B), and the component (C) is 100 parts by mass, the content of the phosphorus atom is 1.0 to The thermosetting resin composition according to any one of claims 1 to 5, which is 4.0 parts by mass. The thermosetting resin composition according to any one of claims 1 to 6, further comprising (E) a curing accelerator. The thermosetting resin composition according to any one of claims 1 to 7, further comprising (F) 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. A high-speed communication compatible module manufactured by using the printed wiring board according to claim 11.