JP2019123769A - Thermosetting resin composition, prepreg, laminate, printed wiring board and high-speed communication adaptive module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which 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 property, low relative permittivity and low dielectric loss tangent. , A prepreg, a laminated board, a printed wiring board, and a high-speed communication compatible module using the prepreg, a laminated board, and a high-speed communication compatible module are provided. SOLUTION: 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. A copolymer resin containing (B) a thermoplastic elastomer, (C) a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride, and (D) a phosphorus-based as a flame retardant. A thermosetting resin composition containing a flame retardant. [Selection diagram] None

Description

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

  With the trend of miniaturization and high performance of electronic devices in recent years, in the printed wiring board, advancement of wiring density and high integration progress, and along with this, in laminated boards for printed wiring boards, The demand for reliability improvement by heat resistance improvement etc. is intensifying. In such applications, particularly in semiconductor package substrate applications, it is required to combine 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-sized computers, etc., semiconductor packages mounted on these electronic equipments need to be compatible with high frequency, and the low dielectric constant enables reduction of transmission loss. There is a need for a substrate material having a modulus and a low dielectric loss tangent.

As a laminate for a printed wiring board, one obtained by curing and integrally molding a prepreg containing a resin composition containing an epoxy resin as a main ingredient and a glass cloth is generally used.
The epoxy resin is excellent in the balance of the insulating property, heat resistance, cost and the like, but further improvement is required to cope with the excellent heat resistance and low thermal expansion required for the recent semiconductor package substrate application. Since the epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selection of the epoxy resin having an aromatic ring and high filling of an inorganic filler such as silica (see, for example, Patent Document 1). However, increasing the filling amount of the inorganic filler is known to cause deterioration in insulation reliability due to moisture absorption, poor adhesion between the resin and the wiring layer, press forming failure, etc. There is a limit to low thermal expansion by only Furthermore, when an epoxy resin is used, it is difficult to obtain a resin cured product having a good dielectric constant and dielectric loss tangent, and improvement of dielectric characteristics has been required as a material for high-speed communication.

  It is known that a modified maleimide resin obtained by introducing a siloxane skeleton into a bismaleimide resin has excellent heat resistance and low thermal expansion without excessively increasing the content of the inorganic filler (see, for example, Patent Document 2) ). In addition, although the modified maleimide resin has a low relative dielectric constant and a low dielectric loss tangent as compared with the epoxy resin, it has not been able to achieve the relative dielectric constant and the dielectric loss tangent which are required in recent years.

For the purpose of improving dielectric properties, laminates to which a polybutadiene resin is added as a thermoplastic elastomer have been studied. The laminate has excellent dielectric properties, but the prepreg has tackiness, low compatibility with other thermosetting resins, high shrinkage rate during curing, copper foil, etc. There is a drawback such as poor adhesion to metal foils.
As a method of improving them, a method using butadiene-vinyl aromatic copolymer has been proposed (see, for example, Patent Document 3), but in order to obtain sufficient compatibility with other thermosetting resins, vinyl is used. 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.

  Further, in recent years, in the package substrate for a semiconductor, the difference in the thermal expansion coefficient between the chip and the substrate, and the warpage caused by the cure shrinkage of the substrate are considered as problems. As a method of improving the warpage, a method of reducing the thermal expansion coefficient of the substrate and reducing the cure shrinkage of the resin has been studied. As an approach example, 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 cure shrinkage rate of the resin. Here, when a hydrogenated styrenic elastomer is used as the thermoplastic elastomer, it shows a low dielectric constant and a low dielectric loss tangent since the polarity of the skeleton is very small. Therefore, by using the modified maleimide resin and the hydrogenated styrenic elastomer in combination, it is possible to achieve both low thermal expansion and excellent dielectric characteristics (low dielectric constant and low dielectric loss tangent).

  Furthermore, in laminates for printed wiring boards, it is required to be environmentally friendly and halogen-free and have flame retardancy. However, although the flame retardancy can be secured by adding a phosphorus-based or inorganic flame retardant as a flame retardant, when the type and amount of the flame retardant are not properly blended, the heat resistance decreases and the dielectric characteristics deteriorate. Will occur. For example, since a phosphorus flame retardant does not contribute to hardening and works as a plasticizer, it causes deterioration in heat resistance due to insufficient hardening. In addition, inorganic flame retardants increase the water absorption rate of the resin composition and cause deterioration of dielectric properties.

JP-A-5-148343 International Publication No. 2012-099133 Japanese Patent Application Laid-Open No. 61-233060 JP, 2014-24926, A

  A resin composition using the above modified maleimide resin and a thermoplastic elastomer in combination has no problem with general heat resistance, but heat resistance under severe conditions associated with recent high density mounting and multilayer construction of printed wiring boards That is, there was a problem that the heat resistance after water absorption was 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 of the present inventors.

  The object of the present invention is, in view of such a present situation, halogen-free and having flame retardancy while suppressing deterioration of heat resistance and deterioration of dielectric characteristics, and having excellent heat resistance, low thermal expansion, low dielectric constant and low dielectric loss tangent. It is an object of the present invention to provide a thermosetting resin composition, a prepreg using the same, a laminate, a printed wiring board and a module for high-speed communication.

The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, a modified maleimide resin having a specific structure, a thermoplastic elastomer, and a copolymer resin using an aromatic vinyl compound and a carboxylic anhydride as raw material monomers The inventors have found that the above object can be achieved by using the present invention, and have completed the present invention. Furthermore, by selecting the phosphorus-based flame retardant as the flame retardant, it was possible to impart sufficient flame retardancy without deteriorating the characteristics.
That is, the present invention provides the following thermosetting resin composition, a prepreg, a laminate, a printed wiring board, and a module for high-speed communication.
[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 A phosphorus-based flame retardant as a flame retardant (D), a copolymer resin containing a reactant, (B) a thermoplastic elastomer, (C) a structural unit derived from an aromatic vinyl compound, and a structural unit derived from a carboxylic acid anhydride Thermosetting resin composition containing a flame retardant.
[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 as described in said [1] which is a structural unit derived from a maleic anhydride represented by these.

（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), R ^C1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ^C2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms Or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and x represents an integer of 0 to 3.)

[3] As the component (C), R ^C1 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 compound [1] containing the copolymer resin whose content ratio [(C-1) / (C-2)] (molar ratio) with the structural unit represented by the formula (C-2) is 5 to 10, Or the thermosetting resin composition as described in [2].
[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 object.
[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 an end.
[6] The thermoplastic elastomer of the component (B) is a hydrogenated styrenic thermoplastic elastomer, and the content of structural units derived from styrene in the hydrogenated styrenic thermoplastic elastomer is 20 to 60% by mass. The thermosetting resin composition according to any one of the above-mentioned [1] to [5].
[7] When the blending amount of the phosphorus-based flame retardant of the component (D) is 100 parts by mass of the total mass of the components (A), (B), and (C), the content of phosphorus atoms is 1 The thermosetting resin composition according to any one of the above [1] to [6], which is from 0 to 4.0 parts by mass.
[8] The thermosetting resin composition according to any one of the above [1] to [7], further comprising (E) a curing accelerator.
[9] The thermosetting resin composition according to any one of the above [1] to [8], further comprising (F) an inorganic filler.
[10] A prepreg formed by impregnating a fiber base material with the thermosetting resin composition according to any one of the above [1] to [9].
[11] A laminate obtained by laminating and forming the prepreg according to [10].
[12] A printed wiring board manufactured using the prepreg according to the above [10] or the laminated board according to the above [11].
[13] A high-speed communication compatible module manufactured using the printed wiring board according to the above [12].

  According to the present invention, a halogen-free, thermosetting resin having excellent flame resistance, low thermal expansion, low dielectric constant and low dielectric loss tangent while having flame retardancy while suppressing deterioration of heat resistance and deterioration of dielectric characteristics. It is possible to provide a resin composition, a prepreg using the same, a laminate, a printed wiring board, and a module for high-speed communication.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention has (A) 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. Addition 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 comprising a copolymer resin containing a structural unit derived from (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 comprises 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. 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. No particular limitation is imposed on the structure, 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), X ^A1 is a group represented by the following general formula (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 general formula (a1-2), R ^A1 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. P 1 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), each R ^A2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^A2 represents an alkylene group having 1 to 5 carbon atoms, and 2 to 5 carbon atoms. 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 each independently an 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 ′), each R ^A3 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^A3 represents an alkylene group having 1 to 5 carbon atoms, 2 to 2 carbon atoms And an alkylidene group, an ether group, a carbonoxy group, a keto group or a single bond, each of 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 general formula (a1-5), each R ^A4 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U 1 is an integer of 1 to 8)

As an aliphatic hydrocarbon group which R ^A1 represents in said general formula (a1-2), a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -C1-C5 alkyl groups, such as a pentyl group, etc. are mentioned.

As a C1-C5 aliphatic hydrocarbon group which R < ^A2 > represents in said general formula (a1-3), the same thing as the case of R ^<A1> is mentioned.
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
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.

As a C1-C5 aliphatic hydrocarbon group which R < ^A3 > represents in said general formula (a1-3 '), the same thing as the case of R ^<A2> is mentioned.
Examples of the alkylene group of 1 to 5 carbon atoms and the alkylidene group of 2 to 5 carbon atoms represented by X ^A3 include the same as the alkylene group of 1 to 5 carbon atoms and X ² to 5 carbon alkylidene groups represented by X ^A2 Be

In the general formula ^(a1-5), examples of the aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R A4} represents may be the same as those in the case of the ^{R A1} in general formula (a1-2).

As the component (a1), N, N'-ethylenebismaleimide, N, N'-hexamethylenebismaleimide, 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- (4-methylphenylene)) bismaleimide Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, Bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-biphenyl (Maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-) Maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-) Maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4 -(3-Maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) pheny ] Propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 4,4-bis (3-maleimidophenoxy) Biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, bis [4- (3- (3-maleimidophenoxy) phenyl] ketone Maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether and the like can be mentioned.
The component (a1) may be used alone or as a mixture of two or more.
Among these, maleimide compounds having a phenoxy group are preferable from the viewpoint of excellent solubility in a solvent, and from the viewpoint of high conversion and higher heat resistance, bis (4-maleimidophenyl) methane, 2, 2- Bis [4- (4-maleimidophenoxy) phenyl] propane is preferred.

(Amine compound having at least two primary amino groups in one molecule (a2))
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), Y ^A1 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 general formula (a2-2), each R ^A5 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. 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), each R ^A6 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Y ^A2 is an alkylene group having 1 to 5 carbon atoms, 2 to 5 carbon atoms Or an alkylidene group, an ether group, a carbonoxy group, a keto group, a single bond or a group represented by the following general formula (a2-3 ′): each independently represents an 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 ′), each R ^A7 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Y ^A3 is an alkylene group having 1 to 5 carbon atoms, 2 to 2 carbon atoms An alkylidene group, an ether group carboxy group, a keto group or a single bond, each independently s1 is an 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), each R ^A8 independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group. Each R ^A9 independently represents a divalent organic group. (M2 is an integer of 1 to 100)

In the general formula (a2-2), as the aliphatic hydrocarbon group represented by R ^A5 , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, n -C1-C5 alkyl groups, such as a pentyl group, etc. are mentioned.

In the general formula ^(a2-3), examples of the aliphatic hydrocarbon group having 1 to 5 ^carbon atoms ^{R A6 represents,} include the same ones as for ^{R A5.}
As a C1-C5 alkylene group which Y ^A2 represents, a methylene group, 1,2-dimethylene group, a 1, 3- trimethylene group, a 1, 4- tetramethylene group, a 1, 5- penta methylene group etc. are mentioned. Be
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.

In the general formula (a2-3 ^'), the aliphatic hydrocarbon group of 1 to 5 carbon atoms ^{which R A7 represents,} include the same ones as for ^{R A6.}
Examples of the alkylene group of 1 to 5 carbon atoms and the alkylidene group of 2 to 5 carbon atoms represented by Y ^A3 include the same as the alkylene group of 1 to 5 carbon atoms represented by Y ^A2 and the alkylidene group of 2 to 5 carbon atoms. Be

As a C1-C5 alkyl group which R < ^A8 > represents in said general formula (a2-4), a C1-C3 alkyl group is more preferable. ^Examples of the alkyl group represented by R ^A8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. Groups are preferred.
An alkyl group, an alkenyl group, an alkynyl group etc. are mentioned as a substituent in the substituted phenyl group which ^RA8 represents, Among these, an alkyl group is preferable. Examples of the alkyl group include the same as the alkyl group represented by R ^A8 .
Examples of the divalent organic group represented by R ^A9 include an alkylene group, an alkylidene group, an alkenylene group, an alkynylene group, an arylene group, -O-, and 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. As an arylene group, a phenylene group, a naphthylene group, etc. are mentioned.

As the component (a2), modified siloxane having an amino group at the end, diaminobenzidine, diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether, 3,3'-dimethoxy-4,4 3'-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 A '-diamino-3,3'-biphenyl diol etc. are mentioned.
The component (a2) may be used alone or as a mixture 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 preferred.
In addition, from the viewpoint of low thermal expansion, modified siloxanes having an amino group at the end are preferable. A commercial item may be used for the modified siloxane which has an amino group at the terminal, As a commercial item, "X-22-161A" (functional equivalent 800 g / mol) which has an amino group at both ends, "X- 22-161 B "(functional group equivalent 1,500 g / mol) (above, Shin-Etsu Chemical Co., Ltd. made)," BY16-853 U "(functional group equivalent 460 g / mol) (above, Toray Dow Corning Co., Ltd.), Examples thereof include “XF42-C5379” (functional group equivalent weight 750 g / mol) (above, Momentive Performance Materials Japan GK Co., Ltd.) and the like.

Further, the component (a2) contains a modified siloxane having an amino group at an end and an amine compound other than a modified siloxane having an amino group at an end, from the viewpoint of achieving both low thermal expansion, high elasticity and high heat resistance. It is preferable to use a modified siloxane having an amino group at the terminal, and 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 end and an amine compound other than a modified siloxane having an amino group at the end are used in combination as component (a2), the mass ratio [modified siloxane having an amino group at the end / terminal 3/97 to 90/10 is preferable, 10/90 to 80/20 is more preferable, and 20/80 to 70/30 is more preferable.

  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).

（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 ^{(A1), 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 the addition reaction of the components (a1) and (a2).
The compounding amount of the component (a1) and the component (a2) in the addition reaction is the equivalent of the maleimide group of the component (a1) from the viewpoint of gelation prevention and heat resistance, that of the primary amino group of the component (a2) 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 preferably 2 to 15 Is preferably, and more preferably 3 to 10.

  The reaction temperature in the addition reaction is preferably 70 to 150 ° C., and 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 performed 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 acetic acid ethyl ester; aromatic solvents such as toluene; Nitrogen atom containing solvents, such as acetamide and N-methyl pyrrolidone, etc. are mentioned. The organic solvents 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 little residual solvent. Is preferred.
The amount of the organic solvent used is preferably 25 to 1,000 parts by mass and 50 to 500 parts by mass with respect to 100 parts by mass in total of the components (a1) and (a2) from the viewpoint of solubility and reaction rate More preferable.

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, 60-90 mass parts are more preferable, and 70-87 mass parts are further more preferable.
In the present specification, “solid content” refers to non-volatile components excluding volatile substances such as solvents, and refers to components remaining without volatilization when the resin composition is dried, at room temperature. It also includes liquid, starch syrup and wax. Here, room temperature refers to 25 ° C. in this specification.
Moreover, a "resin component" is a component used for manufacture of resin or resin except the inorganic filler mentioned later, and, specifically, (A) denaturation maleimide resin, (B) thermoplastic elastomer, ( C) Copolymer resin etc. correspond to a resin component.

In addition, 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 elastic modulus 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 50 to 85 parts by mass The amount which becomes is more preferable.
In addition, 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 adhesion. The amount of component (a2) of the raw material converted from the amount of 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 40 to 40 parts by mass is more preferable.

<(B) Thermoplastic Elastomer>
There is no restriction | limiting in particular as a thermoplastic elastomer (Hereafter, it is also mentioned "the (B) component."), It can select suitably from conventionally well-known thermoplastic elastomers. However, in the present invention, the thermoplastic elastomer (B) is defined as one not including a copolymer resin containing a structural unit derived from an aromatic vinyl compound (C) described later and a structural unit derived from a carboxylic acid anhydride. Ru.
Examples of the thermoplastic elastomer (B) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers, derivatives of these, and the like. The component (B) may be used alone or as a mixture of two or more.

Moreover, as (B) thermoplastic elastomer, what has a reactive functional group in a molecular terminal or a molecular chain can be used. As a reactive functional group, an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amido group, an isocyanate group, an acryl group, a methacryl group, a vinyl group etc. are mentioned. By having these reactive functional groups in the molecular terminal or in the molecular chain, the compatibility can be improved and the heat resistance of the substrate can be improved.
Among these reactive functional groups, from the viewpoint of adhesion to the metal foil, it is more preferable to have a carboxy group, an amino group and a hydroxyl group 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 characteristics, two of these copolymers are preferred. A hydrogenated styrene-based thermoplastic elastomer such as a hydrogenated styrene-butadiene copolymer resin, a hydrogenated styrene-isoprene copolymer resin, and the like in which a heavy bond portion is hydrogenated is more preferable.
Furthermore, the content of the structural unit derived from styrene (hereinafter, also referred to as “styrene content”) in the hydrogenated styrene-based thermoplastic elastomer is preferably 20 to 60% by mass, and 25 to 55% by mass. Is more preferred. (B) Moisture absorption 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 a thermoplastic elastomer In addition to the excellent heat resistance, the appearance of the coated prepreg is excellent, and a resin with a small amount of powder fallout of the prepreg can be achieved. If the amount of styrene is 60% by mass or less, in addition to good base material properties (thermal expansion coefficient, dielectric properties, heat resistance), cracking tends to be less likely to occur in the appearance of the coated prepreg. This is considered to be derived from the suppression of the stacking aggregation of styrene and the excellent flexibility of the resin. When the amount of styrene is 20% by mass or more, in addition to the base material properties (thermal expansion coefficient, dielectric properties, heat resistance) being good, compatibility between (A) modified maleimide resin and (B) thermoplastic elastomer It is excellent, has a small amount of resin powder removal, and tends to be excellent in handleability. This is because the maleimide group of the (A) modified maleimide resin has a structure similar to that of styrene as compared with butadiene, isoprene and the like, so that the amount of styrene of the thermoplastic elastomer (B) is 20% by mass or more. It is considered that (A) is derived from the excellent compatibility between the modified maleimide resin and the styrenic skeleton.
As the styrene-based elastomer, commercially available products may be used, and as commercially available products, “Tuftec (registered trademark) H1051”, “Tuftec H1053”, “Tuftec M1911”, “Tuftec M1913” (all manufactured by Asahi Kasei Chemicals Corporation) And “Septon (registered trademark) 2002”, “Septon HG 252” (manufactured by Kuraray Co., Ltd.), and the like.

  The content of the thermoplastic elastomer (B) in the thermosetting resin composition is preferably 4 to 20 parts by mass, relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and 6 to 15 The parts by mass are more preferred. When the content of the thermoplastic elastomer (B) is 4 parts by mass or more, the effect of lowering the dielectric constant is sufficiently obtained, and when the content is 20 parts by mass or less, (B) the thermoplastic elastomer compatibilizes, the resin is contained in the resin It is well dispersed and excellent in heat resistance and peel strength.

<(C) copolymer resin>
The copolymer resin (C) is a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a carboxylic acid anhydride.
In the thermosetting resin composition of the present invention, the effect of being excellent in heat resistance particularly after water absorption is obtained by containing the (C) copolymer resin. Although the reason which produces such an effect is not certain, it is considered as follows.
Conventionally, a method of adding a thermoplastic elastomer to a modified maleimide resin has been used for the purpose of improving dielectric properties, but the thermoplastic elastomer is compatible with each other because the structure of the modified maleimide resin and the skeleton are largely different. It was a difficult condition. Therefore, when the modified maleimide resin and the thermoplastic elastomer are simply blended, there is a problem in the heat resistance under severe conditions (for example, after the moisture absorption treatment by a pressure cooker) required in recent years.
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 is excellent in compatibility with a thermoplastic elastomer (in particular, an elastomer containing styrene), and the structural unit derived from carboxylic acid anhydride is excellent in compatibility with a modified maleimide resin. Accordingly, 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 used. It is considered that the compatibility is improved and the heat resistance is 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 a structural unit derived from the aromatic vinyl compound of (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 structural units derived from maleic anhydride, structural units derived from phthalic anhydride, structural units derived from succinic anhydride, etc. 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 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), R ^C1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ^C2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms Or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and x represents an integer of 0 to 3.)

As a ^C1- C5 aliphatic hydrocarbon group which R ^{< C1>} and R ^<C2> show, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, an isobutyl group, t-butyl group, n- A pentyl group etc. are mentioned. 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.
The aromatic hydrocarbon group having 6 to 20 carbon atoms R ^C2 represents a phenyl group, a naphthyl group, an anthryl group, etc. biphenylyl group.
In the structural unit represented by the general formula (C-1), a structural unit represented by the following formula (C-1 ′) in which R ^C1 is a hydrogen atom and x is 0 is preferable.

(C) In the copolymer resin, the content ratio [(C-1) / (C) of the structural unit represented by the general formula (C-1) and the structural unit represented by the general formula (C-2) 2-12 are preferable and 2-12 are preferable, and 5-10 are more preferable. When the content ratio is 2 or more, the effect of improving the dielectric properties and heat resistance tends to be sufficient, and when it is 12 or less, the compatibility tends to be good. Furthermore, in addition to having a favorable base-material characteristic as [(C-1) / (C-2)] (molar ratio) is 5-10, it is excellent in compatibility with the (B) thermoplastic elastomer. Since the content of the structural unit derived from styrene is in a preferable range, the compatibility between the (A) modified maleimide resin and the (B) 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 Formula (C-1) and the structural unit represented by Formula (C-2) in the copolymer resin (C) is preferably 50% by mass or more. 70 mass% or more is more preferable, 90 mass% or more is further preferable, and substantially 100 mass% is especially preferable.

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

  A commercial item can also be used as (C) copolymer resin, As a commercial item, "SMA (registered trademark) EF30" (styrene / maleic anhydride = 3, Mw = 9,500), "SMAEF 40" ( Styrene / maleic anhydride = 4, Mw = 11,000), “SMAEF 60” (styrene / maleic anhydride = 6, Mw = 11,500), “SMAEF 80” (styrene / maleic anhydride = 8, Mw = 14, 400) (manufactured by Sartmar Inc.) and the like. Among these, "SMAEF60" and "SMA-EF80" are preferable.

  The content of (C) copolymer resin in the thermosetting resin composition is preferably 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, and 3 to 15 A mass part is more preferable, and 4-13 mass parts is further more preferable. When the content of the copolymer resin (C) 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 copolymer resin (C) is excellent. Excellent heat resistance and peel strength.

<(D) phosphorus flame retardant>
As a flame retardant which provides a flame retardance to the resin composition used for a laminated board, a halogen type flame retardant, a phosphorus type flame retardant, an inorganic type flame retardant etc. are mentioned. In recent years, it is required not to use a halogen-based flame retardant because of the demand for environmental protection. Examples of inorganic flame retardants include antimony trioxide and aluminum hydroxide, but these materials increase the water absorption of the resin composition and deteriorate the dielectric properties. Therefore, application to a resin composition having excellent dielectric properties required in recent years is difficult.
The phosphorus-based flame retardant is free from halogen and can impart flame retardancy without deteriorating the dielectric characteristics.

  Examples of organic phosphorus-based flame retardants include aromatic phosphoric acid esters, mono-substituted phosphonic acid diesters, di-substituted phosphinic acid esters, metal salts of di-substituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organophosphorus compounds, A phosphorus containing phenol resin etc. are mentioned. Among these, aromatic phosphoric acid ester compounds, metal salts of disubstituted phosphinic acids, and cyclic organophosphorus compounds are preferable. Here, the metal salt is preferably any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt, and is preferably aluminum salt. Further, among the organic phosphorus-based flame retardants, aromatic phosphate esters are more preferable.

Examples of the aromatic phosphate include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylene bis (di-2, 6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1, 3- phenylene bis (diphenyl phosphate), etc. are mentioned.
Examples of mono-substituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate and the like.
Examples of the disubstituted phosphinate ester include phenyl diphenylphosphinate, methyl diphenylphosphinate and the like.
Examples of the metal salt of disubstituted phosphinic acid include metal salts of dialkylphosphinic acid, metal salts of diallylphosphinic acid, metal salts of divinylphosphinic acid, metal salts of diarylphosphinic acid, and the like. These metal salts are preferably any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts and zinc salts as described above.

Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate and the like.
As a cyclic organophosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide and the like can be mentioned.
Among these, at least one selected from aromatic phosphate esters, metal salts of disubstituted phosphinic acids and cyclic organophosphorus compounds is preferable, and metal salts of aromatic phosphate esters and disubstituted phosphinic acids are more preferable. preferable.

  The aromatic phosphate is preferably an aromatic phosphate represented by the following general formula (D-1) or (D-2), and the metal salt of the disubstituted phosphinic acid is It is preferable that it is a metal salt of disubstituted phosphinic acid represented by general formula (D-3).

(In the general formulas (D-1) to (D-3), R ^{E1 to} R ^E5 are each independently an aliphatic hydrocarbon group of 1 to 5 carbon atoms or a hydrogen atom. ^E and f are each independently) And g, h and i each independently represent an integer of 0 to 4. R ^E6 and R ^E7 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or 6 carbon atoms. And an aromatic hydrocarbon group of from 14 to 14. M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom or a zinc atom.)
As the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^{E1 to} R ^E5 and the hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, as in the above general formulas An isobutyl group, t-butyl group, n-pentyl group etc. are mentioned. e and f are preferably an integer of 0 to 2, and are preferably 2. g, h and i are preferably an integer of 0 to 2, preferably 0 or 1, and preferably 0.
As a C1-C5 aliphatic hydrocarbon group which R ^E6 and R ^E7 represent, the same thing as said R ^{E1 to} R ^E5 is mentioned. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and is preferably an ethyl group.
As a C6-C14 aromatic hydrocarbon group which R ^{< E6>} and R ^<E7 > represent, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group etc. are mentioned, for example. 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 varies in the range of 1 to 4 corresponding to the type of M. As M, an aluminum atom is preferable. When M is an aluminum atom, j is 3.

The above-mentioned phosphorus flame retardants may be used alone or in combination of two or more.
About the compounding quantity of the phosphorus base flame retardant of (D) component, when the total mass of (A) component, (B) component, and (C) component is 100 mass parts, content of a phosphorus atom is 1.0 It is preferably -4.0 parts by mass, and more preferably 1.2 parts by mass to 3.5 parts by mass. Sufficient flame retardance can not be provided as content of a phosphorus atom is less than 1.0 mass part. When the content of phosphorus atoms exceeds 4.0 parts by mass, the phosphorus-based flame retardant acts as a plasticizer, resulting in the deterioration of heat resistance.

<(E) Hardening accelerator>
The thermosetting resin composition of the present invention may further contain (E) a curing accelerator from the viewpoint of promoting the curing reaction.
(E) As curing accelerators, organophosphorus compounds such as triphenylphosphine; imidazoles and derivatives thereof; nitrogen-containing compounds such as secondary amines, tertiary amines, quaternary ammonium salts; dicumyl Peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α′- Organic peroxides such as bis (t-butylperoxy) diisopropylbenzene; organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate and the like. The curing accelerator (E) 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 0.1 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) As the inorganic filler, silica, alumina, titanium oxide, mica, barium titanate, strontium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, calcium carbonate, silicon nitride, boron nitride, talc, silicon carbide And quartz powder, short glass fiber, fine glass powder, hollow glass and the like. As glass, E glass, T glass, D glass etc. are mentioned preferably.
The inorganic filler (F) may be used alone or as a mixture of two or more.
Among these, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. Examples of the silica include precipitated silica manufactured by a wet method and having a high water content, and dry silica manufactured by a dry method and hardly containing bound water and the like. The dry silica further includes a difference in production method. , Crushed silica, fumed silica, fused spherical silica and the like. Among these, fused spherical silica is preferred from the viewpoints of low thermal expansion and fluidity when filled in a resin.

0.1-10 micrometers is preferable and, as for the average particle diameter of an inorganic filler, 0.3-8 micrometers is more preferable. When the average particle diameter is 0.1 μm or more, the flowability at the time of high loading into the resin can be kept good, and when it is 10 μm or less, the mixing probability of coarse particles is reduced, and defects due to coarse particles The occurrence can be suppressed. Here, the average particle diameter is the particle diameter of a point corresponding to 50% volume when the cumulative frequency distribution curve by particle diameter is determined with the total volume of particles as 100%, and the laser diffraction scattering method is used. It can measure with the particle size distribution measuring device etc.
(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 in which surface treatment is carried out dry or wet with respect to the (F) inorganic filler before blending, and the surface untreated (F) inorganic filler may be other It may be a so-called integral blend processing system in which a silane coupling agent is added to the composition after being formulated into a composition.
As a coupling agent, a silane coupling agent, a titanate coupling agent, a silicone oligomer, etc. are mentioned.

  When the thermosetting resin composition of the present invention contains (F) an inorganic filler, the content thereof is 10 to 300 mass relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. A part is preferable and 50-250 mass parts is more preferable. When the content of the (F) inorganic filler is within the above range, the moldability and the low thermal expansion property become good.

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

<Other ingredients>
The (A) modified maleimide resin of the present invention is a thermosetting resin and has good thermosetting properties alone, but if necessary, it can be used in combination with other thermosetting resins to improve adhesion, 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, triazine resin, etc. These may be used alone or in combination of two or more. Among these, cyanate resins and benzoxazine resins are preferable from the viewpoint of moldability and electrical insulation.
Moreover, although it can have favorable adhesiveness by containing an epoxy resin, it is preferable that the content is 2 mass% or less in solid content of a thermosetting resin composition. By setting the content of the epoxy resin to 2% by mass or less, the dielectric characteristics and storage stability can be made excellent.

The thermosetting resin composition of the present invention may optionally contain known organic fillers, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, adhesion improvers, and the like.
Examples of the organic filler include resin fillers made of polyethylene, polypropylene resin and the like, and resin fillers having a core-shell structure.
As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned.
Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, and the like.
As a photoinitiator, photoinitiators, such as benzophenones, benzyl ketals, and thioxanthone type | system | group, are mentioned.
Examples of the fluorescent whitening agent include fluorescent whitening agents of stilbene derivatives.
Examples of the adhesion improver include urea compounds such as ureasilane, the above-mentioned coupling agent and the like.

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

Organic solvents used for the varnish 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 acetic acid ethyl ester; and aroma such as toluene and xylene Group solvents; solvents containing nitrogen atom such as dimethyl acetamide, N-methyl pyrrolidone and the like; 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.
40-90 mass% is preferable, and, as for solid content concentration of a varnish, 50-80 mass% is more preferable. 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 resin composition attached can be obtained.

[Prepreg]
The prepreg of the present invention is obtained by impregnating the thermosetting resin composition of the present invention into a fiber substrate.
The prepreg of the present invention can be manufactured by impregnating a fiber base material with the thermosetting resin composition of the present invention and semi-curing (B-staging) by heating or the like.
As a fiber base material, the well-known thing used for the laminated board for various electric insulation materials can be used. Examples of the material include inorganic fibers such as E glass, S glass, low dielectric glass, Q glass, etc .; organic fibers such as low dielectric glass polyimide, polyester, tetrafluoroethylene, etc., and mixtures thereof.

  These fiber substrates have shapes such as woven fabrics, non-woven fabrics, rovincks, chopped strand mats, surfacing mats, etc. The material and shape are selected according to the intended use of the molded object, performance, etc. A single material or two or more types of materials and shapes can be combined. The thickness of the fiber substrate can be, for example, about 0.03 to 0.5 mm. As these fiber substrates, those which have been surface-treated with a silane coupling agent or the like, or those which have been subjected to an opening treatment mechanically are preferable in terms of heat resistance, moisture resistance, processability and the like.

  The prepreg of the present invention is, for example, a fiber base such that the adhesion amount of the thermosetting resin composition to the fiber base (content of the thermosetting resin composition in the prepreg) is 20 to 90 mass%. After being impregnated, it is usually dried by heating at a temperature of 100 to 200.degree. C. for 1 to 30 minutes, and can be obtained by semi-curing (B-staging).

[Laminated board]
The laminate of the present invention is obtained by laminating and molding the prepreg of the present invention.
The laminate of the present invention can be produced, for example, by laminating and forming the prepreg of the present invention in a configuration in which 1 to 20 sheets of the laminate of the present invention are stacked and metal foils such as copper and aluminum are disposed on one side or both sides. The metal foil is not particularly limited as long as it is used for an electrical insulating material application.
As the molding conditions for producing the laminated plate, for example, the method of laminated plate for electric insulating material and multi-layer plate can be applied, using multistage press, multistage vacuum press, continuous molding, autoclave molding machine etc. C., pressure 0.2 to 10 MPa, heating time 0.1 to 5 hours. Moreover, the prepreg of this invention and the wiring board for inner layers can be combined, and it can laminate-mold, and can also manufacture a laminated board.

[Printed wiring board]
The printed wiring board of the present invention is manufactured using the prepreg or laminate of the present invention.
The printed wiring board of the present invention can be produced, for example, by forming a circuit on the surface of the laminate of the present invention. In addition, the conductor layer of the laminate of the present invention is subjected to wiring processing by a common etching method, and a plurality of laminates subjected to wiring processing via the prepreg of the present invention are laminated in multiple layers and collectively subjected to multilayering by heat pressing. You can also. Thereafter, a multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling or laser processing and formation of interlayer wiring by plating or conductive paste.

[High-speed communication support module]
The high-speed communication support module of the present invention is a high-speed communication support module manufactured using the printed wiring board of the present invention.
The high-speed communication support module of the present invention is, for example, a communication module or the like obtained by mounting a semiconductor chip or the like on the printed wiring board of the present invention, and in particular, uses signals in high frequency band such as wireless communication devices and network infrastructure devices. It is suitable for applications where the amount of information communication and the speed are large.

The present invention will now be described in more detail by the following examples, which should not be construed as limiting the invention.
In addition, the following evaluation was performed about the thermosetting resin composition and copper clad laminated board which were obtained in each case.

(1) Glass transition temperature (Tg)
An evaluation substrate of 5 mm square was prepared by immersing the copper-clad laminate in a copper etching solution to remove the copper foil, and heat was applied by a compression method using a TMA test apparatus (trade name: Q400, manufactured by TA Instruments). Mechanical analysis was performed. After the evaluation substrate was mounted on the apparatus in the X direction, measurement was performed twice continuously under the measurement conditions of a load of 5 g and a temperature rising rate of 10 ° C./min. The point indicated by the intersection of different tangents of the thermal expansion curve in the second measurement was determined, and this was taken as the glass transition temperature (Tg).

(2) Thermal Expansion Coefficient A 5 mm square evaluation substrate from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus (trade name: Q400, manufactured by TA Instruments) was used. The thermomechanical analysis was performed by the compression method. After the evaluation substrate was mounted on the apparatus in the X direction, measurement was performed twice continuously under the measurement conditions of a load of 5 g and a temperature rising 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 coefficient of thermal expansion.

(3) Dielectric characteristics (relative dielectric constant and dielectric loss tangent)
A copper-clad laminate is immersed in a copper etching solution to prepare a 100mm x 2mm (longitudinal x horizontal) evaluation substrate from which the copper foil has been removed, and a cavity resonator device (manufactured by Kanto Electronics Application Development Co., Ltd.) is used. The relative permittivity and the dielectric loss tangent at a frequency of 10 GHz were measured.

(4) Solder heat resistance with copper An evaluation substrate is prepared by cutting a copper-clad laminate to a size of 25 mm square, and the appearance is observed while the evaluation substrate floats in a solder bath at a temperature of 288 ° C. for up to 60 minutes. The time until blistering occurred was measured. The evaluation results are shown in Table 1 as ">60" in which swelling was not confirmed when floated for 60 minutes.

(5) Soldering heat resistance with copper and copper absorption A copper-clad laminate is cut into a size of 50 mm square, leaving half copper on one surface only and immersing the other surface in a copper etching solution to remove whole copper As a result, a 50 mm square half copper evaluation board was produced. Evaluation board with a half copper after treatment for 5 hours in equipment for pressure cooker test (PCT) (manufactured by Hirayama Seisakusho Co., Ltd. (conditions: 121 ° C, 2.2 atm), each for 20 seconds in a solder bath at 288 ° C After immersion, the heat resistance was evaluated by observing the appearance visually. The evaluation results are shown in Table 1 as "OK" for those in which blister was not confirmed and "Bully" for those in which blister was confirmed.

(6) Flame retardancy A 125 mm long, 12.5 mm wide evaluation substrate was prepared by removing the copper foil by immersing the copper-clad laminate in a copper etching solution, according to the UL-94 vertical test method. It was measured.

Production Example 1: [Production of modified maleimide resin (A-1)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A ) 25.9 g of 15.9 g, 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) A-A), and bis (4-maleimide) 280.5 g of phenyl) methane (manufactured by Kei I Kasei Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether are added and reacted for 5 hours while refluxing at 126 ° C. to obtain a modified maleimide resin (A A solution of -1) was obtained.

Production Example 2: [Production of Modified Maleimide Resin (A-2)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B ) 14.4 g, 56.9 g of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP), and bis (4-maleimidophenyl) Add 253.7 g of methane (Ki Eye Chemical Co., Ltd., trade name: BMI) and 200.0 g of propylene glycol monomethyl ether, and react for 5 hours while refluxing at 126 ° C. to react with modified maleimide resin (A-2) ) Solution was obtained.

Production Example 3: [Production of Modified Maleimide Resin (A-3)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B ) 25.6 g of 15.6 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Co., Ltd., trade name: KAYAHARDA-A), 2,2-bis [4- (4) -Maleimido phenoxy) phenyl] propane (Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) and propylene glycol monomethyl ether: 200.0 g are added and reacted at 120 ° C. for 4 hours for modified maleimide The solution of resin (A-3) was obtained.

Production Example 4: [Production of modified maleimide resin (A-4)]
A 2-liter reaction vessel capable of heating and cooling, equipped with a thermometer, a stirrer and a water content meter with a reflux condenser, both-end diamine modified siloxane (Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A ) 16.6 g, 25.5 g of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (Wakayama Seika Kogyo Co., Ltd., trade name: BAPP), 2,2-bis [4 -(4-Maleimido phenoxy) phenyl] propane (Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) 292.6 g and propylene glycol monomethyl ether 200.0 g are added, and refluxing 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 is blended and mixed according to the blending ratio shown in Table 1 (the numerical values in the table are parts by mass of solid content, and in the case of a solution (excluding organic solvent) or dispersion, it is solid equivalent). Methyl ethyl ketone and toluene were used as the solvent to prepare a varnish having a solid content concentration of 65% by mass.
Next, this varnish is impregnated and coated on an E glass cloth (manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and dried by heating at 160 ° C. for 5 minutes. The content of the thermosetting resin composition is 46% by mass Was obtained.
Four pieces of this prepreg were stacked, 12 μm thick electrodeposited copper foils were vertically disposed, pressed at a pressure of 2.5 MPa and a temperature of 200 ° C. for 90 minutes to obtain a copper-clad laminate. The evaluation results of the obtained copper clad laminate are shown in Table 1.

  It shows below about each component used for combination.

[(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]
Tuff Tech H1051: Hydrogenated styrene-butadiene copolymer resin (styrene content: 42% by mass) (manufactured by Asahi Kasei Chemicals Corporation)
Tuftec H1053: Hydrogenated styrene-butadiene copolymer resin (styrene content: 29% by mass) (manufactured by Asahi Kasei Chemicals Corporation)
Tuftec M1913: carboxylic acid modified hydrogenated styrene-butadiene copolymer resin (styrene content: 30% by mass) (manufactured by Asahi Kasei Chemicals Corporation)
SEPTON 2002: Hydrogenated styrene-isoprene copolymer resin (styrene content: 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) (Sartmar company)

[(D) phosphorus flame retardant]
· PX-200: aromatic phosphoric acid 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 Ltd.)
SPB-100: cyclophosphazene, 13 mass% of phosphorus content (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 (Sanko Co., Ltd., average particle diameter 1.5 μm)

[(E) curing accelerator]
TPP-MK: tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical 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 Kasei Kogyo Co., Ltd.)

[(F) Inorganic filler]
Spherical fused silica (Admatex Co., Ltd., average particle size: 0.5 μm)

As apparent from Table 1, the laminates obtained in Examples 1 to 8 have glass transition temperatures, thermal expansion coefficients, dielectric properties, solder heat resistance with copper, solder heat resistance with water absorption half copper, and flame resistance. Excellent for all.
On the other hand, Comparative Examples 1 to 5 are inferior in any one of the dielectric characteristics or the solder heat resistance with water absorption and copper and the flame resistance.

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

Claims (13)

(A) An addition 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) a thermoplastic elastomer,
(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 flame retardants as flame retardants,
A thermosetting resin composition containing 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), R ^C1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ^C2 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms Or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and x represents an integer of 0 to 3.) As the component (C), R ^C1 in the general formula (C-1) is a hydrogen atom, x is 0, and a structural unit represented by the general formula (C-1) and the general formula (C) The copolymer resin having a content ratio [(C-1) / (C-2)] (molar ratio) with the structural unit represented by -2) of 5 to 10 is contained. The thermosetting resin composition as described in-.   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 thermosetting The thermosetting resin composition according to any one of claims 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 functional resin composition.   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 an end.   The thermoplastic elastomer of the component (B) is a hydrogenated styrenic thermoplastic elastomer, and the content of structural units derived from styrene in the hydrogenated styrenic thermoplastic elastomer is 20 to 60% by mass. The thermosetting resin composition as described in any one of 1-5.   When the compounding quantity of the phosphorus base flame retardant of (D) component makes the total mass of (A) component, (B) component, and (C) component 100 mass parts, content of a phosphorus atom is 1.0- The thermosetting resin composition according to any one of claims 1 to 6, which is 4.0 parts by mass.   Furthermore, the thermosetting resin composition as described in any one of Claims 1-7 containing (E) a hardening accelerator.   Furthermore, the thermosetting resin composition as described in any one of Claims 1-8 containing the (F) inorganic filler.   The prepreg formed by impregnating the thermosetting resin composition as described in any one of Claims 1-9 to a fiber base material.   A laminate obtained by laminating and forming the prepreg according to claim 10.   The printed wiring board manufactured using the prepreg of Claim 10, or the laminated board of Claim 11.   A high-speed communication compatible module manufactured using the printed wiring board according to claim 12.