JP2021011535A - Thermosetting resin composition, prepreg, copper-clad laminate, printed wiring board and semiconductor package - Google Patents

Abstract

To provide a thermosetting resin composition excellent in dielectric characteristics and laser processability, to provide a prepreg using the thermosetting resin composition, to provide a copper-clad laminate, to provide a printed wiring board and to provide a semiconductor package.SOLUTION: A thermosetting resin composition contains: (A) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; (B) an epoxy-modified polybutadiene; (C) an active ester compound; (D) one or more kinds selected from a group consisting of a maleimide compound and a modification product thereof; and (E) an epoxy resin including an alicyclic skeleton. A prepreg using the thermosetting resin composition, a copper-clad laminate, a printed wiring board and a semiconductor package are provided.SELECTED DRAWING: None

Description

The present invention relates to thermosetting resin compositions, prepregs, copper-clad laminates, printed wiring boards and semiconductor packages.

Thermosetting resins are widely used in fields such as electronic components where high reliability is required because their unique crosslinked structure exhibits high heat resistance and dimensional stability. In particular, for copper-clad laminates and interlayer insulating materials, due to the recent demand for higher density wiring, high copper foil adhesiveness for forming fine wiring and workability when drilling holes with a laser or the like are also possible. Needed. Furthermore, in recent years, the mounting of electronic components using lead-free solder has made it necessary to have higher heat resistance than before.

Mobile communication devices such as base station devices, network-related electronic devices such as servers and routers, and large computers are required to transmit and process a large amount of information with low loss and high speed. Information can be transmitted and processed at higher frequencies at higher frequencies, but the higher the frequency, the easier it is for electrical signals to be attenuated, and at shorter transmission distances, the output becomes weaker and the loss tends to increase. Has. Therefore, in order to meet the requirements for low loss and high-speed communication, it is required to reduce the dielectric properties (relative permittivity, dielectric loss tangent) of the printed wiring board itself, especially the relative permittivity and dielectric loss tangent in the high frequency band. There is.

Conventionally, in order to obtain a printed wiring board capable of transmitting information with low loss, a substrate material using a fluororesin having a low relative permittivity and dielectric loss tangent has been used. However, since a fluororesin generally has a high melting temperature and a high melting viscosity and a relatively low fluidity, there is a problem that it is necessary to set high temperature and high pressure conditions at the time of press molding. Moreover, there is a problem that workability, dimensional stability and adhesiveness to metal plating are insufficient for use in a high-multilayer printed wiring board used in the above-mentioned communication equipment and the like.

Therefore, research is being conducted on thermosetting resin materials that can replace fluororesins, which are suitable for high-frequency printed wiring board applications. For example, Patent Document 1 describes a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride as a thermosetting resin composition capable of achieving excellent dielectric properties. A thermosetting resin composition containing epoxy-modified polybutadiene having hydroxyl groups at both ends of the molecule, an active ester compound, and one or more selected from the group consisting of maleimide compounds and modified products thereof is disclosed. ..

JP-A-2018-165340

The thermosetting resin composition described in Patent Document 1 is characterized in that it has excellent moldability and can achieve high heat resistance and excellent dielectric properties while maintaining high adhesiveness to copper foil. However, with the progress of fine wiring in recent years, the printed wiring board is required to have excellent dielectric properties and further excellent laser workability. According to the studies by the present inventors, it has been found that the technique of Patent Document 1 is excellent in dielectric properties, but there is room for further improvement in laser workability.

Therefore, an object of the present invention is to provide a thermosetting resin composition having excellent dielectric properties and laser processability, and a prepreg, a copper-clad laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition. There is.

As a result of diligent research to solve the above problems, the present inventors have obtained (A) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and (B). It contains epoxy-modified polybutadiene, (C) an active ester compound, (D) one or more selected from the group consisting of a maleimide compound and a modified product thereof, and (E) an epoxy resin containing an alicyclic skeleton. We have found that the thermosetting resin composition can solve the above-mentioned problems, and have completed the present invention.

The present invention relates to the following [1] to [14].
[1] (A) A copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride,
(B) Epoxy-modified polybutadiene and
(C) Active ester compound and
(D) One or more selected from the group consisting of maleimide compounds and modified products thereof, and
(E) Epoxy resin containing an alicyclic skeleton and
A thermosetting resin composition comprising.
[2] The component (A) is a structural unit derived from an aromatic vinyl compound represented by the following general formula (Ai) and a structure derived from maleic anhydride represented by the following formula (A-ii). The thermosetting resin composition according to the above [1], which is a copolymer resin having a unit.

(In the formula, ^RA1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^RA2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group, a hydroxyl group or a (meth) acryloyl group. X is an integer of 0 to 3.)
[3] The thermosetting resin composition according to the above [1] or [2], wherein the component (B) is an epoxy-modified polybutadiene represented by the following general formula (B-1).

(In the formula, a, b and c represent the ratio of the structural units in parentheses, respectively, where a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.30. It is 0.80, and further, a + b + c = 1.00 and (a + c)> b are satisfied. Y represents the number of structural units in parentheses and is an integer of 10 to 250.)
[4] The component (C) esterifies a polyvalent carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group represented by any of the following general formulas (C1-1) to (C1-5). The thermosetting resin composition according to any one of the above [1] to [3], which is a compound obtained by conversion.

(In the formula, k1 and k2 are independently 0 or 1, respectively.)
[5] The component (D) comprises reacting a maleimide compound having at least two N-substituted maleimide groups in one molecule with a monoamine compound having (d1) acidic substituents and a (d2) diamine compound. The thermosetting resin composition according to any one of the above [1] to [4], which is a compound.
[6] The thermosetting resin composition according to any one of [1] to [5] above, wherein the alicyclic skeleton contained in the component (E) is a dicyclopentadiene skeleton.
[7] The above-mentioned [1] to [6], wherein the content of the component (A) is 1 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. The thermosetting resin composition according to any one of.
[8] The above [1] to [7], wherein the content of the component (B) is 1 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. The thermosetting resin composition according to any one of.
[9] The above [1] to [8], wherein the content of the component (E) is 1 to 30 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. The thermosetting resin composition according to any one of.
[10] Further, any one of the above [1] to [9], which further contains at least one selected from the group consisting of (F) curing accelerator, (G) flame retardant and (H) inorganic filler. The thermosetting resin composition according to.
[11] A prepreg containing the thermosetting resin composition according to any one of the above [1] to [10].
[12] A copper-clad laminate obtained by laminating the prepreg and copper foil according to the above [11].
[13] A printed wiring board using the copper-clad laminate according to the above [12].
[14] A semiconductor package using the printed wiring board according to the above [13].

According to the present invention, it is possible to provide a thermosetting resin composition having excellent dielectric properties and laser processability, and a prepreg, a copper-clad laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition. ..

[Thermosetting resin composition]
The thermosetting resin composition of the present invention
(A) A copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride (hereinafter, also referred to as "(A) component" or "(A) copolymer resin").
(B) Epoxy-modified polybutadiene (hereinafter, also referred to as “(B) component”),
(C) Active ester compound (hereinafter, also referred to as "(C) component") and
(D) One or more selected from the group consisting of maleimide compounds and modified products thereof (hereinafter, also referred to as "(D) component"),
(E) Epoxy resin containing an alicyclic skeleton (hereinafter, also referred to as "(E) component") and
It is a thermosetting resin composition containing.
Hereinafter, each component contained in the thermosetting resin composition of the present invention will be described in detail.

<(A) Copolymerized resin>
The component (A) is a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride. Since the thermosetting resin composition of the present invention contains the component (A), it has excellent dielectric properties.
As the copolymerization resin (A), one type may be used alone, or two or more types may be used in combination.
Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, 4-methylstyrene, dimethylstyrene and the like. Of these, styrene is preferable.
As the component (A), a structural unit derived from an aromatic vinyl compound represented by the following general formula (Ai) and a structural unit derived from maleic anhydride represented by the following formula (A-ii) are used. The copolymer resin having is preferable.

(In the formula, ^RA1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^RA2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group, a hydroxyl group or a (meth) acryloyl group. X is an integer of 0 to 3.)

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A1 and ^{R A2,} a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, n- pentyl group Can be mentioned. The alkyl group preferably has 1 to 3 carbon atoms.
The alkenyl group having 2 to 5 carbon atoms which R ^A2 represents an allyl group, crotyl group, and the like. The alkenyl group preferably has 3 or 4 carbon atoms.
Examples of the aryl group having 6 to 20 carbon atoms R ^A2 represents a phenyl group, a naphthyl group, an anthryl group, etc. biphenylyl group. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
x is an integer of 0 to 3, preferably 0 or 1, more preferably 0. When x is an integer of 2 or more, the plurality of ^RA2s may be the same or different.
In the structural unit derived from the aromatic vinyl compound represented by the general formula (A-i), it is represented by the following formula (A-i-1) in which ^RA1 is a hydrogen atom and x is 0. Structural units are preferred.

(A) Content ratio of structural unit derived from aromatic vinyl compound to structural unit derived from maleic anhydride in the copolymer resin [Structural unit derived from aromatic vinyl compound / structure derived from maleic anhydride The unit] (molar ratio) is preferably 2 to 9, more preferably 3 to 7, and even more preferably 3 to 5. When the content ratio is 2 or more, the effect of improving the dielectric property and the heat resistance tends to be sufficient, and when the content ratio is 9 or less, the compatibility tends to be good.
The total content of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride in the (A) copolymer resin is preferably 50% by mass or more, more preferably 70% by mass or more, and further. It is preferably 90% by mass or more, and particularly preferably substantially 100% by mass.

The weight average molecular weight (Mw) of the (A) copolymer resin is preferably 5,000 to 18,000, more preferably 6,000 to 17,000, still more preferably 8,000 to 16,000, and particularly preferably 8,000 to 16,000. It is 10,000 to 16,000, most preferably 12,000 to 16,000. The weight average molecular weight in the present specification is a value measured by a gel permeation chromatography (GPC) method (standard polystyrene conversion) using tetrahydrofuran as an eluent.

The copolymerized resin (A) can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride. In addition to the aromatic vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. Examples of various polymerizable components include vinyl compounds such as ethylene, propylene, butadiene, isobutylene and acrylonitrile; and compounds having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
Further, the copolymer obtained by the above copolymer is substituted with an alkenyl group such as an allyl group, a (meth) acryloyl group, a hydroxyl group, etc. through a Friedel-Crafts reaction or a reaction using a metal catalyst such as lithium. A group (corresponding to ^RA2 in the above general formula (Ai)) may be introduced.

As the (A) copolymer resin, a commercially available product can be used, and the commercially available products include "SMA (registered trademark) EF30" (styrene / maleic anhydride = 3, Mw = 9,500) and "SMA (registered)". EF40 (styrene / maleic anhydride = 4, Mw = 11,000), SMA (registered trademark) EF60 (styrene / maleic anhydride = 6, Mw = 11,500), SMA (registered trademark) EF80 ”(styrene / maleic anhydride = 8, Mw = 14,400) (all manufactured by Sartmer) and the like can be mentioned. Among these, "SMA (registered trademark) EF40" is preferable. The above-mentioned "styrene / maleic anhydride" means a content ratio [styrene / maleic anhydride] of a structural unit derived from styrene and a structural unit derived from maleic anhydride.

<(B) Epoxy-modified polybutadiene>
The component (B) is epoxy-modified polybutadiene. Since the thermosetting resin composition of the present invention contains the component (B), it has excellent adhesiveness to a copper foil while maintaining the dielectric properties.
As the component (B), one type may be used alone, or two or more types may be used in combination.

The component (B) preferably has a hydroxyl group at the end of the molecule, more preferably has a hydroxyl group at both ends of the molecule, and further preferably has a hydroxyl group only at both ends of the molecule. The number of hydroxyl groups contained in the component (B) is preferably one or more, more preferably 1 to 5, still more preferably 1 or 2, and particularly preferably 2.
The component (B) is preferably an epoxy-modified polybutadiene represented by the following general formula (B-1) from the viewpoint of adhesiveness to copper foil, heat resistance, coefficient of thermal expansion and flexibility.

(In the formula, a, b and c represent the ratio of the structural units in parentheses, respectively, where a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.30. It is 0.80, and further, a + b + c = 1.00 and (a + c)> b are satisfied. Y represents the number of structural units in parentheses and is an integer of 10 to 250.)

The order of bonding of each structural unit in the above general formula (B-1) is random. That is, the structural unit shown on the left, the structural unit shown in the center, and the structural unit shown on the right may be interchanged, and they are referred to as (a), (b), and (c), respectively. When expressed by,-[(a)-(b)-(c)]-[(a)-(b)-(c)-]-,-[(a)-(c)-(b)]- [(A)-(c)-(b)-]-,-[(b)-(a)-(c)]-[(b)-(a)-(c)-]-,-[( a)-(b)-(c)]-[(c)-(b)-(a)-]-,-[(a)-(b)-(a)]-[(c)-(b) )-(C)-]-,-[(c)-(b)-(c)]-[(b)-(a)-(a)-]-, and so on.
From the viewpoint of adhesiveness to copper foil, heat resistance, coefficient of thermal expansion and flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0. It is 40 to 0.80.

In the above general formula (B-1), as a commercially available product of epoxidized polybutadiene having integers of a = 0.20, b = 0.20, c = 0.60, and y = 10 to 250, "Epolide (Epolide ( Examples thereof include "PB3600" (manufactured by Daicel Co., Ltd.), and it is preferable to use the commercially available product from the viewpoint of flexibility, impact resistance, mechanical strength and adhesiveness.

The component (B) is easily produced, for example, by epoxidizing polybutadiene having hydroxyl groups at both ends of the molecule with hydrogen peroxide or peracids.
As the polybutadiene having hydroxyl groups at both ends of the molecule as a raw material, liquid polybutadiene represented by the following general formula (B'-1) is preferable. That is, the (B) epoxy-modified polybutadiene is preferably obtained by epoxyizing the liquid polybutadiene represented by the following general formula (B'-1).

(In the formula, a, b, c and y are the same as those in the above general formula (B-1).)

As the polybutadiene having hydroxyl groups at both ends of the molecule as a raw material, a commercially available product can be used. Examples of commercially available products include "Poly.BD R-15HT" and "Poly.BD R-45HT" (above, polybutadiene manufactured by Idemitsu Kosan Co., Ltd.).
Polybutadiene having such a hydroxyl group has a hydroxyl group and contains more 1,4-vinyl bond structure of butadiene than 1,2-vinyl bond structure [(a + c)> b], so that the adhesive Is imparted with toughness, and tends to improve impact resistance and adhesion to copper foil.

<(C) Active ester compound>
The component (C) is an active ester compound. Since the thermosetting resin composition of the present invention contains the component (C), the melt viscosity at the time of molding can be reduced, and a particularly excellent moldability tends to be obtained.
Examples of the active ester compound (C) include those having a highly reactive ester group such as a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified compound of a heterocyclic hydroxy compound.
(C) One type of active ester compound may be used alone, or two or more types may be used in combination.
The active ester compound (C) is preferably a compound having two or more ester groups in one molecule.

The (C) active ester compound includes (c1) a polyvalent carboxylic acid compound (hereinafter, also referred to as “(c1) component”) and (c2) an aromatic compound having a phenolic hydroxyl group (hereinafter, also referred to as “(c2) component”). It is preferable that the compound is obtained by esterifying.
The compound obtained by esterifying the component (c1) and the component (c2) is an ester of at least one or more hydroxyl groups of the component (c1) and one or more carboxy groups of the component (c2). It is a compound formed by forming an ester bond by undergoing a conversion reaction (condensation reaction). Such an active ester compound (C) may be linear or multi-branched.

The (c1) polyvalent carboxylic acid compound is a compound having two or more carboxy groups in one molecule, and if the component (c1) is a compound having an aromatic ring, the heat resistance can be increased. .. Examples of the (c1) polyvalent carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable, from the viewpoint of heat resistance.
(C2) Examples of the aromatic compound having a phenolic hydroxyl group include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-. Cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxy Examples thereof include benzophenone, fluoroglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolac and the like.

The component (c2) is preferably an aromatic compound having a phenolic hydroxyl group represented by any of the following general formulas (C1-1) to (C1-5). That is, the component (C) is formed by esterifying the component (c1) and an aromatic compound having a phenolic hydroxyl group represented by any of the following general formulas (C1-1) to (C1-5). It is preferably a compound, and more preferably a compound represented by the following general formula (C-1).

(In the formula, k1 and k2 are independently 0 or 1, respectively.)

(In the formula, ^RC1 and ^RC2 are independently the residue of the general formula (C1-1), the residue of the general formula (C1-2), and k1 in the general formula (C1-4). The residue of the compound which is 1, or the residue of the compound where k2 is 0 in the above general formula (C1-5), and n is an integer of 1 to 5. In the present specification, the residue is referred to as a residue. Means the structure of the portion of the raw material component excluding the functional group provided for bonding, and has, for example, a phenolic hydroxyl group represented by any of the above general formulas (C1-1) to (C1-5). The residue of the aromatic compound is the structure of the portion of the aromatic compound excluding the phenolic hydroxyl group.)

The active ester compound (C) can be produced by a known method. Specifically, it can be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Further, as the (C) active ester compound, the active ester compound described in JP-A-2004-277460 can be used, or a commercially available product can also be used.
As the commercially available active ester compound, those containing a dicyclopentadienyldiphenol structure, acetylated products of phenol novolac, benzoyl products of phenol novolac and the like are preferable, and those containing a dicyclopentadienyl diphenol structure are more preferable. preferable. Specifically, "HPC-8000-65T" (manufactured by DIC Co., Ltd., ester group equivalent 223 g / mol), "SHC-5600TM65" (manufactured by SHIN-A, ester group equivalent 238 g / mol), "EXB9460S-65T". (DIC Co., Ltd., ester group equivalent 223 g / mol), "DC808" (Mitsubishi Chemical Co., Ltd., ester group equivalent 149 g / mol), "YLH1026" (Mitsubishi Chemical Co., Ltd., ester group equivalent 200 g / mol) , "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd., ester group equivalent 201 g / mol), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd., ester group equivalent 245 g / mol) and the like.

<One or more selected from the group consisting of (D) maleimide compound and its modified product>
The component (D) is at least one selected from the group consisting of maleimide compounds and modified products thereof. Since the thermosetting resin composition of the present invention contains the component (D), the adhesiveness to the copper foil tends to be particularly improved.
As the component (D), one or more selected from the group consisting of a compound having at least two N-substituted maleimide groups in one molecule and a modified product thereof is preferable.
As the component (D), one type may be used alone, or two or more types may be used in combination.
Hereinafter, the notation "(D) maleimide compound" refers to both the maleimide compound as the component (D) and the maleimide compound before modification used as a raw material for the modified product of the maleimide compound as the component (D). It shall point.

The weight average molecular weight (Mw) of the component (D) is preferably 400 to 3,000, more preferably 500 to 2,000, still more preferably 700 to 700, from the viewpoint of solubility in an organic solvent and mechanical strength. It is 1,500.

As the maleimide compound (D), for example, a maleimide compound having an aliphatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups (hereinafter, also referred to as “aliphatic hydrocarbon group-containing maleimide”). ), A maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups (hereinafter, also referred to as “aromatic hydrocarbon group-containing maleimide”) and the like. Among these, maleimide containing an aromatic hydrocarbon group is preferable from the viewpoint of adhesiveness to copper foil, heat resistance, and glass transition temperature. The aromatic hydrocarbon group-containing maleimide may contain an aromatic hydrocarbon group between any combination of two optionally selected maleimide groups.
As the maleimide compound (D), a maleimide compound having 2 to 5 N-substituted maleimide groups in one molecule is preferable from the viewpoint of adhesion to a copper foil, heat resistance and glass transition temperature, and the maleimide compound in one molecule is preferable. A maleimide compound having two N-substituted maleimide groups is more preferable.

Examples of the maleimide compound include aliphatic groups such as N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, bis (4-maleimidecyclohexyl) methane, and 1,4-bis (maleimidemethyl) cyclohexane. Hydrogen group-containing maleimide; m-phenylene bismaleimide, N, N'-(2-methyl-1,3-phenylene) bismaleimide, N, N'-(4-methyl-1,3-phenylene) bismaleimide, N, N'-(1,4-phenylene) bismaleimide, 4,4'-diphenylmethane bismaleimide, 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, 1,4- Bis (4-maleimide phenyl) cyclohexane, 1,4-bis (maleimide methyl) cyclohexane, 1,3-bis (4-maleimide phenoxy) benzene, 1,3-bis (3-maleimide phenoxy) benzene, bis [4- (3-Maleimide phenoxy) phenyl] methane, bis [4- (4-maleimide phenoxy) phenyl] methane, 1,1-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,1-bis [4- (4-Maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimide phenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimide phenoxy) phenyl] ethane, 2,2- Bis [4- (3-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (4-maleimide phenoxy) phenyl] butane, 2,2-bis [4- (3-maleimide phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane , 2,2-Bis [4- (4-maleimide phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimide phenoxy) biphenyl, 4,4 -Bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] ketone, bis [4- (4-maleimide phenoki) Benzene] ketone, 2,2'-bis (4-maleimidephenyl) disulfide, bis (4-maleimidephenyl) disulfide, bis [4- (3-maleimidephenoxy) phenyl] sulfide, bis [4- (4- (4- (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] sulfone, bis [4- (3-maleimide phenoxy) phenyl] ether, bis [4- (4-maleimide phenoxy) phenyl] ether, 1,4-bis [4- ( 4-Maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3- (3-) Maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimide phenoxy) ) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidephenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4 -Bis [4- (3-maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) -3,5-dimethyl-α, Examples thereof include aromatic hydrocarbon group-containing maleimides such as α-dimethylbenzyl] benzene and polyphenylmethane maleimide.

The maleimide compound (D) preferably contains the maleimide compound (D1) represented by the following general formula (D1-1) from the viewpoint of adhesiveness to the copper foil, heat resistance and glass transition temperature.

(In the formula, R ^D1 and R ^D2 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms, and X ^D1 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. Alkylidene group, -O-, -C (= O)-, -S-, -SS- or sulfonyl group. P and q are independently integers of 0 to 4).

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms indicated by ^RD1 and ^RD2 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-. Examples include pentyl groups. Among these, a methyl group and an ethyl group are preferable from the viewpoints of adhesiveness to copper foil, heat resistance, and glass transition temperature. The aliphatic hydrocarbon group preferably has 1 to 3 carbon atoms.
Examples of the halogen atom indicated by R ^D1 and R ^D2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As the alkylene group having 1 to 5 carbon atoms represented by X ^D1, methylene group, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like Be done. Among these, a methylene group is preferable from the viewpoints of adhesiveness to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion and moldability. The alkylene group preferably has 1 to 3 carbon atoms.
The alkylidene group having 2 to 5 carbon atoms represented by X ^D1, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, an isopropylidene group is preferable from the viewpoints of adhesiveness to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion and moldability.
Among the above options, X ^D1 preferably has an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. More preferable are as described above.
p and q are each independently an integer of 0 to 4, and are preferably 0 from the viewpoints of adhesiveness to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion, and moldability. An integer of ~ 2, more preferably 0 or 1, and even more preferably 0. When p or q is an integer of 2 or more, the plurality of ^RD1s or the plurality of ^RD2s may be the same or different.

Further, the maleimide compound (D) has the following general formulas (D2-1) to (D2-3) from the viewpoints of adhesion to copper foil, heat resistance, glass transition temperature, dielectric properties, coefficient of thermal expansion and moldability. It is preferable to contain the maleimide compound (D2) represented by any of the above.

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

In the above general formula (D2-1), s is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3 from the viewpoint of availability. In particular, the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (D2-1) is preferably a mixture of s = 0 to 3.

The maleimide compound (D) is a maleimide compound (D1) represented by the above general formula (D1-1) and a maleimide compound represented by any of the above general formulas (D2-1) to (D2-3). When D2) and is contained, the content ratio (mass ratio) of the maleimide compound (D1) and the maleimide compound (D2) is preferably 30:70 to 97: 3, more preferably 50:50 to 95: 5. It is preferable, and 70:30 to 90:10 is more preferable. Even when the pre-reaction described later is carried out, it is preferable that the composition of the maleimide compound (D) used as a raw material thereof satisfies the above-mentioned content ratio.

The component (D) may be a modified product of the maleimide compound from the viewpoints of adhesiveness to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion and moldability.
As modified products of the maleimide compound, the (D) maleimide compound is referred to as (d1) a monoamine compound having an acidic substituent (hereinafter, also referred to as “(d1) component”) and (d2) a diamine compound (hereinafter, “(d2)). It is preferable that the compound is reacted with one or more kinds selected from the group consisting of "components" (hereinafter also referred to as "pre-reaction"), and is selected from the group consisting of a maleimide compound (D1) and a maleimide compound (D2). A compound obtained by reacting one or more maleimide compounds with one or more selected from the group consisting of the (d1) component and the (d2) component is more preferable, and the maleimide compound (D1) and the maleimide compound (D2) are (1). A compound obtained by reacting with the component d1) and the component (d2) is more preferable.

((D1) Monoamine compound having an acidic substituent)
The component (d1) is preferably a compound represented by the following general formula (d1-1).

(In the formula, R ^d1 is an acidic substituent selected from the group consisting of a hydroxyl group, a carboxy group and a sulfonic acid group, R ^d2 is an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is 1 to 1. The integer of 5 and u are integers of 0 to 4 and satisfy 1 ≦ t + u ≦ 5).

The acidic substituent indicated by R ^d1 is preferably a hydroxyl group or a carboxy group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
t is an integer of 1 to 5, and is preferably an integer of 1 to 3, more preferably 1 or, from the viewpoint of adhesiveness to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion, and moldability. 2, more preferably 1. When t is an integer of 2 or more, a plurality of R ^d1s may be the same or different.
Examples of the alkyl group having 1 to 5 carbon atoms indicated by R ^d2 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. .. The alkyl group preferably has 1 to 3 carbon atoms.
Examples of the halogen atom indicated by R ^d2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
u is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 to 3, from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion and moldability. It is an integer of 2, more preferably 0 or 1, and particularly preferably 0. When u is an integer of 2 or more, the plurality of R ^d2s may be the same or different.
The component (d1) is more preferably the following general formula (d1-1') or (d1-) from the viewpoint of adhesiveness to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion and moldability. It is a monoamine compound represented by 1''), and more preferably a monoamine compound represented by the following general formula (d1-1''). However, R ^d1 , R ^d2 and u in the general formula (d1-1') or (d1-1'') are the same as those in the general formula (d1-1), and the preferred ones are also the same. ..

As the component (d1), o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-amino Benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and reactivity, and o-aminophenol is preferable from the viewpoint of heat resistance. , M-Aminophenol and p-Aminophenol are preferable, and p-Aminophenol is more preferable in consideration of dielectric properties, thermal expansion coefficient and production cost.
As the component (d1), one type may be used alone, or two or more types may be used in combination.

((D2) diamine compound)
The component (d2) is preferably a diamine compound having at least two benzene rings, more preferably a diamine compound having at least two benzene rings linearly between two amino groups, and the following general formula (d2-). The diamine compound represented by any of 1) to (d2-3) is more preferable. That is, in the compound obtained by reacting the maleimide compound (D1) and the maleimide compound (D2) with the components (d1) and (d2), the component (d1) is represented by the above general formula (d1-1), and ( It is preferable that the component d2) is represented by any of the following general formulas (d2-1) to (d2-3).

(In the formula, X ^d1 is a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, -C (= O)-, a fluorenylene group or a phenylenedioxy. The groups, R ^d3 and R ^d4, are independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxy group or a sulfonic acid group, respectively. Are independently integers from 0 to 4.
Each of X ^d2 and X ^d3 is independently a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an -O- or a sulfonyl group. )

Examples of the alkylene group having 1 to 5 carbon atoms indicated by X ^d1 include a methylene group, an ethylene group, a propylene group, a propylene group and the like. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.
Examples of the alkylidene group having 2 to 5 carbon atoms indicated by X ^d1 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. The alkylidene group is preferably an isopropylidene group.
As X ^d1 , a single bond, an alkylene group having 1 to 5 carbon atoms, —O— is preferable, and a methylene group, —O− is more preferable.

^Examples of the alkyl group having 1 to 5 carbon atoms indicated by R ^d3 and 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. Can be mentioned. The alkyl group preferably has 1 to 3 carbon atoms.
^Examples of the alkoxy group having 1 to 5 carbon atoms indicated by R ^d3 and R ^d4 include a methoxy group, an ethoxy group, a propoxy group and the like. As the alkoxy group, a methoxy group is preferable.
Examples of the halogen atom indicated by R ^d3 and R ^d4 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
v and w are each independently, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^d2 and X ^d3 will be described in the same manner as X ^d1 in the above general formula (d2-1).
As X ^d2 , a single bond, an alkylidene group having 2 to 5 carbon atoms, and a sulfonyl group are preferable.
As X ^d3 , an alkylidene group having 2 to 5 carbon atoms is preferable, and an isopropylidene group is more preferable.

As the component (d2), 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4 ′ -Diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylketone, benzidine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-dimethyl-5,5'-Diethyl-4,4'-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-) Aminophenoxy benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- ( 4-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-Aminophenyl) -1-methylethyl] benzene and the like can be mentioned. Among these, from the viewpoints of reactivity, adhesion to copper foil and dielectric properties, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'- Diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl ether, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,4-bis [1-( 4-Aminophenyl) -1-methylethyl] benzene is preferred, and 4,4'-diaminodiphenylmethane is more preferred. From the viewpoint of manufacturing cost, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4 , 4'-diaminodiphenyl ether is preferable, and 4,4'-diaminodiphenylmethane is more preferable.
As the component (d2), one type may be used alone, or two or more types may be used in combination.

The pre-reaction is preferably carried out by reacting at a reaction temperature of 70 to 200 ° C. for 0.1 to 10 hours in the presence of an organic solvent described later.
The reaction temperature is more preferably 70 to 160 ° C, still more preferably 70 to 130 ° C, and particularly preferably 80 to 120 ° C. The reaction time is more preferably 1 to 6 hours, still more preferably 2 to 5 hours.

The amount of the component (d1) used in the pre-reaction is such that the number of moles of the component (d1) is in the range of 0.2 to 0.5, assuming that the total number of moles of the (D) maleimide compound is 1. Is preferable. When the amount of the component (d1) used is 0.2 or more, the decrease in reactivity tends to be suppressed, and when it is 0.5 or less, the heat resistance, the dielectric property and the glass transition temperature tend to be good. is there.
As for the amount of the component (d2) to be used, it is preferable that the number of moles of the component (d2) is in the range of 0.05 to 0.25, assuming that the total number of moles of the (D) maleimide compound is 1. When the amount of the component (d2) used is 0.05 or more, the decrease in reactivity tends to be suppressed, and when it is 0.25 or less, the heat resistance and the dielectric property tend to be good.

In the reaction of the maleimide compound, the component (d1) and the component (d2), the amounts used by the three parties are the primary amino group equivalents of the components (d1) and (d2) [-NH ₂ group equivalents and the equivalents. It is preferable that the relationship between the sum of [Note] and the sum of the maleimide group equivalents of the maleimide compound (D) satisfies the following formula.
1.5 ≤ [sum of maleimide group equivalents] / [sum of -NH ₂ group equivalents] ≤ 10
By setting [total maleimide group equivalents] / [total sum of -NH ₂ group equivalents] to 1.5 or more, gelation tends to be difficult and heat resistance tends to be difficult to decrease, and by setting it to 10 or less, it tends to be difficult. It is preferable because the solubility in an organic solvent, the adhesiveness with a copper foil, and the heat resistance tend to be difficult to decrease.
From the same point of view, more preferably
Satisfy 2 ≤ [sum of maleimide group equivalents] / [sum of -NH ₂ group equivalents] ≤ 8
More preferably
3 ≦ [sum of maleimide group equivalents] / [sum of -NH ₂ group equivalents] ≦ 6 is satisfied.
More preferably
4 ≤ [sum of maleimide group equivalents] / [sum of -NH ₂ group equivalents] ≤ 6 is satisfied.

(Organic solvent)
The organic solvent used for the pre-reaction is not particularly limited as long as it does not adversely affect the reaction. 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; ether solvents such as tetrahydrofuran; toluene, Aromatic solvents such as xylene and mesitylen; nitrogen atom-containing solvents including amide solvents such as dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents including sulfoxide solvents such as dimethylsulfooxide. Solvent; Examples thereof include ester solvents such as ethyl acetate and γ-butyrolactone. Among these, cyclohexanone, propylene glycol monomethyl ether, and N, N-dimethylacetamide are preferable, and N, N-dimethylacetamide is preferable from the viewpoint of excellent solubility, high volatility, and less likely to remain as a residual solvent during the production of prepreg. More preferred.
As the organic solvent, one type may be used alone, or two or more types may be used in combination.

From the viewpoint of solubility and reaction efficiency, the amount of the organic solvent used is preferably 25 to 1,000 parts by mass with respect to 100 parts by mass of the total of the (D) maleimide compound, the (d1) component and the (d2) component. It is more preferably 40 to 250 parts by mass, and further preferably 50 to 150 parts by mass. When the amount of the organic solvent used is not less than the above lower limit value, it tends to be easy to secure solubility, and when it is not more than the above upper limit value, it tends to be easy to suppress a significant decrease in reaction efficiency.

The pre-reaction may be carried out in the presence of a reaction catalyst, if necessary. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine.
One type of reaction catalyst may be used alone, or two or more types may be used in combination.

<(E) Epoxy resin containing an alicyclic skeleton>
The component (E) is an epoxy resin containing an alicyclic skeleton. The thermosetting resin composition of the present invention has excellent dielectric properties and laser processability by containing the component (E).
As the component (E), one type may be used alone, or two or more types may be used in combination.

As the alicyclic skeleton contained in the component (E), an alicyclic skeleton having 5 to 20 ring-forming carbon atoms is preferable, an alicyclic skeleton having 5 to 18 ring-forming carbon atoms is more preferable, and an alicyclic skeleton having 6 to 18 ring-forming carbon atoms is more preferable. The alicyclic skeleton of 18 is more preferable, the alicyclic skeleton having 8 to 14 ring-forming carbon atoms is particularly preferable, and the alicyclic skeleton having 8 to 12 ring-forming carbon atoms is most preferable.
Further, the alicyclic skeleton is preferably composed of 2 or more rings, more preferably 2 to 4 rings, and further preferably 3 rings. Examples of the alicyclic skeleton having two or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, and a dicyclopentadiene skeleton.
As the alicyclic skeleton, a dicyclopentadiene skeleton is preferable, and an alicyclic skeleton represented by the following general formula (E-1) is more preferable.

(Wherein, R ^E1 is an alkyl group having 1 to 12 carbon atoms, optionally .m ^E1 wherever substituted in the alicyclic skeleton is an integer from 0 to 6. * Are the other structures It is the binding site of.)

In the general formula ^(E1), the alkyl group having 1 to 12 ^carbon atoms ^{R E1} represents a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl Groups, n-pentyl groups and the like can be mentioned. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
m ^E1 is an integer of 0 to 6, preferably an integer of 0 to 2, and more preferably 0.
When m ^E1 is an integer of 2 to 6, the plurality of ^RE1s may be the same or different. Further, the plurality of ^RE1s may be substituted on the same carbon atom to the extent possible, or may be substituted on different carbon atoms.
* Is a binding site to another structure and may be bonded by any carbon atom on the alicyclic skeleton, but the carbon atom represented by 1 or 2 in the following general formula (E-1'). And, it is preferable that they are bonded by a carbon atom represented by any of 3 to 4.

(In the formula, ^RE1 , m ^E1 and * are the same as those in the above general formula (E-1).)

The component (E) is not particularly limited as long as it is an epoxy resin having an alicyclic skeleton, but is preferably an epoxy resin having two or more epoxy groups. The component (E) is classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among these, a glycidyl ether type epoxy resin is preferable.

As the component (E), a dicyclopentadiene type epoxy resin is preferable.
The dicyclopentadiene type epoxy resin preferably has a structural unit represented by the following general formula (E-2).

The number of structural units of the structural unit in the epoxy resin having the structural unit represented by the general formula (E-2) is 1 or more, preferably 1 to 10, and more preferably 3 to 7. Is the number of.
Here, the number of structural units indicates an integer value in a single molecule and a rational number which is an average value in an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units.

As the epoxy resin having the structural unit represented by the general formula (E-2), the epoxy resin represented by the following general formula (E-3) is preferable.

(In the formula, n ^E1 is a number of 1 or more)

N ^E1 in the general formula (E-3) is a number of 1 or more, preferably 1 to 10, and more preferably 3 to 7. When n ^E1 is within the above range, the resolution and the adhesion to the inner layer circuit tend to be further improved.

The epoxy resin represented by the above general formula (E-3) is commercially available as, for example, HP-7200H (manufactured by DIC Corporation, trade name) and XD-1000 (manufactured by Nippon Kayaku Co., Ltd., trade name). It is possible.

Further, as the component (E), an epoxy resin represented by the following general formula (E-4) is also preferably mentioned.

The epoxy resin represented by the general formula (E-4) is commercially available as, for example, ADEKA REGIN EP-4088S and EP-4088L (both manufactured by ADEKA Corporation, trade names).

[Contents of components (A) to (E) in the thermosetting resin composition]
The content of each component in the thermosetting resin composition of the present invention will be described. In the following description of the content, each component is not necessarily contained in the thermosetting resin composition in the same structure, that is, some components are reacting, but here, for convenience, the use of each component is used. The amount is referred to as "content".
The content of the component (A) in the thermosetting resin composition of the present invention is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. It is preferably 3 to 15 parts by mass, more preferably 4 to 10 parts by mass, and particularly preferably 5 to 9 parts by mass. When the content of the component (A) is at least the above lower limit value, the dielectric property tends to be good, and further, the solubility is ensured and it tends to be difficult to precipitate during the production of the resin varnish, which is below the above upper limit value. Since the unreacted component is unlikely to remain, there is a tendency that a decrease in adhesiveness with the copper foil can be suppressed.
The content of the component (B) in the thermosetting resin composition of the present invention is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. It is preferably 2 to 15 parts by mass, more preferably 3 to 12 parts by mass, and particularly preferably 4 to 7 parts by mass. When the content of the component (B) is at least the above lower limit value, the adhesiveness with the copper foil tends to be good, and when it is at least the above upper limit value, the heat resistance tends to be good.
The content of the component (C) in the thermosetting resin composition of the present invention is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. It is preferably 3 to 20 parts by mass, more preferably 4 to 17 parts by mass. When the content of the component (C) is at least the above lower limit value, the moldability tends to be good, and when it is at least the above upper limit value, the adhesiveness with the copper foil tends to be good.
The content of the component (D) in the thermosetting resin composition of the present invention is preferably 40 to 85 parts by mass, based on 100 parts by mass of the total of the components (A) to (E) in terms of solid content. It is preferably 45 to 80 parts by mass, more preferably 50 to 75 parts by mass. When the content of the component (D) is at least the above lower limit value, the heat resistance tends to be excellent, and when it is at least the above upper limit value, the fluidity and moldability of the thermosetting resin composition tend to be good. is there.
The content of the component (E) in the thermosetting resin composition of the present invention is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. It is preferably 2 to 20 parts by mass, more preferably 3 to 15 parts by mass, and particularly preferably 3 to 12 parts by mass. When the content of the component (E) is at least the above lower limit value, the heat resistance tends to be excellent, and when it is at least the above upper limit value, the fluidity and moldability of the thermosetting resin composition tend to be good. is there.

<Other ingredients>
The thermosetting resin composition of the present invention may contain components other than the components (A) to (E). Other components include, for example, (F) curing accelerator, (G) flame retardant, (H) inorganic filler, colorant, antioxidant, reducing agent, ultraviolet absorber, fluorescent whitening agent, and adhesion improvement. Examples include agents and organic fillers. One of these may be used alone, or two or more thereof may be used in combination. Among these, the thermosetting resin composition of the present invention further comprises (F) a curing accelerator, (G) a flame retardant, and (H) an inorganic filler in addition to the components (A) to (E). It is preferable that it contains at least one selected from the group.

((F) Curing accelerator)
The curing reaction can be promoted by containing (F) a curing accelerator (hereinafter, also referred to as “component (F)”) in the thermosetting resin composition of the present invention.
(F) Ingredients include imidazoles and their derivatives; organophosphorus compounds such as phosphines and phosphonium salts, and adducts of tertiary phosphines and quinones; secondary amines, tertiary amines, quaternary amines. Examples include ammonium salts. Among these, imidazoles and derivatives thereof are preferable from the viewpoint of adhesiveness to copper foil, heat resistance and flame retardancy.
As the component (F), 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 the component (F), the content thereof is the component (A) in terms of solid mass, from the viewpoint of curing acceleration effect and storage stability. With respect to 100 parts by mass of the total of the components C) and (E), preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and further preferably 0.5 to 1.5 parts by mass. Is.

((G) Flame Retardant)
By incorporating a flame retardant into the thermosetting resin composition of the present invention, flame retardancy is improved.
As the flame retardant (G), metal hydrates such as aluminum hydroxide and magnesium hydroxide having a thermal decomposition temperature of less than 300 ° C.; halogen-containing flame retardants containing bromine, chlorine and the like; phosphorus flame retardants; sulfamic acid. Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate, melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide and zinc molybdate. .. Among these, from the viewpoint of environmental protection, flame retardants other than halogen-containing flame retardants are preferable, and heat resistance, adhesion to copper foil, elastic modulus, thermal expansion coefficient, etc. are less likely to decrease, and high flame retardancy is achieved. From the viewpoint of imparting, a phosphorus-based flame retardant is more preferable.
Phosphorus-based flame retardants include inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants.
Examples of the inorganic phosphorus-based flame retardant include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide; phosphorus. Acid; phosphine oxide and the like.
Examples of the organic phosphorus flame retardant include aromatic phosphoric acid ester, monosubstituted phosphonic acid diester, disubstituted phosphinic acid ester, metal salt of disubstituted phosphinic acid, organic nitrogen-containing phosphorus compound, cyclic organic phosphorus compound, and phosphorus. Examples include phenolic resin. Among these, a metal salt of an aromatic phosphoric acid ester and a disubstituted phosphinic acid is preferable. Here, as the metal salt, any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt is preferable, and aluminum salt is more preferable.
Among these phosphorus-based flame retardants, one or more selected from the group consisting of a metal salt of an aromatic phosphoric acid ester and a disubstituted phosphinic acid is more preferable from the viewpoint of dielectric properties and glass transition temperature.

Aromatic phosphates include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresildiphenyl phosphate, cresildi-2,6-xylenyl phosphate, resorcinolbis (diphenyl phosphate), 1,3-phenylene. Examples thereof include bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), and 1,3-phenylene bis (diphenyl phosphate).
Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, and a metal salt of diarylphosphinic acid.
(G) One type of flame retardant may be used alone, or two or more types may be used in combination.

When the thermosetting resin composition of the present invention contains (G) a flame retardant, the content thereof is the solid content-equivalent components (A) to (E) from the viewpoint of flame retardancy. It is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 1 to 8 parts by mass with respect to 100 parts by mass of the total.

((H) Inorganic filler)
By incorporating the (H) inorganic filler in the thermosetting resin composition of the present invention, the coefficient of thermal expansion can be reduced and the elastic modulus, heat resistance and flame retardancy can be improved.
Examples of the inorganic filler (H) include silica, alumina, titanium oxide, mica, berylia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide and aluminum silicate. , Calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fibers, fine glass powder, hollow glass, etc. .. As the glass, E glass, T glass, D glass and the like are preferably mentioned. Among these, silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is further preferable, from the viewpoint of adhesiveness to copper foil, heat resistance, and flame retardancy.
Examples of silica include crushed silica, fumed silica, and spherical silica. As the silica, spherical silica is preferable from the viewpoint of the coefficient of thermal expansion and the fluidity when filled in the thermosetting resin composition.

The average particle size of the inorganic filler (H) is not particularly limited, but is preferably 0.01 to 30 μm, more preferably 0.1 to 10 μm, and even more preferably 0.5 to 6 μm. By setting the average particle size of silica to 0.01 μm or more, the fluidity tends to be maintained well even when highly filled, and by setting it to 30 μm or less, the probability of mixing coarse particles is reduced and the coarse particles are coarse particles. There is a tendency to suppress the occurrence of defects caused by. Here, the average particle size is the particle size of a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%, and the laser diffraction scattering method is used. It can be measured with the particle size distribution measuring device or the like.
The specific surface area of the (H) inorganic filler is preferably 4 m ² / g or more, more preferably 4 to 9 m ² / g, and further preferably 5 to 7 m ² / g.
As the (H) inorganic filler, one type may be used alone, or two or more types may be used in combination.

The inorganic filler (H) may be surface-treated with a coupling agent. That is, it is also preferable to directly surface-treat the (H) inorganic filler such as silica by a dry method or a wet method, and then use it as it is at the time of blending or as a slurry. On the other hand, a so-called integral blend treatment method may be adopted in which a (H) inorganic filler such as silica whose surface has not been treated is mixed in the resin composition, and then a surface treatment agent is added to the resin composition.

When the thermosetting resin composition of the present invention contains (H) an inorganic filler, the content thereof is the solid content-equivalent components (A) to (E) from the viewpoint of flame retardancy. It is preferably 20 to 110 parts by mass, more preferably 30 to 90 parts by mass, still more preferably 40 to 80 parts by mass, and particularly preferably 45 to 75 parts by mass with respect to 100 parts by mass of the total.

(Organic solvent)
The thermosetting resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating handling by diluting and facilitating the production of a prepreg described later. In this specification, the thermosetting resin composition containing an organic solvent may be referred to as a resin varnish.
Examples of the organic solvent include methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, and dipropylene. Alcohol-based solvents such as glycol monomethyl ether, propylene glycol monopropyl ether and dipropylene glycol monopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran; toluene, xylene, mesityrene and the like. Aromatic solvents; nitrogen atom-containing solvents such as formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide; methoxyethyl acetate. , Ethyl ethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ester-based solvents such as γ-butyrolactone and the like.
Among these, an alcohol solvent, a ketone solvent, an aromatic solvent, and a nitrogen atom-containing solvent are preferable, and methyl ethyl ketone is more preferable, from the viewpoint of solubility.
As the organic solvent, one type may be used alone, or two or more types may be used in combination.
The content of the organic solvent in the thermosetting resin composition of the present invention may be appropriately adjusted to such an extent that the thermosetting resin composition can be easily handled, and the range in which the coatability of the resin varnish is good. However, the solid content concentration (concentration of components other than the organic solvent) of the thermosetting resin composition is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and further preferably. It should be 50 to 70% by mass.

(Physical characteristics and characteristics of thermosetting resin composition)
The thermosetting resin composition of the present invention has a low melt viscosity in the B stage state, has good press moldability, and is excellent in adhesiveness to copper foil, dielectric properties, and the like. In addition, the thermosetting resin composition is also excellent in solubility in an organic solvent.
The dielectric properties of the thermosetting resin composition of the present invention are preferably 4.05 or less, more preferably 4.00 or less, and further preferably 3. in terms of the relative permittivity measured by the method described in Examples. It is 98 or less. The dielectric loss tangent measured by the method described in Examples is preferably 0.0080 or less, more preferably 0.0070 or less, still more preferably 0.0068 or less.
The glass transition temperature (Tg) of the thermosetting resin composition of the present invention is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 210 ° C. in terms of Tg measured by the method described in Examples. That is all.

[Prepreg]
The prepreg of the present invention contains the thermosetting resin composition of the present invention.
The prepreg of the present invention can be produced by impregnating or coating a sheet-shaped reinforcing base material with the thermosetting resin composition and semi-curing (B-staged) by heating or the like.
As the sheet-shaped reinforcing base material of the prepreg, well-known materials used for various laminated plates for electrical insulating materials can be used. As the material of the sheet-like reinforcing base material, natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber and asbestos; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, polytetrafluoroethylene and acrylic; Examples include mixtures. Among these, glass fiber is preferable from the viewpoint of flame retardancy. As the glass fiber base material, a woven cloth using E glass, C glass, D glass, S glass, etc. or a glass woven cloth in which short fibers are bonded with an organic binder; a mixture of glass fibers and cellulose fibers, etc. Can be mentioned. More preferably, it is a glass woven cloth using E glass.
These sheet-shaped reinforcing base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats. The material and shape are selected according to the intended use and performance of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as needed.

The following hot melt method or solvent method is preferable as a method for impregnating or coating the sheet-shaped reinforcing base material with the thermosetting resin composition.
In the hot melt method, the thermosetting resin composition does not substantially contain an organic solvent, and (1) once coats a coated paper having good peelability from the composition, and then the sheet-like reinforcing base material is used. It is a method of laminating, or (2) a method of directly coating a sheet-shaped reinforcing base material with a die coater.
On the other hand, in the solvent method, a resin varnish is prepared by impregnating a thermosetting resin composition with an organic solvent, the sheet-shaped reinforcing base material is immersed in the resin varnish, and the sheet-shaped reinforcing base material is impregnated with the resin varnish. After that, it is a method of drying.

The thickness of the sheet-shaped reinforcing base material can be, for example, about 0.03 to 0.5 mm, and the one surface-treated with a silane coupling agent or the like or the one mechanically opened. It is preferable from the viewpoint of heat resistance, moisture resistance and processability. After impregnating or coating a base material with a thermosetting resin composition, the substrate is usually semi-cured (B-staged) by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes. You can get a prepreg.
One prepreg may be used, or preferably 2 to 20 prepregs may be stacked as required.

[Copper-clad laminate]
The copper-clad laminate of the present invention is formed by laminating the above prepreg and copper foil. For example, it can be manufactured by using one of the above prepregs, or by stacking 2 to 20 prepregs as needed and laminating and molding them in a configuration in which copper foils are arranged on one side or both sides.
As the molding conditions for the copper-clad laminate, a known molding method for an electrically insulating material laminate and a multilayer plate can be applied, and a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, or the like can be used, for example. It can be molded under the conditions of a temperature of 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
Further, the prepreg of the present invention and the printed wiring board for the inner layer can be combined and laminated to produce a multilayer board.
The thickness of the copper foil may be appropriately selected depending on the intended use of the printed wiring board and the like, and is not particularly limited, but is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 50 μm, and particularly preferably. It is 5 to 30 μm.

It is also preferable to form a plating layer by plating the copper foil.
The metal of the plating layer is not particularly limited as long as it is a metal that can be used for plating. The metal of the plating layer is preferably copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. It is preferably selected.
The plating method is not particularly limited, and known methods such as an electrolytic plating method and an electroless plating method can be used.

[Printed circuit board]
The printed wiring board of the present invention is made by using the copper-clad laminate of the present invention.
The printed wiring board of the present invention can be manufactured by applying circuit processing to the metal foil of a copper-clad laminate. In circuit processing, for example, after forming a resist pattern on the copper foil surface, removing unnecessary parts of the copper foil by etching, peeling the resist pattern, forming necessary through holes with a drill, and forming the resist pattern again, the resist pattern is formed. This can be done by plating the through holes to make them conductive, and finally peeling off the resist pattern. The copper-clad laminate described above is further laminated on the surface of the printed wiring board thus obtained under the same conditions as described above, and further circuit-processed in the same manner as described above to obtain a multilayer printed wiring board. Can be done. In this case, it is not always necessary to form through holes, and via holes may be formed or both may be formed. Such multi-layering may be performed on the required number of sheets.

[Semiconductor package]
The semiconductor package of the present invention is made by using the printed wiring board of the present invention.
The semiconductor package of the present invention can be manufactured by mounting a semiconductor chip, a memory, or the like at a predetermined position on the printed wiring board of the present invention.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention in any sense.

[Evaluation method]
<1. Minimum melt viscosity temperature, 2. Minimum melt viscosity>
Using the thermosetting resin component powder collected by kneading the prepreg prepared in each example as a tablet and using the TMA test device "Q400EM" (manufactured by TA Instruments), 100 ° C to 180 ° C (heating rate: 10 ° C) The flow value when extruded at a predetermined pressure while increasing to (/ min) was measured, and the temperature at which the minimum melt viscosity and the minimum melt viscosity of the apparent melt viscosity calculated by the following formula were obtained (minimum melt viscosity temperature) was determined. It was measured.

η = apparent minimum melt viscosity (unit: Pa · s)
P: Extrusion pressure (unit: Pa)
R: Extruded plastometer nozzle radius (unit: cm)
L: Extruded plastometer nozzle length (unit: cm)
Q = Flow value (Unit: cm ³ / s)

<3. Solder heat resistance>
The copper-clad laminates produced in each example were cut into 25 mm squares, floated in a solder bath at 288 ° C., visually observed, and the time (unit: seconds) until the substrate swelled was measured. The maximum observation time is 1800 seconds, and if no swelling is observed even after 1800 seconds, it is uniformly indicated as ">1800". The longer the time, the better the heat resistance.

<4. Glass transition temperature (Tg)>
The copper-clad laminate prepared in each example was immersed in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to prepare a 5 mm square evaluation substrate from which the copper foil was removed, and the TMA test apparatus "Q400EM" was prepared. (Manufactured by TA Instruments), observe the thermal expansion characteristics in the plane direction (Z direction) of the evaluation substrate at 25 to 280 ° C (heating rate: 10 ° C / min), and set the bending point of the expansion amount to glass. The transition temperature was used.

<5. Adhesion with copper foil (copper foil peel strength)>
By immersing the copper-clad laminates produced in each example in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Corporation), a copper foil having a width of 3 mm was formed to produce an evaluation substrate, and a tensile tester " The peel strength of the copper foil was measured using "Ez-Test" (manufactured by Shimadzu Corporation), and used as an index of the adhesiveness with the copper foil.
(Evaluation criteria)
A: 0.80 kN / m or more B: 0.70 kN / m or more, less than 0.80 kN / m

<6. Dielectric properties (relative permittivity Dk, dielectric loss tangent Df)>
After removing the copper foil by immersing the copper-clad laminate produced in each example in the copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.), the copper foil was cut into 2 mm x 85 mm, and the network analyzer "E8364B" was used. The relative permittivity and dielectric loss tangent of the copper-clad laminate at 5 GHz were measured by a cavity resonator persulfation method using (manufactured by Aglient Technologies).

<7. Laser workability>
(1) Beer hole formation For the double-sided copper-clad laminates obtained in each example, a CO ₂ laser machine (manufactured by Hitachi Via Mechanics, Ltd., trade name: LC-2E21B / 1C) was used, and the mask diameter was 1. Drill holes under the conditions of 60 mm, focus offset value 0.050, pulse width 18 μs, power 0.66 W, aperture 2, number of shots 5, burst mode, and make a via hole with a via hole top diameter (diameter) of 50 μm on the laminated plate surface. Formed.
(2) Desmear treatment The laminated board on which the via hole is formed is immersed in a swelling liquid, "Swelling Dip Securigant P" (glycol ethers, aqueous solution of sodium hydroxide, manufactured by Atotech Japan Co., Ltd.) at 60 ° C. for 10 minutes. Then, as a roughening solution, soak in "Concentrate Compact P" (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution, manufactured by Atotech Japan Co., Ltd.) at 80 ° C. for 20 minutes, and finally inside. As a Japanese solution, an evaluation substrate was prepared by immersing in "Reduction Shorusin Securigant P" (aqueous solution of sulfuric acid, manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes and then drying at 80 ° C. for 10 minutes.
(3) Measurement of maximum smear length The circumference of the bottom of the via hole of the evaluation substrate obtained above is observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole is measured from the image to measure the diameter of the via hole. The ratio of the maximum smear length to the ratio was calculated and used as an index for evaluating laser workability. The smaller the ratio, the better the laser workability.

[Manufacturing Example 1]
(Preparation of BMI and BMI-4000 modified product)
As maleimide compounds, 627 g (1.75 mol) of 4,4'-diphenylmethanebismaleimide (corresponding to the compound represented by the above general formula (D1-1)) and 2,2-bis [4- (4-maleimide phenoxy)). Phenyl] propane (corresponding to the compound represented by the above general formula (D2-2)) 143 g (0.25 mol), p-aminophenol [(d1) component] 55 g (0.50 mol), 4,4'-diamino -3,3'-Diethyldiphenylmethane [(d2) component] 48 g (0.19 mol) and N, N-dimethylacetamide were mixed so that the solid content concentration was 60% by mass, and reacted at 125 ° C. for 240 minutes. A solution of the modified product of BMI and BMI-4000 was obtained. Incidentally, the maleimide group equivalent of from maleimide compound, (d1) component and (d2) the ratio of the sum of -NH ₂ group equivalents from components ([maleimide group equivalent) / (- NH ₂ groups sum of equivalents] of 4 It was set to .57.

[Examples 1 to 5, Comparative Example 1]
Each component shown above is blended in the composition shown in Table 1 (unit: parts by mass. However, in the case of a solution, the solid content conversion amount is shown), and the solid content concentration (including an inorganic filler) is 65. Methyl ethyl ketone was added so as to be .5% by mass, and a thermosetting resin composition (resin varnish) of each Example and each Comparative Example was prepared.
Each of the obtained thermosetting resin compositions was impregnated with a 0.1 mm thick E glass cloth "# 3313" (model number, manufactured by Nitto Boseki Co., Ltd.) and dried by heating at 135 ° C. for 3.5 minutes. A prepreg (content of thermosetting resin composition: 56 ± 2% by mass) was obtained.
18 μm copper foil “YGP-18” (manufactured by Nippon Denki Co., Ltd.) was layered on both sides of a stack of eight prepregs, and heated at a temperature of 210 ° C. and a pressure of 25 kgf / cm ² (= 2.45 MPa) for 80 minutes. Pressure molding was performed to prepare a double-sided copper-clad laminate having a thickness of 0.8 mm (for eight prepregs). Each evaluation was carried out according to the above method using the prepared copper-clad laminate. The results are shown in Table 1.

Hereinafter, each component used in each example will be described.

(A) Component: Copolymer resin SMA-EF40 (copolymer resin of styrene and maleic anhydride, styrene / maleic anhydride = 4, Mw = 11,000, manufactured by Sartmer, trade name)

(B) Component: Epoxy-modified polybutadiene, PB3600 (epoxy-modified polybutadiene having hydroxyl groups at both ends of the molecule, manufactured by Daicel Corporation, trade name)

Ingredient (C): Active ester compound HPC-8000-65T (active ester compound containing a dicyclopentadiene type diphenol structure, manufactured by DIC Corporation, trade name)

(D) Component: One or more selected from the group consisting of a maleimide compound and a modified product thereof-Modified product of BMI and BMI-4000: Modified product of the maleimide compound synthesized in Production Example 1.

(E) Component: Epoxy resin containing an alicyclic skeleton, HP-7200H (dicyclopentadiene type epoxy resin, epoxy equivalent 280 g / eq, manufactured by DIC Corporation, trade name)

(F) Ingredient: Curing accelerator G-8009L (isocyanate mask imidazole, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name)

(G) Ingredient: Flame Retardant OP935 (Aluminum dialkylphosphinate salt, metal salt of disubstituted phosphinic acid, manufactured by Clariant AG, trade name)
PX-200 (1,3-phenylenebis (di-2,6-xylenyl phosphate), phosphorus content = 9% by mass, manufactured by Daihachi Chemical Industry Co., Ltd.)

Component (H): Inorganic filler / fused silica (average particle size = 1.9 μm, specific surface area = 5.8 m ² / g)

Other ingredients:
・ Yoshinox BB (4,4'-butylidenebis- (6-t-butyl-3-methylphenol, manufactured by Mitsubishi Chemical Corporation, trade name))

From Table 1, the thermosetting resin compositions obtained in Examples 1 to 5 have better dielectric properties, but are more laser-processable than the thermosetting resin compositions obtained in Comparative Example 1. It turns out that it is excellent. In addition, the thermosetting resin compositions of Examples 1 to 5 had good minimum melt viscosity, solder heat resistance, glass transition temperature, and copper foil peel strength.
Based on the above, according to the present invention, it is possible to provide a thermosetting resin composition having excellent dielectric properties and laser processability, and a prepreg, a copper-clad laminate, a printed wiring board, and a semiconductor package using the thermosetting resin composition. I understand.

Since the thermosetting resin composition of the present invention and the prepreg formed by using the thermosetting resin composition are excellent in dielectric properties and laser workability, copper-clad laminates, printed wiring boards and semiconductors for electronic devices Useful as a package.

Claims (14)

(A) A copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride,
(B) Epoxy-modified polybutadiene and
(C) Active ester compound and
(D) One or more selected from the group consisting of maleimide compounds and modified products thereof, and
(E) Epoxy resin containing an alicyclic skeleton and
A thermosetting resin composition comprising. The component (A) is a structural unit derived from an aromatic vinyl compound represented by the following general formula (Ai) and a structural unit derived from maleic anhydride represented by the following formula (A-ii). The thermosetting resin composition according to claim 1, which is a copolymerized resin having.

(In the formula, ^RA1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^RA2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group, a hydroxyl group or a (meth) acryloyl group. X is an integer of 0 to 3.) The thermosetting resin composition according to claim 1 or 2, wherein the component (B) is an epoxy-modified polybutadiene represented by the following general formula (B-1).

(In the formula, a, b and c represent the ratio of the structural units in parentheses, respectively, where a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.30. It is 0.80, and further, a + b + c = 1.00 and (a + c)> b are satisfied. Y represents the number of structural units in parentheses and is an integer of 10 to 250.) The component (C) is formed by esterifying a polyvalent carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group represented by any of the following general formulas (C1-1) to (C1-5). The thermosetting resin composition according to any one of claims 1 to 3, which is a compound.

(In the formula, k1 and k2 are independently 0 or 1, respectively.) The component (D) is a compound obtained by reacting a maleimide compound having at least two N-substituted maleimide groups in one molecule with a monoamine compound having an acidic substituent (d1) and a diamine compound (d2). , The thermosetting resin composition according to any one of claims 1 to 4. The thermosetting resin composition according to any one of claims 1 to 5, wherein the alicyclic skeleton contained in the component (E) is a dicyclopentadiene skeleton. According to any one of claims 1 to 6, the content of the component (A) is 1 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. The thermosetting resin composition according to the above. According to any one of claims 1 to 7, the content of the component (B) is 1 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. The thermosetting resin composition according to the above. According to any one of claims 1 to 8, the content of the component (E) is 1 to 30 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) in terms of solid content. The thermosetting resin composition according to the above. The heat according to any one of claims 1 to 9, further comprising at least one selected from the group consisting of (F) curing accelerator, (G) flame retardant and (H) inorganic filler. Curable resin composition. A prepreg containing the thermosetting resin composition according to any one of claims 1 to 10. A copper-clad laminate obtained by laminating the prepreg and copper foil according to claim 11. A printed wiring board using the copper-clad laminate according to claim 12. A semiconductor package using the printed wiring board according to claim 13.