JP6988059B2 - Thermosetting resin composition, prepreg using it, laminated board and printed wiring board - Google Patents

Description

The present invention relates to a thermosetting resin composition, a prepreg using the same, a laminated board, and a printed wiring board.

With the recent trend toward miniaturization and higher performance of electronic devices, the wiring density of printed wiring boards has become more sophisticated and highly integrated, and along with this, laminated boards for printed wiring boards have become more popular. There is an increasing demand for improved reliability by improving heat resistance. In such applications, particularly semiconductor package substrate applications, it is required to have both excellent heat resistance and low thermal expansion.

As a laminated board for a printed wiring board, a prepreg containing a resin composition containing an epoxy resin as a main component and a glass cloth is generally cured and integrally molded.
Epoxy resin has an excellent balance of insulation, heat resistance, cost, etc., but further improvement is required to meet the demand for improved heat resistance due to the recent high-density mounting of printed wiring boards and high-multilayer configurations. Will be. Further, since the epoxy resin has a large coefficient of thermal expansion, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring and increasing the filling of an inorganic filler such as silica (see, for example, Patent 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, for the purpose of improving moisture resistance and adhesiveness, a thermosetting resin composition containing an epoxy resin, a phenol resin and a modified imide resin as main components has been studied (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 5-148343 Japanese Unexamined Patent Publication No. 6-263843

However, although the thermosetting resin composition of Patent Document 2 has improved moisture resistance and adhesiveness, the imide resin contains a hydroxyl group and an epoxy group in order to ensure solubility in a general-purpose solvent such as methyl ethyl ketone. Since it is modified with a molecular compound, there is a problem that the heat resistance of the obtained modified imide resin is significantly inferior to that of the polybismaleimide resin.
Furthermore, in recent years, especially in semiconductor package substrates, due to the difference in thermal expansion coefficient between the chip and the substrate, and the curing shrinkage and elastic modulus of the substrate at the time of component mounting and package assembly due to the miniaturization and thinning. Warpage has become a major issue. Therefore, a laminated board for a semiconductor package substrate is required to have good low thermal expansion, low cure shrinkage and elastic modulus.

An object of the present invention is to provide a thermosetting resin composition having excellent low thermal expansion while maintaining heat resistance, a prepreg using the same, a laminated board, and a printed wiring board. ..

As a result of diligent research to achieve the above object, the present inventors have found that the following invention can achieve the subject.
That is, the present invention provides the following [1] to [16].
[1] Contains (a) a polybutadiene compound, (b) an adduct of tertiary phosphine and quinones, and (c) a maleimide compound having at least two N-substituted maleimide groups in one molecule. Thermosetting resin composition.
[2] The thermosetting resin composition according to the above [1], further (d) containing an amine compound having at least two primary amino groups in one molecule.
[3] The thermosetting resin composition according to the above [1] or [2], which further contains (e) an amine compound having an acidic substituent.
[4] (a) Any of the above [1] to [3], wherein the content of the polybutadiene compound is 1 to 40 parts by mass with respect to 100 parts by mass of the solid content of the resin component of the thermosetting resin composition. The thermosetting resin composition described in Crab.
[5] The component (c) is any of the above [1] to [4], which is an (X) amino-modified resin having at least two N-substituted maleimide groups and an amino group in one molecule. The thermosetting resin composition according to the above.
[6] The thermosetting resin composition according to the above [5], wherein the component (X) has an acidic substituent.
[7] The component (X) has a structure derived from a maleimide compound having (c) at least two N-substituted maleimide groups in one molecule, and (d) at least two primary amino groups in one molecule. The thermosetting resin composition according to the above [5] or [6], which contains a structure derived from an amine compound having.
[8] The thermosetting resin composition according to any one of [5] to [7] above, wherein the component (X) has a structure derived from an amine compound having an acidic substituent (e).
[9] The thermosetting resin composition according to any one of the above [1] to [8], wherein the polybutadiene compound is liquid polybutadiene.
[10] (a) Any one of the above [1] to [9], wherein the polybutadiene compound is subjected to at least one modification selected from the group consisting of epoxy modification, maleic acid modification, maleic anhydride modification and hydroxyl group modification. The thermosetting resin composition according to.
[11] The thermosetting resin according to any one of the above [1] to [10], which further contains (f) at least one selected from the group consisting of an epoxy resin and a cyanate resin as the thermosetting resin. Composition.
[12] The thermosetting resin composition according to any one of the above [1] to [11], which further contains (g) an inorganic filler.
[13] A prepreg containing a thermosetting resin composition obtained by B-stage the thermosetting resin composition according to any one of the above [1] to [12].
[14] A laminated board containing an insulating layer formed by using the prepreg according to the above [13].
[15] The laminated board according to the above [14], comprising an insulating layer formed by using the prepreg according to the above [13] and a metal foil arranged on one side or both sides thereof.
[16] A printed wiring board obtained by circuit processing the metal foil of the laminated board according to the above [15].

According to the present invention, it is possible to provide a thermosetting resin composition having excellent low thermal expansion while maintaining heat resistance, and a prepreg, a laminated board and a printed wiring board using the same.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises (a) a polybutadiene compound (hereinafter, also referred to as “(a) component”) and (b) an adduct of tertiary phosphine and quinones (hereinafter, “(b)”. A thermosetting resin composition containing (c) a maleimide compound having at least two N-substituted maleimide groups in one molecule (hereinafter, also referred to as “component (c)”). It is a thing.

<(A) Polybutadiene compound>
The thermosetting resin composition of the present invention contains a polybutadiene compound as the component (a). The thermosetting resin composition of the present invention can reduce the coefficient of thermal expansion by containing (a) a polybutadiene compound. This is a resin composition containing a specific maleimide compound and an adduct of a tertiary phosphine and quinones, and by further blending (a) a polybutadiene compound, (a) the polybutadiene compound is added to the resin composition. It is considered that this is because the uniformly dispersed (a) polybutadiene compound can be uniformly dispersed therein, and the stress generated by the thermal expansion of the thermosetting resin composition can be relaxed.

(A) The polybutadiene compound is preferably liquid polybutadiene from the viewpoint of dispersibility and low thermal expansion of the obtained cured product. In addition, in this specification, "liquid" means the thing which shows fluidity in a normal state (25 degreeC, 1 atm).

(A) As the polybutadiene compound, a compound having a reactive functional group at the molecular terminal or in the molecular chain can be used. Examples of the reactive functional group include an epoxy group, a maleic acid group, a maleic anhydride group, a hydroxyl group, a carboxy group, an amino group, an amide group, an isocyanato group, an acrylic group, a methacrylic group and a vinyl group. By having these reactive functional groups at the molecular ends or in the molecular chain, the compatibility can be improved and the internal stress generated at the time of curing of the thermosetting resin composition can be more effectively reduced. Among these, it is preferable to have at least one selected from the group consisting of an epoxy group, a maleic acid group, a maleic anhydride group and a hydroxyl group. That is, it is preferable that the (a) polybutadiene compound has at least one modification selected from the group consisting of epoxy modification, maleic acid modification, maleic anhydride modification and hydroxyl group modification.
Examples of the polybutadiene compound include polybutadiene, vinyl-modified polybutadiene, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, carboxy-modified polybutadiene, hydroxyl group-modified polybutadiene, and the like, and the thermal expansion rate while maintaining heat resistance. Maleic anhydride-modified polybutadiene is preferable from the viewpoint of reducing the amount of water. (A) The polybutadiene compound may be used alone or in combination of two or more. The number of maleic anhydride groups in maleic anhydride-modified polybutadiene is preferably 1 to 5 and more preferably 1 to 3 in one molecule.

(A) The weight average molecular weight (Mw) of the polybutadiene compound is preferably 1,000 to 300,000, more preferably 2,000 to 100,000, still more preferably 5,000 to 20,000. When the weight average molecular weight (Mw) is at least the lower limit value, the low thermal expansion property is excellent, and when the weight average molecular weight (Mw) is at least the upper limit value, the compatibility is excellent.
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene.

The content of the (a) polybutadiene compound in the thermosetting resin composition of the present invention is preferably 1 to 40 parts by mass, preferably 5 to 40 parts by mass, based on 100 parts by mass of the solid content of the resin component of the thermosetting resin composition. 35 parts by mass is more preferable, and 5 to 30 parts by mass is further preferable. (A) When the content of the polybutadiene compound is 1 part by mass or more, a low thermal expansion effect by stress relaxation is obtained while maintaining heat resistance, and when it is 40 parts by mass or less, a thermosetting resin composition is obtained. The heat resistance of is maintained well.
In the present specification, the "solid content" is a non-volatile content excluding a volatile substance such as a solvent, and indicates a component that remains unvolatile when the resin composition is dried, and at room temperature. Includes liquid, starch syrup and waxy ones. Here, the room temperature is 25 ° C. in the present specification.
The "resin component" is a component used in the production of a resin or a resin, excluding (g) an inorganic filler described later, and specifically, in addition to the component (a), (b) described later. ~ (F) component, (X) component and the like correspond to the resin component.

<(B) Adducts of tertiary phosphine and quinones>
The thermosetting resin composition of the present invention can improve low thermal expansion and heat resistance by containing (b) an adduct of tertiary phosphine and quinones.
The component (b) is preferably an addition reaction product of a phosphine compound represented by the following general formula (b-1) and a quinone compound represented by the following general formula (b-2).

（一般式（ｂ−１）中、Ｒ^ｂ１〜Ｒ^ｂ３は、各々独立に、水素原子又は炭素数１〜１２の炭化水素基を示す。一般式（ｂ−２）中、Ｒ^ｂ４〜Ｒ^ｂ６は、各々独立に、水素原子又は炭素数１〜１８の炭化水素基を示し、Ｒ^ｂ４とＲ^ｂ５は互いに結合して環状構造となっていてもよい。）

(In the general formula (b-1), R ^{b1 to} R ^b3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. In the general formula (b-2), R ^{b4 to} R ^b6. Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ^b4 and R ^b5 may be bonded to each other to form a cyclic structure.)

^{The hydrocarbon groups having 1 to 12 carbon atoms represented by R b1 to} R ^b3 in the general formula (b-1) include substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 12 carbon atoms and carbon atoms. Examples thereof include 1 to 12 substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted aromatic hydrocarbon groups having 1 to 12 carbon atoms, and the like.
The substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R ^{b1 to} R ^b3 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-. Alkyl groups having 1 to 12 carbon atoms such as butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group; these are substituted with alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen and the like. And so on.
Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms represented by R ^{b1 to} R ^b3 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and an alkyl group thereof. Examples thereof include those substituted with an alkoxy group, an aryl group, a hydroxyl group, an amino group, a halogen and the like.
Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms represented by R ^{b1 to} R ^b3 include an aryl group such as a phenyl group and a naphthyl group; a trill group, a dimethylphenyl group, an ethylphenyl group and a butylphenyl group. , T-butylphenyl group, alkyl group substituted aryl group such as dimethylnaphthyl group; methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, alkoxy group substituted aryl group such as methoxynaphthyl group; dimethylaminophenyl Amino group substituted aryl group such as group, diethylaminophenyl group; halogen substituted aryl group such as hydroxyphenyl group and dihydroxyphenyl group; allyloxy group such as phenoxy group and crezoxy group; phenylthio group, trilthio group, diphenylamino group and amino Examples thereof include those substituted with groups, halogens and the like.
Among these, as R ^{b1 to} R ^b3 , an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 1 to 12 carbon atoms are preferable, and an n-butyl group, a phenyl group and a tolyl group are more preferable.

Examples of the phosphine compound represented by the general formula (b-1) include trialkylphosphine such as tricyclohexylphosphine, tri-n-butylphosphine, and trioctylphosphine; cyclohexylphosphinephosphine, dicyclohexylphosphinephosphine, butyldiphenylphosphine, and dibutyl. Examples thereof include alkyldiphenylphosphine such as phenylphosphine, octyldiphenylphosphine and dioctylphenylphosphine; dialkylphenylphosphine; triarylphosphine such as triphenylphosphine and tri-p-trilphosphine. Among these, trialkylphosphine and triarylphosphine are preferable, and tri-n-butylphosphine and triphenylphosphine are more preferable.

^{The hydrocarbon group having 1 to 18 carbon atoms represented by R b4 to} R ^b6 in the general formula (b-2) includes a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms and a carbon number of carbon atoms. Examples thereof include 1-18 substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted aromatic hydrocarbon groups having 1 to 18 carbon atoms, and the like.
The substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R ^{b4 to} R ^b6 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-. Alkoxy groups such as butyl group, pentyl group, hexyl group, octyl group, decyl group and dodecyl group; alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; methoxy group, ethoxy group, propoxy group and n-butoxy. Group, alkoxy group such as tert-butoxy group; alkylamino group such as dimethylamino group and diethylamino group; alkylthio group such as methylthio group, ethylthio group, butylthio group and dodecylthio group; amino group substituted alkyl group, alkoxy substituted alkyl group, Substituent alkyl groups such as hydroxyl group substituted alkyl group and aryl group substituted alkyl group; substituted alkoxy groups such as amino group substituted alkoxy group, hydroxyl group substituted alkoxy group and aryl group substituted alkoxy group can be mentioned.
Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms represented by R ^{b4 to} R ^b6 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and an alkyl group thereof. Examples thereof include those substituted with an alkoxy group, an aryl group, a hydroxyl group, an amino group, a halogen and the like.
Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 18 carbon atoms represented by R ^{b4 to} R ^b6 include an aryl group such as a phenyl group and a trill group; a dimethylphenyl group, an ethylphenyl group, a butylphenyl group and t-. Alkyl substituted aryl group such as butylphenyl group; alkoxy group substituted aryl group such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group; allyloxy group such as phenoxy group and crezoxy group; phenylthio group, trilthio Examples thereof include groups, diphenylamino groups, and those substituted with amino groups, halogens and the like.
Among these, hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted allyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted. Substituted arylthio groups are preferred, and hydrogen atoms are more preferred.

Examples of the quinone compound represented by the general formula (b-2) include 1,4-benzoquinone; 2,3-dimethoxy-1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, and methoxy-1. , 4-benzoquinone and other alkoxy group substitutions 1,4-benzoquinone; methyl-1,4-benzoquinone, 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone and other alkyl groups Substitution 1,4-benzoquinone and the like can be mentioned. Of these, 1,4-benzoquinone is preferred.

The addition reaction product of the phosphine compound represented by the general formula (b-1) and the quinone compound represented by the general formula (b-2) is a compound represented by the following general formula (b-3). And so on.

（式中、Ｒ^ｂ１〜Ｒ^ｂ６は、前記一般式（ｂ−１）及び（ｂ−２）と同様である。）

(In the formula, R ^{b1 to} R ^b6 are the same as the general formulas (b-1) and (b-2).)

(B) As a method for producing an adduct of a tertiary phosphine and a quinone, for example, a phosphine compound and a quinone compound used as raw materials are subjected to an addition reaction in an organic solvent in which both are dissolved, and then isolated. There is a way to do it.
(B) As the adduct of the tertiary phosphine and quinones, one type may be used alone or two or more types may be used in combination.

The content of the additive of (b) tertiary phosphine and quinones in the thermosetting resin composition of the present invention is from the viewpoint of reducing the thermal expansion rate while maintaining heat resistance, as well as storage stability and storage stability. From the viewpoint of curability, 0.01 to 2 parts by mass is preferable, 0.05 to 1.5 parts by mass is more preferable, and 0. 1 to 1 part by mass is more preferable.

<(C) Maleimide compound having at least two N-substituted maleimide groups in one molecule>
The thermosetting resin composition of the present invention can improve heat resistance by (c) containing a maleimide compound having at least two N-substituted maleimide groups in one molecule.
As the component (c), a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (c-1) is more preferable.

（式中、Ｘ^ｃ１は、下記一般式（ｃ−２）、（ｃ−３）、（ｃ−４）又は（ｃ−５）で表される基である。）

(In the formula, X ^c1 is a group represented by the following general formulas (c-2), (c-3), (c-4) or (c-5)).

（式中、Ｒ^ｃ１は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｐ１は、０〜４の整数である。）

(In the formula, R ^c1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. P1 is an integer of 0 to 4.)

（式中、Ｒ^ｃ２は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ｘ^ｃ２は、炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、−Ｏ−、スルフィド基、スルホニル基、カルボオキシ基、−Ｃ（＝Ｏ）−、単結合又は下記一般式（ｃ−３’）で表される基である。ｑ１は、各々独立に、０〜４の整数である。）

(In the formula, R ^c2 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. X ^c2 is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , -O-, sulfide group, sulfonyl group, carbooxy group, -C (= O)-, single bond or group represented by the following general formula (c-3'). Q1 is 0 independently. It is an integer of ~ 4.

（式中、Ｒ^ｃ３は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ｘ^ｃ３は、炭素数１〜５のアルキレン基、炭素数２〜５のアルキリデン基、−Ｏ−、スルフィド基、スルホニル基、カルボオキシ基、−Ｃ（＝Ｏ）−、又は単結合である。ｒ１は、各々独立に、０〜４の整数である。）

(In the formula, R ^c3 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. X ^c3 is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , -O-, sulfide group, sulfonyl group, carbooxy group, -C (= O)-, or single bond. R1 is an independently integer of 0 to 4).

（式中、ｎ１は、１〜１０の整数である。）

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

（式中、Ｒ^ｃ４は、各々独立に、水素原子又は炭素数１〜５の脂肪族炭化水素基である。ｕ１は、１〜８の整数である。）

(In the formula, R ^c4 is an independent 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 (c-2), the ^{aliphatic hydrocarbon group represented by R c1} 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. -Centyl group and the like can be mentioned. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
p1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the general formula (c-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented ^{by R c2} and the halogen atom are the same as those in the case of ^{R c1.} The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^c2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Be done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^c2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group is preferable.
q1 is an integer of 0 to 4 independently, and is preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability.

In the general formula (c-3'), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented ^{by R c3} and the halogen atom are the same as in the case of ^{R c2.
Examples} of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X c3 include the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented ^{by X c2.} Be done.
Among the above options, X ^c3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
r1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the general formula (c-4), n1 is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3 from the viewpoint of availability.
In the general formula (c-5), the same as the case ^{of R c1 in} the general formula (c-2) is mentioned as the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented ^{by R c4 and the halogen atom.} And the preferred ones are the same.
u1 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

As the component (c), N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-(1,3-phenylene) bismaleimide, N, N'-[1,3 -(2-Methylphenylene)] bismaleimide, N, N'-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4-) Maleimidephenyl) methane, bis (3-methyl-4-maleimidephenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidephenyl) ether, Bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ketone, bis (4-maleimidecyclohexyl) methane, 1,4-bis (4-maleimidephenyl) cyclohexane, 1 , 4-bis (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-maleimidephenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidephenoxy) phenyl] ethane, 1,1-bis [4 -(4-Maleimidephenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidephenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidephenoxy) phenyl] ethane, 2,2 -Bis [4- (3-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] butane , 2,2-bis [4- (4-maleimidephenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidephenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidephenoxy) biphenyl, 4, 4-Bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] ketone, bis [4- (4-maleimide phenoxy) phenyl] ketone, 2,2' -Bis (4-maleimide phenyl) disulfide, bis (4-maleimide phenyl) disulfide, bis [4- (3-maleimide phenoxy) phenyl] sulfide, bis [4- (4-maleimide phenoxy) phenyl] sulfide, bis [4 -(3-Maleimide phenoxy) phenyl] sulfoxide, bis [4- (4-maleimide phenoxy) phenyl] sulfoxide, bis [4- (3-maleimide phenoxy) phenyl] sulfone, bis [4- (4-maleimide phenoxy) phenyl ] Cythone, bis [4- (3-maleimide phenoxy) phenyl] ether, bis [4- (4-maleimide phenoxy) phenyl] ether and the like. As the component (c), one type may be used alone or two or more types may be used in combination.

Among these, bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl- 4,4'-Diphenylmethanebismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane are preferable, and 3,3'-dimethyl-5,5'- from the viewpoint of solubility in a solvent. Diethyl-4,4'-diphenylmethane bismaleimide, bis (4-maleimidephenyl) methane is more preferable, and bis (4-maleimidephenyl) methane is particularly preferable because it is inexpensive.

The content of the component (c) in the thermosetting resin composition of the present invention is 100% by mass of the solid content of the resin component of the thermosetting resin composition from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. 10 to 70 parts by mass is preferable, 15 to 65 parts by mass is more preferable, and 20 to 60 parts by mass is further preferable.

<(D) Amine compound having at least two primary amino groups in one molecule>
The thermosetting resin composition of the present invention preferably further contains (d) an amine compound having at least two primary amino groups in one molecule (hereinafter, also referred to as “component (d)”). .. The thermosetting resin composition of the present invention can further improve the heat resistance by containing the component (d).
As the component (d), an amine compound having two primary amino groups in one molecule is preferable, and a compound represented by the following general formula (d-1) is more preferable.

（式中、Ｙ^ｄ１は、下記一般式（ｄ−２）、（ｄ−３）又は（ｄ−４）で表される基である。）

(In the formula, Y ^d1 is a group represented by the following general formula (d-2), (d-3) or (d-4).)

（式中、Ｒ^ｄ１は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｐ２は、０〜４の整数である。）

(In the formula, R ^d1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. P2 is an integer of 0 to 4.)

（式中、Ｒ^ｄ２は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ｙ^ｄ２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、−Ｏ−、スルフィド基、スルホニル基、カルボオキシ基、−Ｃ（＝Ｏ）−、単結合又は下記一般式（ｄ−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 formula, R ^d2 is an aliphatic hydrocarbon group or a halogen atom ^{having 1 to 5 carbon atoms, respectively. Y d2} is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , -O-, sulfide group, sulfonyl group, carbooxy group, -C (= O)-, single bond or group represented by the following general formula (d-3'). Q2 is 0 independently. It is an integer of ~ 4.

（式中、Ｒ^ｄ３は、各々独立に、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。Ｙ^ｄ３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、−Ｏ−、スルフィド基、スルホニル基、カルボオキシ基、−Ｃ（＝Ｏ）−、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 formula, R ^d3 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms independently. Y ^d3 is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms. , -O-, sulfide group, sulfonyl group, carbooxy group, -C (= O)-, or single bond. S1 is an independently integer of 0 to 4).

（式中、Ｒ^ｄ４は、各々独立に、炭素数１〜５のアルキル基、フェニル基又は置換フェニル基を示し、Ｒ^ｄ５は、各々独立に、２価の有機基を示す。ｍ２は、１〜１００の整数を示す。）

(In the formula, R ^d4 independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group, and R ^d5 independently represents a divalent organic group. M2 is 1 Indicates an integer of ~ 100.)

In the general formula (d-2), the ^{aliphatic hydrocarbon group represented by R d1} 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. -Centyl group and the like can be mentioned. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
p2 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 2 from the viewpoint of availability.

In the general formula (d-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented ^{by R d2} are the same as in the case of ^{R d1.} The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and further preferably an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by Y ^d2 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. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by Y ^d2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group is preferable.
q2 is an integer of 0 to 4 independently, and is preferably an integer of 0 to 2, more preferably 0 or 2, from the viewpoint of availability.

In the general formula (d-3'), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented ^{by R d3} are the same as those in the case of ^{R d2.
Examples} of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by Y d3 include the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented ^{by Y d2.} Be done.
Among the above options, Y ^d3 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.
s1 is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability.

In the general formula (d-4), ^{the alkyl group having 1 to 5 carbon atoms represented by R d4} is preferably an alkyl group having 1 to 3 carbon atoms. ^Examples of the alkyl group represented by R d4 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. Groups are preferred.
Examples of the substituent in the substituted phenyl group represented by R ^d4 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 R d4.}
Among the groups represented by R ^d4 , a phenyl group or a methyl group is preferable, and a methyl group is more preferable, from the viewpoint of solubility with other resins.
^Examples of the divalent organic group represented by R d5 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.
m2 is an integer of 1 to 100, and an integer of 2 to 50 is preferable from the viewpoint of compatibility and high elastic modulus.

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

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

Further, the component (d) contains a modified siloxane having an amino group at the terminal and an amine compound other than the modified siloxane having an amino group at the terminal from the viewpoint of achieving both low thermal expansion, high elasticity and high heat resistance. It is preferably composed of a modified siloxane having an amino group at the terminal, 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. It is more preferable to use in combination with one or more selected from the group.
(D) 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 a component, the mass ratio thereof [modified siloxane having an amino group at the terminal / at the end The amine compound other than the modified siloxane having an amino group] is preferably 30/70 to 85/15, more preferably 40/60 to 80/20, and even more preferably 50/50 to 75/25.

When the thermosetting resin composition of the present invention contains the component (d), the content of the component (c) and the component (d) is from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. , The equivalent of the maleimide group of the component (c) preferably exceeds the equivalent of the primary amino group of the component (d), and the equivalent of the maleimide group of the component (c) and the primary amino group of the component (d). The ratio [(c) component / (d) component] to the equivalent amount is preferably 1 to 15, and more preferably 2 to 10.

<(E) Amine compound having an acidic substituent>
The thermosetting resin composition of the present invention preferably further contains (e) an amine compound having an acidic substituent (hereinafter, also referred to as “component (e)”). The thermosetting resin composition of the present invention can further improve the heat resistance by containing the component (e).
As the component (e), a compound represented by the following general formula (e-1) is preferable.

（式中、Ｒ^ｅ１は、各々独立に、酸性置換基である水酸基、カルボキシ基又はスルホン酸基であり、Ｒ^ｅ２は、各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子である。ｘは１〜５の整数、ｙは０〜４の整数であり、ｘとｙの和は５である。）

(In the formula, R ^e1 is independently an acidic substituent, a hydroxyl group, a carboxy group, or a sulfonic acid group, and R ^e2 is independently a hydrogen atom and an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Alternatively, it is a halogen atom. X is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

As the component (e), m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-amino Benzene sulfonic acid, p-aminobenzene sulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. Among these, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and synthetic yield. From the viewpoint of heat resistance, m-aminophenol and p-aminophenol are more preferable, and from the viewpoint of low thermal expansion, p-aminophenol is further preferable.

When the thermosetting resin composition of the present invention contains (e) an amine compound having an acidic substituent, the content thereof is a thermosetting resin from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. With respect to 100 parts by mass of the solid content of the resin component of the composition, 0.2 to 5 parts by mass is preferable, 0.4 to 4 parts by mass is more preferable, and 0.6 to 3 parts by mass is further preferable.

<(X) Amino modified resin>
The thermosetting resin composition of the present invention preferably contains (X) an amino-modified resin having at least two N-substituted maleimide groups and an amino group in one molecule as the component (c).
The amino-modified resin (X) preferably has an acidic substituent from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance, and has a structure derived from the component (c) and a structure derived from the component (d). It is more preferable to contain the structure, and it is more preferable to contain the structure derived from the component (c), the structure derived from the component (d), and the structure derived from the component (e).

The (X) amino-modified resin can be produced by reacting the component (c) and the component (d), and if necessary, the component (e).
In this reaction, the amount of the component (d), the component (c) and the component (e) used is such that the equivalent of the maleimide group of the component (c) is used from the viewpoint of reducing the coefficient of thermal expansion while maintaining the heat resistance. The range is preferably in the range exceeding the total equivalent of the primary amino groups of the component (d) and the component (e), and the equivalent of the maleimide group of the component (c) and the primary amino group of the component (d) and the component (e). The ratio [(c) component / (d) component and (e) component] to the equivalent amount is preferably 1 to 15, and more preferably 2 to 10.
The reaction temperature in the reaction is preferably 70 to 200 ° C., more preferably 100 to 150 ° C. from the viewpoint of productivity and uniform progress of the reaction. The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 6 hours.
The reaction is preferably carried out in an organic solvent. Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate ethyl ester, γ-butyrolactone, and the like. Ester-based solvent; Ether-based solvent such as tetrahydrofuran; Fragrant solvent such as toluene, xylene, mesitylen, etc .; Nitrogen atom-containing solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Sulfur atom-containing solvent such as dimethylsulfoxide, etc. Can be mentioned. As the organic solvent, one type may be used alone or two or more types may be used in combination.

When the thermosetting resin composition of the present invention contains (X) amino-modified resin, the content thereof is the resin of the thermosetting resin composition from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance. With respect to 100 parts by mass of the solid content of the component, 30 to 80 parts by mass is preferable, 40 to 75 parts by mass is more preferable, and 45 to 70 parts by mass is further preferable.

<(F) Thermosetting resin>
The thermosetting resin composition of the present invention preferably further contains (f) a thermosetting resin (hereinafter, also referred to as “(f) component”). By containing the component (f), the thermosetting resin composition of the present invention can further improve the adhesiveness with metal wiring such as copper.
As the component (f), epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, etc. Examples thereof include triazine resin and melamine resin. (F) As the thermosetting resin, one type may be used alone or two or more types may be used in combination. Among these, one or more selected from the group consisting of epoxy resin and cyanate resin is preferable, and epoxy resin is more preferable, from the viewpoint of moldability and electrical insulation, and from the viewpoint of improving the adhesiveness with metal wiring.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, and stillben. Type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy Examples thereof include resins, alicyclic epoxy resins, polyfunctional phenols, polycyclic aromatic diglycidyl ether compounds such as anthracene, and phosphorus-containing epoxy resins in which a phosphorus compound is introduced. Among these, biphenyl aralkyl type epoxy resin and naphthalene type epoxy resin are preferable from the viewpoint of heat resistance and flame retardancy.

When the thermosetting resin composition of the present invention contains (f) a thermosetting resin, the content thereof is from the viewpoint of reducing the coefficient of thermal expansion while maintaining heat resistance, and adhesiveness to metal wiring. From the viewpoint of improvement, 5 to 50 parts by mass is preferable, 10 to 40 parts by mass is more preferable, and 15 to 35 parts by mass is further preferable with respect to 100 parts by mass of the solid content of the resin component of the thermosetting resin composition.

<(G) Inorganic filler>
The thermosetting resin composition of the present invention preferably further contains (g) an inorganic filler (hereinafter, also referred to as “(g) component”).
(G) Examples of the inorganic filler include silica, alumina, titanium oxide, mica, verilia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide and aluminum silicate. , Calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fiber, fine glass powder, hollow glass and the like. .. As the glass, E glass, T glass, D glass and the like are preferably mentioned. (G) As the inorganic filler, one type may be used alone or two or more types may be used in combination.
Among these, silica is preferable from the viewpoint of dielectric properties, heat resistance and low thermal expansion. Examples of the silica include precipitated silica having a high water content produced by a wet method and dry silica produced by a dry method containing almost no bound water and the like, and further examples of the dry silica include a production method. It is classified into crushed silica, fumed silica, fused spherical silica and the like according to the difference. Among these, fused spherical silica is preferable from the viewpoint of low thermal expansion and fluidity when filled in the resin.

(G) 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 the coarse particles is reduced and the defects caused by the coarse particles are reduced. 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.

(G) 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 (g) inorganic filler before compounding by a dry method or a wet method, and the surface-untreated (g) inorganic filler may be used by 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. Among these, a silane-based coupling agent is preferable, and an aminosilane-based coupling agent is more preferable.

When the thermosetting resin composition of the present invention contains (g) 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, 50 to 250 parts by mass are more preferable, and 80 to 230 parts by mass are further preferable. (G) When the content of the inorganic filler is within the above range, the moldability and low thermal expansion of the thermosetting resin composition are good.

<Other ingredients>
The thermosetting resin composition of the present invention is an optionally known thermoplastic resin, organic filler, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, to the extent that the thermosetting property is not impaired. It may contain a fluorescent whitening agent, an adhesiveness improving agent and the like.

Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, and polyether ether. Examples thereof include ketone resins, polyetherimide resins, silicone resins, tetrafluoroethylene resins and the like.

Examples of the organic filler include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin and the like, resin fillers having a core-shell structure, and the like.
Flame retardants include aromatic phosphoric acid ester compounds, phosphazene compounds, phosphinic acid esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itss. Phosphorus flame retardants such as derivatives; Nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate; Halogen-containing flame retardants containing bromine, chlorine, etc .; Inorganic flame retardants such as antimony trioxide Examples include flame retardants.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.
Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, and the like.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals, thioxanthone-based photopolymerization initiators, and the like.
Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative.
Examples of the adhesiveness improving agent include urea compounds such as ureasilane and the coupling agent.

The thermosetting resin composition of the present invention may be in the state of a varnish in which each component is dissolved or dispersed in an organic solvent for use in the production of a prepreg or the like.
Examples of the organic solvent used for the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; butyl acetate and propylene. Ester-based solvents such as glycol monomethyl ether acetate; Ether-based solvents such as tetrahydrofuran; Fragrant solvents such as toluene, xylene, and mesitylen; Nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Examples include a sulfur atom-containing solvent. These organic solvents may be used alone or in combination of two or more.
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
The solid content concentration of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the above range, the coatability can be kept good and a prepreg having an appropriate amount of the resin composition adhered can be obtained.

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

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

The prepreg of the present invention is, for example, a fiber base material so that the amount of the thermosetting resin composition adhered to the fiber base material (the content of the thermosetting resin composition in the prepreg) is 20 to 90% by mass. After impregnating with, it is usually obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-staged).

[Laminate board]
The laminated board of the present invention contains an insulating layer formed by using the prepreg of the present invention.
The laminated board of the present invention can be obtained by laminating and molding the prepreg of the present invention. Specifically, the prepreg of the present invention can be manufactured, for example, by stacking 1 to 20 sheets and laminating and molding them in a configuration in which metal foils such as copper and aluminum are arranged on one side or both sides thereof. By the manufacturing method, a laminated board having an insulating layer formed by using the prepreg of the present invention and a metal foil arranged on one side or both sides thereof can be obtained. The metal foil is not particularly limited as long as it is used for an electric 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 plate.

[Printed wiring board]
The printed wiring board of the present invention is a printed wiring board obtained by circuit processing the metal foil of the laminated board of the present invention.
The circuit processing of the metal foil can be wiring processing by an ordinary etching method. Further, it is also possible to stack a plurality of laminated boards that have been wiring-processed via the prepreg of the present invention and heat-press them to form a plurality of layers at once. After that, a multi-layer printed wiring board can be manufactured through the formation of through holes or blind via holes by drilling or laser processing and the formation of interlayer wiring by plating or conductive paste.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
The performance of the copper-clad laminates obtained in each example was measured and evaluated by the following methods.

(1) Glass transition temperature (Tg)
A 5 mm square evaluation substrate from which the copper foil has been removed is prepared by immersing the copper-clad laminate in a copper etching solution, and thermomechanical analysis is performed by a compression method using a TMA test device (manufactured by DuPont, trade name: TMA2940). gone. After the evaluation substrate is mounted on the device in the X direction, measurements are made twice in succession under the measurement conditions of a load of 5 g and a temperature rise rate of 10 ° C./min, and are indicated by the intersections of tangents of different thermal expansion curves in the second measurement. Tg was determined and the heat resistance was evaluated.

(2) Coefficient of thermal expansion Using the device and evaluation substrate used to measure the glass transition temperature, measure twice in succession under the same measurement conditions as the measurement of the glass transition temperature, from 30 ° C in the second measurement. The average coefficient of thermal expansion up to 100 ° C. was calculated and used as the value of the coefficient of thermal expansion.

(3) Bending elastic modulus A 50 mm × 25 mm evaluation substrate from which the copper foil was removed was prepared by immersing a copper-clad laminate in a copper etching solution, and a crosshead speed was used using 5 ton tencilon (manufactured by Orientec Co., Ltd.). The measurement was performed under the conditions of 1 mm / min and a distance between spans of 20 mm.

Examples 1-11, Comparative Examples 1-2
The composition was blended and mixed according to the blending ratio shown in Table 2 (the numerical value in the table is the mass part of the solid content, and in the case of a solution or dispersion, the solid content equivalent amount), and methyl ethyl ketone was used as a solvent. A varnish having a solid content of 65% by mass was prepared.
Next, this varnish was impregnated and coated on an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a thermosetting resin composition content of 48% by mass.
Four of these prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 240 ° C. for 60 minutes to obtain a copper-clad laminate. Table 2 shows the evaluation results of the obtained copper-clad laminate.

Each component used in the formulation is shown below.

[(A) Polybutadiene compound]
Maleic anhydride-modified polybutadiene (manufactured by Clay Valley, trade name: Ricon (registered trademark) 130MA8, average molecular weight: 10,000, number of maleic anhydride groups: 2)

[(B) Adducts of tertiary phosphine and quinones]
(B-1) Adduct of triphenylphosphine and p-benzoquinone (manufactured by Seiko Kagaku Co., Ltd.)
(B-2) Adduct of tri-p-tolylphosphine and p-benzoquinone (manufactured by Seiko Kagaku Co., Ltd.)
(B-3) Adduct of tri (n-butyl) phosphine and p-benzoquinone (manufactured by Seiko Kagaku Co., Ltd.)

[(C) Maleimide compound having at least two N-substituted maleimide groups]
(C-1) Bis (4-maleimidephenyl) Methane (manufactured by KI Kasei Co., Ltd., trade name: BMI)
(C-2) 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000)

[(D) Amine compound having at least two primary amino groups in one molecule]
(D-1) Diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A, functional group equivalent: 800 g / mol)
(D-2) Diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B, functional group equivalent: 1,500 g / mol)
(D-3) 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD (registered trademark) A-A)
(D-4) 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd., trade name: BAPP)

[(E) Amine compound having an acidic substituent]
・ (E-1) p-aminophenol (manufactured by Kanto Chemical Co., Inc.)
・ (E-2) m-aminophenol (manufactured by Kanto Chemical Co., Inc.)

[(F) Thermosetting resin]
(F-1) α-naphthol / cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-7000L)
(F-2) Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000-H)

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

[(X) Amino modified resin]
Production Example 1: (X-1) Siloxane-modified polyimide In 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 cooling tube, both-terminal diamine-modified siloxane (Shinetsu Chemical Industry Co., Ltd.) Made by Co., Ltd., trade name: X-22-161A, functional group equivalent: 800 g / mol) 99.2 g and 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name) : KAYAHARD (registered trademark) A-A) 54.4 g, p-aminophenol (manufactured by Kanto Chemical Co., Ltd.) 4.8 g, and bis (4-maleimidephenyl) methane (manufactured by KAI Kasei Co., Ltd., trade name) : BMI) 125.3 g and propylene glycol monomethyl ether 250.0 g are added and reacted at 100 ° C. for 3 hours to prepare a solution containing (X-1) a siloxane-modified polyimide having an acidic substituent as a component (X). Obtained.

Production Example 2: (X-2) Siloxane-modified polyimide A reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux cooling tube is placed in a reaction vessel with a 2-terminal diamine-modified siloxane (Shinetsu Chemical Industry Co., Ltd.) Company, product name: X-22-161B, functional group equivalent: 1,500 g / mol) 23.8 g and 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., product) Name: KAYAHARD (registered trademark) A-A) 15.0 g, p-aminophenol (manufactured by Kanto Chemical Co., Ltd.) 4.7 g, and 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane ( 123.2 g of Daiwa Kasei Kogyo Co., Ltd., trade name: BMI-4000) and 250.0 g of propylene glycol monomethyl ether were added and reacted at 115 ° C. for 3 hours to obtain (X-2) acidic substitution as the (X) component. A siloxane-modified polyimide-containing solution having a group was obtained.

As is clear from Table 2, the laminated boards obtained in Examples 1 to 11 have excellent low thermal expansion while maintaining heat resistance. On the other hand, the laminated board of Comparative Example 1 was inferior in low thermal expansion, and in Comparative Example 2, the curing of the thermosetting resin composition did not proceed sufficiently, so that the laminated board could not be produced.

Since the thermosetting resin composition of the present invention can obtain a laminated board having a particularly excellent low thermal expansion rate, it is possible to manufacture a printed wiring board having a high density and a high number of layers, and a large amount of data can be obtained at high speed. It is suitably used for wiring boards of electronic devices used such as computers and information device terminals to be processed by.

Claims (15)

Thermosetting containing (a) a polybutadiene compound, (b) an adduct of tertiary phosphine and quinones, and (c) a maleimide compound having at least two N-substituted maleimide groups in one molecule. It is a sex resin composition and
Wherein (a) the polybutadiene compound, at least one modified member selected from Ma maleic acid-modified and maleic anhydride denatured or Ranaru group have been made, the thermosetting resin composition. (D) The thermosetting resin composition according to claim 1, which contains (d) an amine compound having at least two primary amino groups in one molecule. The thermosetting resin composition according to claim 1 or 2, further comprising (e) an amine compound having an acidic substituent. (A) The invention according to any one of claims 1 to 3, wherein the content of the polybutadiene compound is 1 to 40 parts by mass with respect to 100 parts by mass of the solid content of the resin component of the thermosetting resin composition. Thermosetting resin composition. The thermosetting according to any one of claims 1 to 4, wherein the component (c) is an (X) amino-modified resin having at least two N-substituted maleimide groups and an amino group in one molecule. Sex resin composition. The thermosetting resin composition according to claim 5, wherein the component (X) has an acidic substituent. The component (X) is (c) a structure derived from a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (d) an amine having at least two primary amino groups in one molecule. The thermosetting resin composition according to claim 5 or 6, which comprises a structure derived from a compound. The thermosetting resin composition according to any one of claims 5 to 7, wherein the component (X) has a structure derived from an amine compound having an acidic substituent (e). (A) The thermosetting resin composition according to any one of claims 1 to 8, wherein the polybutadiene compound is liquid polybutadiene. The thermosetting resin composition according to any one of claims 1 to 9, further comprising (f) at least one selected from the group consisting of an epoxy resin and a cyanate resin as the thermosetting resin. The thermosetting resin composition according to any one of claims 1 to 10, further comprising (g) an inorganic filler. A prepreg containing a thermosetting resin composition obtained by B-stage the thermosetting resin composition according to any one of claims 1 to 11. A laminated board containing an insulating layer formed by using the prepreg according to claim 12. The laminated board according to claim 13, further comprising an insulating layer formed by using the prepreg according to claim 12, and a metal foil arranged on one side or both sides thereof. A printed wiring board obtained by circuit processing the metal foil of the laminated board according to claim 14.