JP2017115020A - Thermosetting resin composition, prepreg, copper-clad laminate and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that can achieve high adhesiveness to a copper foil, high heat resistance, and excellent dielectric properties, and a prepreg, a copper-clad laminate and a printed wiring board.SOLUTION: A thermosetting resin composition comprises (A) a copolymer resin comprising a structural unit derived from an aromatic vinyl compound and a structural unit derived from a maleic anhydride resin, (B) epoxy modified polybutadiene having a hydroxy group, and (C) a maleimide compound.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition, a prepreg, a copper clad laminate, and a printed wiring board that are suitable as materials for electronic devices and the like.

  Thermosetting resins are widely used in fields that require high reliability, such as electronic parts, because their unique cross-linked structure exhibits high heat resistance and dimensional stability. Especially in copper-clad laminates and interlayer insulation materials, due to recent demands for higher wiring density, high copper foil adhesion for fine wiring formation, and drilling or laser punching when processing such as drilling Workability is also required. In recent years, the mounting of electronic components using lead-free solder has required higher heat resistance than conventional ones.

  Mobile communication devices such as mobile phones, base station devices, network-related electronic devices such as servers and routers, and large computers are required to transmit and process large amounts of information with low loss and high speed. ing. When transmitting and processing a large amount of information, the electrical signal having a higher frequency can be transmitted and processed at a higher speed. However, an electrical signal basically has a property that the higher the frequency, the easier it is to attenuate, and the output tends to be weak at a shorter transmission distance and the loss tends to increase. Therefore, in order to satisfy the above-mentioned requirements for low loss and high-speed communication, in the characteristics of the printed wiring board itself that performs transmission and processing mounted on the device, dielectric characteristics (relative permittivity, dielectric loss tangent), particularly in a high frequency band. Therefore, it is required to reduce the relative dielectric constant and the dielectric loss tangent.

  Conventionally, in order to obtain a printed wiring board capable of transmitting information with low loss, a substrate material using a fluorine-based resin having a low relative dielectric constant and dielectric loss tangent has been used. However, since the fluorine-based resin generally has a high melting temperature and melt viscosity and relatively low fluidity, there is a problem that it is necessary to set high-temperature and high-pressure conditions during press molding. In addition, the processability, dimensional stability, and adhesion to metal plating are insufficient for use in high-layer printed wiring boards used in the above communication devices, network-related electronic devices, and large computers. There is a problem.

Accordingly, research is being made on thermosetting resin materials that can be used for high-frequency printed wiring boards instead of fluororesins. For example, a resin composition containing an epoxy resin (see Patent Document 1), a resin composition containing polyphenylene ether and bismaleimide (see Patent Document 2), and a resin composition containing polyphenylene ether and a cyanate resin (patent Reference 3), resin compositions containing styrene-butadiene copolymer or polystyrene and triallyl cyanurate or triallyl isocyanurate (for example, see Patent Documents 4 and 5) have been proposed.
Furthermore, a resin composition (for example, see Patent Document 6) containing a reaction product of polyphenylene ether and an unsaturated carboxylic acid or an unsaturated acid anhydride and a polyfunctional maleimide has been proposed.

Japanese Patent Laid-Open No. 58-069046 JP-A-56-133355 JP-A-56-141349 JP-A-61-286130 Japanese Patent Laid-Open No. 03-275760 Japanese Patent Laid-Open No. 06-179734

However, the resin composition described in Patent Literature 1, 2, or 6 is inferior in dielectric properties after curing due to the influence of a highly polar epoxy resin, and is unsuitable for high frequency applications.
In the resin composition described in Patent Document 3, although the dielectric properties are excellent, the heat resistance may be insufficient.
In the resin composition described in Patent Document 4 or 5, there was a tendency that the relative dielectric constant was slightly high.
Furthermore, the resin composition described in Patent Document 6 has a problem that the dielectric properties are deteriorated as compared with the case of using polyphenylene ether before modification due to the effect of modification with highly polar unsaturated carboxylic acid and unsaturated anhydride. It has been found that the use of a compound having a large number of polar groups in order to improve the adhesion to the copper foil results in a decrease in dielectric properties.

  Then, the subject of this invention is providing the thermosetting resin composition which can achieve the high adhesiveness with copper foil, high heat resistance, and the outstanding dielectric characteristic, a prepreg, a copper clad laminated board, and a printed wiring board. is there.

  As a result of diligent research to solve the above problems, the present inventors have found that (A) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, (B) a hydroxyl group The present inventors have found that a thermosetting resin composition comprising an epoxy-modified polybutadiene having a (C) maleimide compound and (C) a maleimide compound can solve the above problems, and has completed the present invention. The present invention has been completed based on such knowledge.

The present invention relates to the following [1] to [11].
[1] (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 having a hydroxyl group, and (C) a maleimide compound,
A thermosetting resin composition comprising:
[2] A structure in which the component (A) is derived from a structural unit derived from an aromatic vinyl compound represented by the following general formula (A-i) and a 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, R ^A1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^A2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 6 to 20 carbon atoms. An aryl group, a hydroxyl group or a (meth) acryloyl group, wherein x is an integer of 0 to 3. However, when x is 2 or 3, a plurality of R ^A2 may be the same or different. May be.)
[3] In the component (A), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [the structural unit derived from the aromatic vinyl compound / the structural unit derived from maleic anhydride] ] (Molar ratio) is 2-9, The thermosetting resin composition as described in said [1] or [2].
[4] The thermosetting resin composition according to any one of [1] to [3], wherein the component (B) is an epoxy-modified polybutadiene represented by the following general formula (B).

(In the formula, a, b and c each represent a ratio of structural units in parentheses, a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.30. 0.80, and a + b + c = 1.00 and (a + c)> b are satisfied, and y represents the number of structural units in parentheses and is an integer of 10 to 250.)
[5] The thermosetting resin composition according to any one of [1] to [4], wherein the component (C) is a maleimide compound having at least two N-substituted maleimide groups in one molecule. .
[6] The maleimide compound (c1) in which the component (C) is represented by any one of the following general formulas (c1-1) to (c1-5) is a monoamine compound (c2) and a diamine having an acidic substituent The thermosetting resin composition according to any one of the above [1] to [5], which is a maleimide compound modified with the compound (c3).

(Wherein R ^{C1 to} R ^C3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^C1 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. An alkylidene group, -O-, -C (= O)-, -S-, -SS- or a sulfonyl group, wherein p, q and r are each independently an integer of 0 to 4; s is an integer of 0-10.)
[7] The monoamine compound (c2) having the acidic substituent is represented by the following general formula (c2-1), and the diamine compound (c3) is any of the following general formulas (c3-1) to (c3-3). The thermosetting resin composition according to [6] above, represented by:

(Wherein R ^C4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ^C5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. T represents 1 to 5) Integer, u is an integer of 0 to 4 and satisfies 1 ≦ t + u ≦ 5, provided that when t is an integer of 2 to 5, a plurality of R ^C4 may be the same or different. In addition, when u is an integer of 2 to 4, a plurality of R ^C5 may be the same or different.

(X ^C2 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 group. R ^C6 and R ^C7 each independently represent 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, and v and w are each Independently, it is an integer of 0-4.
X ^C3 and X ^C4 are each independently a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O- or a sulfonyl group. )
[8] The above [D] further comprising at least one selected from the group consisting of (D) a radical reaction initiator, (E) a curing accelerator, (F) a flame retardant, and (G) an inorganic filler. The thermosetting resin composition according to any one of [1] to [7].
[9] A prepreg comprising the thermosetting resin composition according to any one of [1] to [8].
[10] A copper-clad laminate obtained by laminating the prepreg according to [9] and a copper foil.
[11] A printed wiring board using the copper-clad laminate according to [10].

  The present invention can provide a thermosetting resin composition that can achieve high adhesion to copper foil, high heat resistance, and excellent dielectric properties. Also provided are a prepreg comprising the thermosetting resin composition, a copper-clad laminate obtained by laminating the prepreg and a copper foil, and a printed wiring board using the copper-clad laminate. it can.

Hereinafter, the present invention will be described in detail.
[Thermosetting resin composition]
The thermosetting resin composition of the present invention is
(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 having a hydroxyl group, and (C) a maleimide compound,
Is a thermosetting resin composition.
Hereinafter, each component contained in the thermosetting resin composition of the present invention will be described in detail.

<(A) Copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride>
The component (A) is a copolymer resin [hereinafter sometimes referred to as copolymer resin (A)] having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride. The dielectric property is particularly improved by the component (A).
Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, and dimethylstyrene. Among these, styrene is preferable.
As the component (A), in particular, 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 preferable.

(In the formula, R ^A1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^A2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 6 to 20 carbon atoms. An aryl group, a hydroxyl group or a (meth) acryloyl group, wherein x is an integer of 0 to 3. However, when x is 2 or 3, a plurality of R ^A2 may be the same or different. May be.)

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A1 and R ^A2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Is mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ^A2 include an allyl group and a crotyl group. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, more preferably an alkenyl group having 3 or 4 carbon atoms.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^A2 include a phenyl group, a naphthyl group, an anthryl group, and a biphenylyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.
x is preferably 0 or 1, more preferably 0.
In the structural unit derived from the aromatic vinyl compound represented by the general formula (A-i), R ^A1 is a hydrogen atom and x is 0, and is represented by the following formula (A-i-1). Structural units are preferred.

Content ratio of structural unit derived from aromatic vinyl compound and structural unit derived from maleic anhydride in copolymer resin (A) [structural unit derived from aromatic vinyl compound / structural unit derived from maleic anhydride] (Molar ratio) is preferably 2 to 9, more preferably 4 to 9, and further preferably 6 to 9. The content ratio of the structural unit derived from the aromatic vinyl compound represented by the general formula (Ai) to the structural unit derived from maleic anhydride represented by the formula (A-ii) [(A- i) / (A-ii)] (molar ratio) is also preferably 2 to 9, more preferably 4 to 9, and still more preferably 6 to 9. If the content ratio is 2 or more, the effect of improving the dielectric properties and heat resistance tends to be sufficient, and if it 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 copolymer resin (A), and the aromatic vinyl compound represented by the general formula (Ai) The total content of the structural unit derived from the structural unit derived from maleic anhydride represented by the formula (A-ii) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably Is 90% by mass or more, particularly preferably substantially 100% by mass.
The weight average molecular weight (Mw) of the copolymer resin (A) is preferably 5,000 to 18,000, more preferably 6,000 to 17,000, still more preferably 8,000 to 16,000, particularly preferably. It is 10,000 to 16,000, most preferably 12,000 to 16,000. In addition, all the weight average molecular weights in this specification are values measured by gel permeation chromatography (GPC) method (standard polystyrene conversion) using tetrahydrofuran as an eluent.

  As a method for reducing the dielectric constant of an epoxy resin, there is a method using a copolymer resin of styrene and maleic anhydride. When this method is applied to a printed wiring board material, the impregnation property to the substrate and the copper Generally, it tends to be avoided due to insufficient adhesion to the foil. For this reason, it is apt to be avoided to use the copolymer resin (A), but the present invention contains both the component (B) and the component (C) while using the copolymer resin (A). Has succeeded in improving the adhesiveness with copper foil while having excellent dielectric properties, and also has excellent heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient and moldability The resin composition was found and achieved.

(Method for producing copolymer resin (A))
The copolymer resin (A) can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride.
Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, and dimethylstyrene as described above. These may be used individually by 1 type and may use 2 or more types together.
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; compounds having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
In addition, substitution of alkenyl groups such as allyl groups, (meth) acryloyl groups, hydroxyl groups, etc., through Friedel-Crafts reaction or reaction using a metal catalyst such as lithium to the copolymer obtained by the above copolymerization A group (corresponding to R ^A2 in formula (Ai)) may be introduced.

  As the copolymer resin (A), a commercially available product can be used. As the commercially available product, “SMA (registered trademark) EF30” (styrene / maleic anhydride = 3, Mw = 9,500), “SMA (registered) (Trademark) 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) [above, manufactured by Sartomer] and the like. Among these, “SMA (registered trademark) EF80” is preferable.

<(B) Epoxy-modified polybutadiene having a hydroxyl group>
The component (B) is an epoxy-modified polybutadiene having a hydroxyl group [hereinafter sometimes referred to as epoxy-modified polybutadiene (B)]. The component (B) exhibits the effect of improving the adhesiveness with the copper foil while maintaining the dielectric characteristics. In order to improve the adhesiveness with the copper foil, an epoxy resin having a polar group can be used, but in that case, the dielectric properties tend to deteriorate. However, if it is (B) component used by this invention, as above-mentioned, adhesiveness with copper foil can be improved, without producing such a problem.
Moreover, (B) component contributes also to a heat-resistant improvement and the fall of a thermal expansion coefficient, when polybutadiene is epoxy-modified.

Although there is no restriction | limiting in particular in the position of the hydroxyl group which epoxy-modified polybutadiene (B) has, It is preferable to have a hydroxyl group at a molecular terminal, It is more preferable to have a hydroxyl group at both molecular terminals, It has a hydroxyl group only at both molecular terminals. Further preferred. The number of hydroxyl groups contained in the epoxy-modified polybutadiene (B) is not particularly limited as long as it is 1 or more, but 1 to 5 is preferable, 1 or 2 is more preferable, and 2 is more preferable.
The epoxy-modified polybutadiene (B) is not particularly limited as long as it is a polybutadiene containing an epoxy group, but from the viewpoints of adhesion to copper foil, heat resistance, thermal expansion coefficient and flexibility, the following general formula (B) The epoxy-modified polybutadiene represented is preferable.

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

The order of bonding of the structural units in the general formula (B) is in no particular order. That is, the structural unit shown on the left, the structural unit shown on the center, and the structural unit shown on the right may be interchanged, and (a), (b), (c) -[(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 the like.
From the viewpoints of adhesion to copper foil, heat resistance, thermal expansion coefficient and flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0.00. 40-0.80.
The epoxy-modified polybutadiene (B) is easily produced by, for example, epoxidizing polybutadiene having hydroxyl groups at both molecular ends with hydrogen peroxide or peracids, and represented by the general formula (B). Is manufactured in the same manner.
As the raw material “polybutadiene having hydroxyl groups at both molecular ends”, liquid polybutadiene represented by the following general formula (B ′) is preferable. That is, the epoxy-modified polybutadiene (B) is preferably obtained by epoxidizing a liquid polybutadiene represented by the following general formula (B ′).

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

Commercially available products can be used as the polybutadiene having hydroxyl groups at both molecular ends as a raw material (including liquid polybutadiene having hydroxyl groups at both molecular ends represented by the general formula (B ′)). As a commercial item, "Poly.BD R-15HT", "Poly.BD R-45HT" (above, Idemitsu Kosan Co., Ltd. polybutadiene) etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Such a polybutadiene having a hydroxyl group has a hydroxyl group and has an amount of 1,4-vinyl bond structure of butadiene more than 1,2-vinyl bond structure [(a + c)> b]. The toughness is imparted to the steel, and the impact resistance and the adhesion to the copper foil tend to be improved.

  In the general formula (B), commercially available products of epoxidized polybutadiene having an integer of a = 0.20, b = 0.20, c = 0.60, and y = 10 to 250 include “Epolide (registered trademark)”. PB3600 "(manufactured by Daicel Corporation) and the like. From the viewpoint of flexibility, impact resistance, mechanical strength, and adhesiveness, it is preferable to use the commercial product.

<(C) Maleimide compound>
As the component (C), a maleimide compound [hereinafter referred to as a maleimide compound (C)] is used. By this (C) component, especially adhesiveness with copper foil improves. As the maleimide compound (C), a compound having at least two N-substituted maleimide groups in one molecule is preferable.
The weight average molecular weight (Mw) of the maleimide compound (C) is preferably 400 to 3500, more preferably 600 to 1000, and still more preferably 650 to 950, from the viewpoints of solubility in organic solvents and mechanical strength. .
Moreover, it is preferable that a maleimide compound (C) has an acidic substituent from a viewpoint of the rigidity and mechanical strength of the hardened | cured material of a thermosetting resin composition. Specifically, in the maleimide compound (C), the maleimide compound (c1) described later is modified with at least one selected from the group consisting of a monoamine compound (c2) having an acidic substituent and a diamine compound (c3). The maleimide compound (c1) described later is more preferably a maleimide compound modified with a monoamine compound (c2) having an acidic substituent and a diamine compound (c3).

(Maleimide compound (c1))
The maleimide compound (c1) is a maleimide compound having at least two N-substituted maleimide groups in one molecule.
Whether the maleimide compound (c1) is a maleimide compound having an aliphatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups [hereinafter referred to as an aliphatic hydrocarbon group-containing maleimide] Or a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups of the plurality of maleimide groups [hereinafter referred to as an aromatic hydrocarbon group-containing maleimide]. Among these, an aromatic hydrocarbon group-containing maleimide is preferable from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability. The aromatic hydrocarbon group-containing maleimide only needs to contain an aromatic hydrocarbon group between any combination of two maleimide groups selected arbitrarily.
The maleimide compound (c1) includes 2 to 5 N-substituted maleimide groups in one molecule from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient and moldability. Are preferred, and maleimide compounds having two N-substituted maleimide groups in one molecule are more preferred. Moreover, as a maleimide compound (c1), from a viewpoint of adhesiveness with copper foil, heat resistance, a dielectric characteristic, a glass transition temperature, a thermal expansion coefficient, and a moldability, the following general formula (c1-1)-(c1-5) Is more preferably an aromatic hydrocarbon group-containing maleimide represented by any one of the following general formulas (c1-2) to (c1-5): More preferably.

In the above formula, R ^{C1 to} R ^C3 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^C1 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, —O—, —C (═O) —, —S—, —SS— or a sulfonyl group. p, q, and r are each independently an integer of 0-4. s is an integer of 0-10.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^{C1 to} R ^C3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n- A pentyl group etc. are mentioned. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability. More preferably a methyl group or an ethyl group.
Examples of the halogen atom represented by R ^{C1 to} R ^C3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^C1 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. It is done. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably methylene, from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability. It is a group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^C1 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability.
X ^C1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms, among the above options. Further preferred are as described above.
p, q and r are each independently an integer of 0 to 4, and are preferably all from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient and formability. Is an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
s is an integer of 0 to 10, and is preferably an integer of 0 to 5, 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 (c1-3) is preferably a mixture of s = 0-3.

  As the maleimide compound (c1), aliphatic such as N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, bis (4-maleimidocyclohexyl) methane, 1,4-bis (maleimidomethyl) cyclohexane Hydrocarbon 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-maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl -4,4'-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimide) Phenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,3- Bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) Phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) ) Phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3 3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) Biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidopheno) Xyl) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4- Maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-Maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- ( 4-maleimidophenoxy) -α, α-dimethylbenze L] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] Benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α -Dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, poly Examples thereof include aromatic hydrocarbon group-containing maleimides such as rephenylmethane maleimide.

Among these, 4,4′-diphenylmethane bismaleimide, polyphenylmethane bismaleimide, m-phenylene from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient and moldability Bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, N, N ′-(4 -Methyl-1,3-phenylene) bismaleimide is preferred.
As the maleimide compound (c1), one type may be used alone, or two or more types may be used in combination, but it is preferable to use one type alone.

(Monoamine compound having acidic substituent (c2))
The monoamine compound (c2) having an acidic substituent is preferably a monoamine compound represented by the following general formula (c2-1).

In the general formula (c2-1), R ^C4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ^C5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and 1 ≦ t + u ≦ 5 is satisfied. However, when t is an integer of 2 to 5, the plurality of R ^C4 may be the same or different. Moreover, when u is an integer of 2-4, several ^RC5 may be the same and may differ.
The acidic substituent represented by R ^C4 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 from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability. 2, more preferably 1.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. . The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the halogen atom represented by R ^C5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
u is an integer of 0 to 4, and is preferably an integer of 0 to 3, more preferably 0 to 0, from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability. An integer of 2, more preferably 0 or 1, particularly preferably 0.
The monoamine compound (c2) having an acidic substituent is more preferably the following general formula (c2-2) from the viewpoints of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, thermal expansion coefficient, and moldability. ) Or (c2-3), more preferably a monoamine compound represented by the following general formula (c2-2). However, R ^C4 , R ^C5 and u in the general formulas (c2-2) and (c2-3) are the same as those in the general formula (c2-1), and preferable ones are also the same.

Examples of the monoamine compound (c2) having an acidic substituent include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and o-aminobenzene. Examples include sulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, and the like. 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 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.
The monoamine compound (c2) having an acidic substituent may be used alone or in combination of two or more.

(Diamine compound (c3))
The diamine compound (c3) is preferably a diamine compound having at least two benzene rings, more preferably a diamine compound having at least two benzene rings in a straight chain between two amino groups. A diamine compound represented by any one of (-1) to (c3-3) is more preferable.

(X ^C2 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 group. R ^C6 and R ^C7 each independently represent 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, and v and w are each Independently, it is an integer of 0-4.
X ^C3 and X ^C4 are each independently a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O- or a sulfonyl group. )

As the alkylene group having 1 to 5 carbon atoms which X ^C2 represents a methylene group, an ethylene group, a propylene group, propylidene group, and the like. As this alkylene group, a C1-C3 alkylene group is preferable and a methylene group is more preferable.
The alkylidene group having 2 to 5 carbon atoms which X ^C2 shows, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. As the alkylidene group, an isopropylidene group is preferable.
X ^C2 is preferably a single bond, an alkylene group having 1 to 5 carbon atoms, or —O—, and more preferably a methylene group or —O—.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C6 and R ^C7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Is mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the alkoxy group having 1 to 5 carbon atoms represented by R ^C6 and R ^C7 include a methoxy group, an ethoxy group, and a propoxy group. The alkoxy group is preferably a methoxy group.
Examples of the halogen atom represented by R ^C6 and R ^C7 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
v and w are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^C3 and X ^C4 include a methylene group, an ethylene group, a propylene group, and a propylidene group. As this alkylene group, a C1-C3 alkylene group is preferable and a methylene group is more preferable.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^C3 and X ^C4 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. As the alkylidene group, an isopropylidene group is preferable.
X ^C3 is preferably a single bond, an alkylidene group having 2 to 5 carbon atoms, or a sulfonyl group.
X ^C4 is preferably an alkylidene group having 2 to 5 carbon atoms, and more preferably an isopropylidene group.

  Specific examples of the diamine compound (c3) include 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, and 4,4′-diamino-3,3′-diethyl. -Diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 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. 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 production cost, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4 4,4′-diaminodiphenyl ether is preferred, and 4,4′-diaminodiphenylmethane is more preferred.

The reaction of the maleimide compound (c1), the monoamine compound (c2) having an acidic substituent and the diamine compound (c3) is preferably performed in the presence of an organic solvent described later at a reaction temperature of 70 to 200 ° C. for 0.1 to 10 hours. It is preferable to carry out.
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 1 to 4 hours.

The amount of the monoamine compound (c2) having an acidic substituent is such that the number of moles of the maleimide compound (c1) is 1, and the number of moles of the monoamine compound (c2) having an acidic substituent is 0.25 to 0.5. It is preferably used in a range. If the amount of the monoamine compound (c2) having an acidic substituent is 0.25 or more, there is a tendency to suppress a decrease in reactivity, and if it is 0.5 or less, heat resistance, dielectric properties, and glass transition temperature. Tends to be good.
As for the usage-amount of a diamine compound (c3), when the number of moles of a maleimide compound (c1) is 1, it is preferable that the number of moles of a diamine compound (c3) is used in the range of 0.1-0.25. If the usage-amount of a diamine compound (c3) is 0.1 or more, it exists in the tendency which can suppress a reactive fall, and if it is 0.25 or less, it exists in the tendency for heat resistance and a dielectric characteristic to become favorable.
Further, in the reaction of the maleimide compound (c1), the monoamine compound (c2) having an acidic substituent, and the diamine compound (c3), the three amounts used are the monoamine compound (c2) and diamine compound (c3) having an acidic substituent. ) Has a primary amino group equivalent [denoted as —NH ₂ group equivalent] and the maleimide group equivalent of the maleimide compound (c1) preferably satisfies the following formula.
1.5 ≦ [maleimide group equivalent] / [-NH ₂ group equivalent] ≦ 10
By setting [maleimide group equivalent] / [-NH ₂ group equivalent] to 1.5 or more, gelation is less likely to occur and heat resistance is less likely to be reduced. It is preferable because solubility in a solvent, adhesion to copper foil, and heat resistance tend not to decrease.
From the same viewpoint, more preferably,
2 ≦ [maleimide group equivalent] / [-NH ₂ group equivalent] ≦ 8
More preferably,
3 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalent] ≦ 6.
More preferably,
4 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalents] ≦ 6.

(Organic solvent)
As described above, the reaction of the maleimide compound (c1), the monoamine compound (c2) having an acidic substituent and the diamine compound (c3) is preferably performed in an organic solvent.
The organic solvent 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 mesitylene; nitrogen atom-containing solvents including amide solvents such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; sulfur atoms including sulfoxide solvents such as dimethyl sulfoxide Solvent; ester solvents such as ethyl acetate and γ-butyrolactone are listed.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, ester solvents, nitrogen atom-containing solvents are preferable, and from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone. Is more preferable, considering that it is highly volatile and hardly remains as a residual solvent during the production of the prepreg, cyclohexanone, propylene glycol monomethyl ether, and N, N-dimethylacetamide are more preferable, and N, N-dimethylacetamide is particularly preferable.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, From a viewpoint of solubility and reaction efficiency, with respect to 100 mass parts in total of a maleimide compound (c1), the monoamine compound (c2) which has an acidic substituent, and a diamine compound (c3). Thus, it is preferably 25 to 1000 parts by mass, more preferably 40 to 700 parts by mass, further preferably 50 to 250 parts by mass, and particularly preferably 50 to 150 parts by mass. There exists a tendency which becomes easy to ensure solubility by setting it as 25 mass parts or more with respect to a total of 100 mass parts of a maleimide compound (c1), the monoamine compound (c2) which has an acidic substituent, and a diamine compound (c3), 1000 By setting it as a mass part or less, there exists a tendency which is easy to suppress the significant fall of reaction efficiency.

(Reaction catalyst)
You may implement reaction of the maleimide compound (c1), the monoamine compound (c2) which has an acidic substituent, and a diamine compound (c3) in presence of a reaction catalyst as needed. Examples of the reaction catalyst include amine catalysts such as triethylamine, pyridine, and tributylamine; imidazole catalysts such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine.
A reaction catalyst may be used individually by 1 type, and may use 2 or more types together.
When using a reaction catalyst, the amount used is not particularly limited, but with respect to 100 parts by mass of the total mass of maleimide compound (c1), monoamine compound (c2) having an acidic substituent, and diamine compound (c3). The amount is preferably 0.001 to 5 parts by mass.
The reaction proceeds sufficiently even without using a reaction catalyst.

[Contents of Component (A) to Component (C) in Thermosetting Resin Composition]
The thermosetting resin composition of the present invention comprises the components (A) to (C). Content of each component (however, each component is not necessarily contained in the thermosetting resin composition in the structure as it is, that is, some components are reacted, but here, for convenience, use of each component is used. The amount is referred to as “content”.) Is preferably 5 to 25 parts by mass of component (A) with respect to 100 parts by mass of the total mass of components (A) to (C) in terms of solid content. 10-20 parts by mass, component (B) is preferably 5-30 parts by mass, more preferably 10-25 parts by mass, and component (C) is preferably 45-80 parts by mass, more preferably 60-75 parts by mass. It is.
If the content of the component (A) is 5 parts by mass or more with respect to 100 parts by mass of the total mass of the components (A) to (C) in terms of solid content, the dielectric properties tend to be good, and further Solubility is ensured and it tends to be difficult to deposit during the production of the resin varnish. Moreover, since it is hard to remain an unreacted component if it is 25 mass parts or less, it exists in the tendency which can suppress the adhesive fall with copper foil.
If the content of the component (B) is 5 parts by mass or more with respect to 100 parts by mass of the total mass of the components (A) to (C) in terms of solid content, the adhesiveness with the copper foil tends to be good. It is in. Moreover, if it is 30 mass parts or less, it exists in the tendency for heat resistance to become favorable.
If the content of the component (C) is 45 parts by mass or more with respect to 100 parts by mass of the total mass of the components (A) to (C) in terms of solid content, the heat resistance tends to be excellent. Moreover, if it is 80 mass parts or less, it exists in the tendency for the fluidity | liquidity and moldability of a thermosetting resin composition to become favorable.

<Other ingredients>
The thermosetting resin composition of the present invention may contain other components other than the components (A) to (C). As other components, for example, (D) radical reaction initiator, (E) curing accelerator, (F) flame retardant, (G) inorganic filler, colorant, antioxidant, reducing agent, ultraviolet absorber, A fluorescent brightening agent, an adhesion improver, an organic filler, and the like can be mentioned, but are not particularly limited thereto. These may be used individually by 1 type and may use 2 or more types together.
In particular, in addition to the components (A) to (C), the thermosetting resin composition of the present invention further includes (D) a radical reaction initiator, (E) a curing accelerator, (F) a flame retardant, and ( G) It is preferable to contain at least one selected from the group consisting of inorganic fillers.

((D) radical reaction initiator)
By containing a radical reaction initiator [hereinafter referred to as radical reaction initiator (D)], the curing reaction of the thermosetting resin composition of the present invention is likely to occur.
The radical reaction initiator (D) has an effect of initiating or accelerating the curing reaction of the cured product of the thermosetting resin composition when producing a copper-clad laminate or a multilayer printed wiring board.
As the radical reaction initiator (D), α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-bis Dialkyl peroxide radical initiators such as (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne, di-t-butyl peroxide; p-mentor And hydroperoxide radical reaction initiators such as hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and the like. However, it is not limited to these. A radical reaction initiator (D) may be used individually by 1 type, and may use 2 or more types together.
In addition, radical reaction initiators having different half-life temperatures can be combined from the viewpoint of improving the moldability of the prepreg. From the viewpoints of dielectric properties, thermal expansion coefficient, etc., p- having a reaction initiation temperature higher than dialkyl peroxide radical initiators such as α, α′-bis (t-butylperoxy) diisopropylbenzene and the like. It is preferable to use one or more radical reaction initiators selected from hydroperoxide-based radical reaction initiators such as mentahydroperoxide, diisopropylbenzene hydroperoxide and t-hexyl hydroperoxide.
When the thermosetting resin composition of the present invention contains the radical reaction initiator (D), the content is 100 mass of the total mass of the components (A) to (C) in terms of solid content. Preferably it is 0.01-5 mass parts with respect to a part, More preferably, it is 0.1-3 mass part.

((E) Curing accelerator)
By containing a curing accelerator [hereinafter referred to as curing accelerator (E)], the curing reaction of the thermosetting resin composition of the present invention can be promoted.
Curing accelerators (E) include imidazoles and derivatives thereof; phosphines and phosphonium salts, organophosphorus compounds such as adducts of tertiary phosphines and quinones; secondary amines, tertiary amines, and And quaternary ammonium salts. A hardening accelerator (E) may be used individually by 1 type, and may use 2 or more types together.
As the curing accelerator (E), imidazoles and derivatives thereof are preferable from the viewpoints of adhesion to copper foil, heat resistance and flame retardancy.
A commercial item may be used as a hardening accelerator (E). Commercially available products include isocyanate mask imidazole (Daiichi Kogyo Seiyaku Co., Ltd., trade name: G-809L), tetraphenylphosphonium tetra-p-tolylborate (Hokuko Chemical Co., Ltd., trade name: TPP-MK), Examples include triphenylphosphine triphenylborane (trade name: TPP-S, manufactured by Hokuko Chemical Co., Ltd.).
In the case where the thermosetting resin composition of the present invention contains a curing accelerator (E), the content thereof is (A) to (A) to solid content conversion from the viewpoint of curing acceleration effect and storage stability. The total mass of the component (C) is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 1.5 parts by mass, and still more preferably 0.1 to 0.8 parts by mass with respect to 100 parts by mass. It is.

((F) flame retardant)
By containing a flame retardant [hereinafter referred to as a flame retardant (F)], the flame retardancy of the thermosetting resin composition of the present invention is improved.
Examples of the flame retardant (F) include metal hydrates such as aluminum hydroxide and magnesium hydroxide having a thermal decomposition temperature of less than 300 ° C .; halogen-containing flame retardant containing bromine, chlorine, etc .; phosphorus flame retardant; sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardant aids 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, heat resistance, adhesiveness with copper foil, elastic modulus, thermal expansion coefficient, etc. are small, and high flame retardancy. From the viewpoint of imparting, a phosphorus-based flame retardant is more preferable. A flame retardant may be used individually by 1 type, and may use 2 or more types together.
Examples of the phosphorus flame retardant include an inorganic phosphorus flame retardant and an organic phosphorus flame retardant.
Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides; phosphorus Acid; phosphine oxide and the like.
Organic phosphorus flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorous compounds, cyclic organophosphorus compounds, and phosphorus content A phenol resin etc. are mentioned. Among these, aromatic phosphate esters and metal salts of disubstituted phosphinic acids are preferred. Here, the metal salt is preferably any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt, and preferably an aluminum salt. Among organic phosphorus flame retardants, aromatic phosphates are more preferable.

Aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3-phenylene Examples thereof include bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylenebis (diphenyl phosphate) and the like.
Examples of the monosubstituted phosphonic acid diester include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, and a metal salt of diarylphosphinic acid. As described above, these metal salts are preferably any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt.
Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and the like.
As the cyclic organic phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- And phosphaphenanthrene-10-oxide.
Among these, from the viewpoint of dielectric properties and glass transition temperature, at least one selected from an aromatic phosphate ester, a metal salt of a disubstituted phosphinic acid, and a cyclic organic phosphorus compound is preferable. More preferred is at least one selected from metal salts of phosphinic acid.

In addition, the aromatic phosphate ester is preferably an aromatic phosphate ester represented by the following general formula (F-1) or (F-2) from the viewpoint of dielectric properties and glass transition temperature, The metal salt of disubstituted phosphinic acid is preferably a metal salt of disubstituted phosphinic acid represented by the following general formula (F-3).

(Wherein R ^{F1 to} R ^F5 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom. E and f are each independently an integer of 0 to 5, and g, h and i are each It is an integer of 0-4 independently.
R ^F6 and R ^F7 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 14 carbon atoms. M is a lithium atom, sodium atom, potassium atom, calcium atom, magnesium atom, aluminum atom, titanium atom or zinc atom. j is an integer of 1 to 4. )

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^{F1 to} R ^F5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Is mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^{F1 to} R ^F5 include a fluorine atom.
e and f are preferably integers of 0 to 2, and more preferably 2. g, h and i are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F6 and R ^F7 include the same groups as in R ^{F1 to} R ^F5 .
Examples of the aryl group having 6 to 14 carbon atoms represented by R ^F6 and R ^F7 include a phenyl group, a naphthyl group, a biphenylyl group, and an anthryl group. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms.
j represents the valence of the metal ion, that is, changes within a range of 1 to 4 corresponding to the type of M.
M is preferably an aluminum atom. In addition, j is 3 when M is an aluminum atom.

  A commercially available product may be used as the flame retardant (F). Commercially available products include “PX-200” (1,3-phenylenebis (di-2,6-xylenyl phosphate), phosphorus content = 9% by mass, manufactured by Daihachi Chemical Industry Co., Ltd.), “OP- 935 "(aluminum salt of dialkylphosphinic acid, phosphorus content = 23.5% by mass, manufactured by Clariant).

  When the thermosetting resin composition of the present invention contains a flame retardant (F), the content is from the viewpoint of flame retardancy of the components (A) to (C) in terms of solid content. Preferably it is 0.01-15 mass parts with respect to 100 mass parts of total mass, More preferably, it is 0.1-10 mass parts, More preferably, it is 1-8 mass parts.

((G) inorganic filler)
With an inorganic filler [hereinafter referred to as inorganic filler (G)], the thermal expansion coefficient of the thermosetting resin composition of the present invention can be reduced, and the elastic modulus, heat resistance and flame retardancy can be improved.
As inorganic filler (G), silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate , Calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fiber, fine glass powder, hollow glass, etc. . Preferred examples of the glass include E glass, T glass, and D glass. An inorganic filler (G) may be used individually by 1 type, and may use 2 or more types together. Among these, silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is more preferable from the viewpoints of adhesiveness to copper foil, heat resistance, and flame retardancy. Examples of silica include crushed silica, fumed silica, and spherical silica. The silica is preferably spherical silica from the viewpoint of thermal expansion coefficient and fluidity when filled into the thermosetting resin composition.
Although there is no restriction | limiting in particular in the average particle diameter of a silica, 0.01-30 micrometers is preferable, 0.1-10 micrometers is more preferable, 0.5-6 micrometers is further more preferable. By making the average particle diameter of silica 0.01 μm or more, there is a tendency to maintain good fluidity even when highly packed, and by making it 30 μm or less, the mixing probability of coarse particles is reduced and coarse particles It tends to be possible to suppress the occurrence of defects due to. Here, the average particle size is a particle size at a point corresponding to a volume of just 50% when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.
The specific surface area of silica is preferably 4 cm ² / g or more, more preferably 4 to 9 cm ² / g, and still more preferably 5 to 7 cm ² / g. The specific surface area can be determined by the BET method. For example, it can be obtained by a BET method in which nitrogen is adsorbed on the surface of a powder sample at a liquid nitrogen temperature and the specific surface area of the powder sample is obtained from the adsorption amount.

The inorganic filler (G) may be surface-treated with a coupling agent. That is, it is also preferable to employ a method in which an inorganic filler (G) such as silica is directly subjected to dry or wet surface treatment and then used as it is or in a slurry state during blending. On the other hand, after blending an inorganic filler (G) such as untreated silica in the resin composition containing the component (A) and the component (B), a surface treatment agent is added to the resin composition. A blending method may be employed.
Examples of the coupling agent include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, and haloalkylsilanes. Coupling agent, siloxane coupling agent, hydrosilane coupling agent, silazane coupling agent, alkoxysilane coupling agent, chlorosilane coupling agent, (meth) acrylsilane coupling agent, aminosilane coupling Agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, sulfide silane coupling agents, isocyanate silane coupling agents, and the like. Of these, aminosilane coupling agents are preferred.
From the viewpoint of thermal expansion coefficient and adhesiveness with other components, the inorganic filler (G) is preferably silica treated with an aminosilane coupling agent.

As an aminosilane coupling agent, specifically, a silane coupling agent having a silicon-containing group represented by the following general formula (G-1) and an amino group is preferable.

(In the formula, R ^G1 is an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms. Z is an integer of 0 to 2)

Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^G1 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, a methyl group is preferable.
Examples of the acyl group having 2 to 4 carbon atoms represented by R ^G1 include an acetyl group, a propionyl group, and an acrylic group. Among these, an acetyl group is preferable.
z is preferably 0 or 1, more preferably 0.

The aminosilane coupling agent may have one amino group, two amino groups, or three or more, but usually one amino group or Have two.
Examples of the aminosilane coupling agent having one amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-trimethoxysilyl-N-. (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, 2-propynyl [3- (Trimethoxysilyl) propyl] carbamate and the like can be mentioned, but the invention is not particularly limited thereto.
Examples of aminosilane coupling agents having two amino groups include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 1- [3- (trimethoxysilyl) propyl] urea, 1- [3- (triethoxysilyl) propyl] urea and the like Although it is mentioned, it is not particularly limited to these.

  When the thermosetting resin composition of the present invention contains an inorganic filler (G), the content thereof is a component (A) to (C) in terms of solid content from the viewpoint of flame retardancy. Preferably it is 20-110 mass parts, More preferably, it is 20-80 mass parts, More preferably, it is 30-80 mass parts, Especially preferably, it is 45-70 mass parts with respect to 100 mass parts of total of mass.

(Organic solvent)
The thermosetting resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating handling by dilution and easy manufacture of a prepreg described later. In this specification, the thermosetting resin composition containing an organic solvent may be referred to as a resin varnish.
The organic solvent is not particularly limited, but 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 Alcohol solvents such as monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as tetrahydrofuran; toluene , Xylene, mesitylene and other aromatic solvents; formamide, A nitrogen atom-containing solvent such as methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; a sulfur atom-containing solvent such as dimethylsulfoxide; methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, Examples thereof include ester solvents such as propylene glycol monomethyl ether acetate, ethyl acetate, and γ-butyrolactone.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, aromatic solvents, nitrogen atom-containing solvents are preferable, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, propylene glycol monomethyl ether, γ-butyrolactone, Toluene, dimethylformamide, and N, N-dimethylacetamide are more preferable, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, toluene, and N, N-dimethylacetamide are more preferable, and methyl isobutyl ketone and N, N-dimethylacetamide are particularly preferable. preferable.
An organic solvent may be used individually by 1 type, and may use 2 or more types together. When using together, the combined use of a ketone solvent and an aromatic solvent is particularly preferable, and the combined use of methyl isobutyl ketone and toluene is more preferable.
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 coating property of the resin varnish is good. If it is, there will be no restriction | limiting in particular, However, Solid content concentration (concentration of components other than an organic solvent) of a thermosetting resin composition becomes like this. Preferably it is 30-90 mass%, More preferably, it is 40-80 mass%, More preferably, it is 50 ˜80 mass%.

(Physical properties and properties of thermosetting resin composition)
The thermosetting resin composition of the present invention is excellent in adhesion to copper foil, heat resistance and dielectric properties, has a high glass transition temperature, a low thermal expansion coefficient, and is excellent in moldability. Moreover, this thermosetting resin composition is excellent also in the solubility with respect to the organic solvent.
About the adhesiveness with the copper foil of the thermosetting resin composition of this invention, when it says with the peel strength of the copper foil measured by the method as described in an Example, it is preferable that it is 0.70 kN / m or more, 0 More preferably, it is 0.75 kN / m or more, and further preferably in the range of 0.75 to 0.95 kN / m.
The dielectric property of the thermosetting resin composition of the present invention is preferably 4.0 or less, more preferably 3.90 or less in terms of the dielectric constant measured by the method described in Examples. More preferably, it is in the range of 3.80 to 3.90. Moreover, the dielectric loss tangent measured by the method described in the examples is preferably 0.009 or less, more preferably 0.0085 or less, and further in the range of 0.0060 to 0.0085. preferable.
The glass transition temperature (Tg) of the thermosetting resin composition of the present invention is preferably 180 ° C. or higher, preferably 190 ° C. or higher, in terms of Tg measured by the method described in Examples. More preferably, it is in the range of 193 to 198 ° C.
The thermal expansion coefficient of the thermosetting resin composition of the present invention is preferably 50 ppm / ° C. or less in terms of the thermal expansion coefficient measured by the method described in the examples, and is in the range of 40 to 49 ppm / ° C. It is preferable. More preferably, it is 45 ppm / degrees C or less, More preferably, it is 40-45 ppm / degrees C.

[Prepreg]
The present invention also provides a prepreg comprising the thermosetting resin composition.
The prepreg of the present invention can be produced by impregnating or coating the thermosetting resin composition on a sheet-like reinforcing base material and semi-curing (B-stage) by heating or the like.
As the prepreg sheet-like reinforcing substrate, known materials used for various types of laminates for electrical insulating materials can be used. The material of the sheet-like reinforcing substrate includes 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; And the like. Among these, glass fiber is preferable from the viewpoint of flame retardancy. Glass fiber base materials include woven fabrics using E glass, C glass, D glass, S glass, etc., or glass woven fabrics in which short fibers are bonded with an organic binder; Can be mentioned. More preferably, it is a glass woven fabric using E glass.
These sheet-like reinforcing base materials have a shape such as a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, or a surfacing mat. In addition, a material and a shape are selected by the use and performance of the target molding, and 1 type may be used independently and 2 or more types of materials and shapes can also be combined as needed.

As a method for impregnating or applying the thermosetting resin composition to the sheet-like reinforcing base material, the following hot melt method or solvent method is preferable.
The hot melt method is a method in which an organic solvent is not contained in a thermosetting resin composition, and (1) a coated paper having good peelability from the composition is once coated and laminated on a sheet-like reinforcing substrate. Or (2) A method of directly coating the sheet-like reinforcing substrate with a die coater.
On the other hand, in the solvent method, a resin varnish is prepared by adding an organic solvent to a thermosetting resin composition, and a sheet-like reinforcing base material is immersed in the resin varnish to impregnate the sheet-like reinforcing base material. Then, it is a method of drying.

The thickness of the sheet-like reinforcing base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface treatment with a silane coupling agent or the like or mechanical fiber opening treatment is performed. What has been applied is preferred from the viewpoints of heat resistance, moisture resistance and processability. After impregnating or coating the base material with the thermosetting resin composition, it is usually preferably dried by heating at 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage). A prepreg can be obtained.
The obtained prepreg is used as a single sheet, or preferably 2 to 20 sheets are used in an overlapping manner as necessary.

[Copper laminate]
The copper clad laminate of the present invention is obtained by laminating the prepreg and copper foil. For example, it can be manufactured by using one sheet of the prepreg or stacking 2 to 20 sheets as necessary, and laminating with a structure in which a copper foil is disposed on one or both sides.
As the molding conditions of the copper-clad laminate, a known molding method for laminates for electrical insulation materials and multilayer plates can be applied, and a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. It can be molded at 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
Moreover, the prepreg of the present invention and the printed wiring board for inner layer can be combined and laminated to produce a multilayer board.
There is no restriction | limiting in particular in the thickness of copper foil, According to the use etc. of a printed wiring board, it can select suitably. The thickness of the copper foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

In addition, it is also preferable to form a plating layer by plating copper foil.
The metal of the plating layer is not particularly limited as long as it can be used for plating. The metal of the plating layer is preferably made of copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. Preferably it is selected.
There is no restriction | limiting in particular as a plating method, For example, a well-known method, for example, the electroplating method and the electroless-plating method, can be utilized.

[Printed wiring board]
The present invention also provides a printed wiring board using the copper clad laminate.
The printed wiring board of the present invention can be produced by subjecting a metal foil of a copper-clad laminate to circuit processing. For example, after forming a resist pattern on the surface of the copper foil, the unnecessary portion of the copper foil is removed by etching, the resist pattern is peeled off, a necessary through hole is formed by a drill, and a resist pattern is formed again. It can be performed by plating for conducting through holes and finally peeling off the resist pattern. The copper-clad laminate is further laminated on the surface of the printed wiring board thus obtained under the same conditions as described above, and further, the circuit is processed in the same manner as described above to obtain a multilayer printed wiring board. Can do. In this case, it is not always necessary to form a through hole, a via hole may be formed, and both can be formed. Such multi-layering is performed as many times as necessary.

  Next, the present invention will be described in more detail with reference to the following examples, but these examples are not intended to limit the present invention in any way. Using the thermosetting resin composition according to the present invention, a prepreg and a copper-clad laminate were produced, and the produced copper-clad laminate was evaluated. The evaluation method is shown below.

[Evaluation method]
<1. Presence or absence of precipitates in resin varnish>
The resin varnish was passed through a # 200 sieve made of nylon, and the presence or absence of precipitates was confirmed visually.

<2. Adhesiveness with copper foil (copper foil peel strength)>
The copper clad laminate produced in each example was immersed in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA Corporation) to form a copper foil having a width of 3 mm to produce an evaluation board, 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 adhesiveness with the copper foil. It shows that it is excellent in adhesiveness with copper foil, so that a value is large. In particular, 0.70 kN / m or more is preferable, and 0.75 kN / m or more is more preferable.

<3. Heat resistance (solder heat resistance)>
The copper-clad laminate produced in each example was cut into 25 mm squares, floated on a 288 ° C. solder bath, visually observed, and the time (unit: minute) until the substrate expanded was measured. In addition, since it was set as the observation for 30 minutes at the longest, when a swelling is not observed even if 30 minutes pass, it will show as ">30" uniformly.
It shows that it is excellent in heat resistance, so that time is long.

<4. Dielectric properties (dielectric constant Dk, dielectric loss tangent Df)>
The copper clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to remove the copper foil, and then cut to 2 mm × 85 mm to obtain a network analyzer “E8364B”. The relative permittivity and dielectric loss tangent of the copper-clad laminate at 5 GHz were measured by a cavity resonator perturbation method using (Agilent Technologies).
The smaller the relative dielectric constant and the dielectric loss tangent, the better. In particular, the relative dielectric constant is preferably 4.0 or less, and the dielectric loss tangent is preferably 0.009 or less.

<5. Glass transition temperature (Tg)>
The copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to produce a 5 mm square evaluation board from which the copper foil was removed, and a TMA test apparatus “Q400EM ”(Manufactured by TA Instruments Co., Ltd.), the thermal expansion characteristics in the surface direction (Z direction) of the evaluation substrate at 25 to 280 ° C. (temperature increase rate: 10 ° C./min) were observed, and the inflection point of the expansion amount was glass. The transition temperature was used.
The glass transition temperature is preferably 180 ° C. or higher, and more preferably 190 ° C. or higher.

<6. Thermal expansion coefficient>
The copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to produce a 5 mm square evaluation board from which the copper foil was removed, and a TMA test apparatus “Q400EM ”(Manufactured by TA Instruments) was used to measure the coefficient of thermal expansion (linear expansion coefficient) in the surface direction (Z direction) of the evaluation substrate. In addition, in order to remove the influence of the thermal strain which a sample has, the temperature rising-cooling cycle was repeated twice, and the thermal expansion coefficient [ppm / ° C.] of 30 to 100 ° C. of the second temperature displacement chart was measured. The smaller the value, the better.
Measurement conditions 1st Run: room temperature → 210 ° C. (temperature increase rate 10 ° C./min)
2nd Run: 0 ° C. → 280 ° C. (temperature increase rate 10 ° C./min)
The copper-clad laminate is desired to be further reduced in thickness, and in conjunction with this, the prepreg constituting the copper-clad laminate is also being considered to be thinner. Since the thinned prepreg is likely to warp, it is preferable that the prepreg warp during heat treatment is small. In order to reduce the warpage, it is effective that the thermal expansion coefficient in the surface direction of the base material is small.
The thermal expansion coefficient is particularly preferably 50 ppm / ° C. or less, and more preferably 45 ppm / ° C. or less.

<7. Formability>
A prepreg with a thickness of 0.05 mm is stacked on each side of a moldability confirmation substrate on which a pattern having a copper thickness of 18 μm and a residual copper ratio of 60% is fabricated, and further, a 18 μm copper foil “YGP-18” (NIPPON ELECTRIC CO., LTD.) One by one was piled up one by one, and heat-pressed for 90 minutes at a temperature of 200 ° C. and a pressure of 25 kgf / cm ² (= 2.45 MPa) to produce a four-layer copper-clad laminate. After removing the outer layer copper of the four-layer copper-clad laminate, the resin embedding property, void, fading, and the like were visually confirmed. When the embedding property of the resin was good and there was no void or blur, the moldability was evaluated as good.

  Hereinafter, each component used in Examples and Comparative Examples will be described.

(A) component:
"SMA (registered trademark) EF80" (styrene / maleic anhydride = 8, Mw = 14,400, manufactured by Sartomer)

(B) component:
・ "Epolide (registered trademark) PB3600" (epoxy-modified polybutadiene, molecular both-end OH group, manufactured by Daicel Corporation)
(For comparison)
・ "Epolide (registered trademark) PB4700" (epoxy-modified polybutadiene, H groups at both ends of the molecule, manufactured by Daicel Corporation)
"B-3000" (polybutadiene (unmodified), Mn = 3,200, manufactured by Nippon Soda Co., Ltd.)
"HP-7200H" (dicyclopentadiene type epoxy resin, epoxy equivalent = 283 g / eq, manufactured by Dainippon Ink and Chemicals, Inc.)

(C) Component: The maleimide compound manufactured according to the following manufacture example was used.
[Production example]
1,000 g of the following maleimide compound (c1), p-aminophenol (manufactured by Ihara Chemical Industry Co., Ltd.) [component (c2)] 72.5 g (0.66 mol), 4,4′-diaminodiphenylmethane (Tokyo Chemical Industry Co., Ltd.) (Made by company) [(c3) component] 64.3 g (0.32 mol) and N, N-dimethylacetamide 720 g were mixed ([maleimide group equivalent] / [-NH ₂ group equivalent]] ≈3.4-4. 5) and reacted at 100 ° C. for 100 minutes to obtain a solution of the maleimide compound, and the maleimide compound (C) [modified BMI (Mw = 358.4) and modified BMI-2300 (Mw = 424), respectively] , Modified body of BMI-4000 (Mw = 570.6), modified body of BMI-5100 (Mw = 440.6)].
(Maleimide compound (c1))
"BMI"(4,4'-diphenylmethane bismaleimide, manufactured by KAI Kasei Co., Ltd., included in the general formula (c1-2))
"BMI-2300" (polyphenylmethane maleimide, manufactured by Daiwa Kasei Co., Ltd., included in the general formula (c1-3))
"BMI-4000" (2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, manufactured by Daiwa Kasei Co., Ltd., corresponding to the general formula (c1-4))
"BMI-5100"(3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Co., Ltd., corresponding to the general formula (c1-5))

Component (D): Radical reaction initiator “Perbutyl (registered trademark) P” (α, α′-bis (t-butylperoxy) diisopropylbenzene, manufactured by NOF Corporation)

(E) Component: Curing accelerator “G-8809L” (isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Component (F): Flame retardant / Flame retardant 1: “PX-200” (1,3-phenylenebis (di-2,6-xylenyl phosphate), phosphorus content = 9% by mass, Daihachi Chemical Co., Ltd. Company-made)
Flame retardant 2: “OP-935” (aluminum salt of dialkylphosphinic acid, phosphorus content = 23.5% by mass, manufactured by Clariant)

(G) Component: Inorganic filler / Inorganic filler 1: “Megasil 525 ARI” (spherical silica treated with an aminosilane coupling agent, average particle size = 1.9 μm, specific surface area = 5.8 m ² / g, Sibelco Japan Co., Ltd.)
Inorganic filler 2: “F05-30” (untreated crushed silica, average particle size = 4.2 μm, specific surface area = 5.8 m ² / g, manufactured by Fukushima Ceramics Co., Ltd.)

[Examples 1 to 9, Comparative Examples 1 to 12]
Each component shown above is mix | blended (unit: mass part. However, in the case of a solution, solid content conversion amount is shown.), And also the non-volatile part of a solution (an inorganic filler is included). Methyl ethyl ketone was added so that it might become 64 mass%, and the thermosetting resin composition (resin varnish) of each Example and each comparative example was prepared. Using the thermosetting resin composition, the presence or absence of precipitates was confirmed according to the method described above.
Each obtained thermosetting resin composition was impregnated into 0.1 mm thick E glass cloth “# 3313” (model number, manufactured by Nitto Boseki Co., Ltd.), and heated and dried at 140 ° C. for 3.5 minutes. A prepreg (resin content: 57 ± 2% by mass) was obtained.
18 μm copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) is stacked on both sides of the 8 prepregs stacked, and 80 minutes at a temperature of 200 ° C. and a pressure of 25 kgf / cm ² (= 2.45 MPa). Heat-press molding was performed to prepare a double-sided copper-clad laminate having a thickness of 0.8 mm (eight prepregs).
Using the copper-clad laminate thus produced, measurement and evaluation of adhesion to copper foil, heat resistance, dielectric properties, glass transition temperature, coefficient of thermal expansion, and formability were carried out according to the above methods. The results are shown in Tables 1-2.

From Table 1, Examples 1-9 showed excellent dielectric properties while maintaining high adhesion to the copper foil. Furthermore, it has high heat resistance and high glass transition temperature, and has a low coefficient of thermal expansion. Moreover, abnormality, such as a void and a blur, is not confirmed but it turns out that a moldability is also favorable. Excellent solubility in organic solvents.
On the other hand, in Comparative Examples 1 to 4 using epoxidized polybutadiene having no hydroxyl group at the molecular end instead of the component (B), the adhesiveness with the copper foil was lowered. Further, in Comparative Examples 5 to 8 using a polybutadiene resin not modified with epoxy instead of the component (B), the adhesiveness with the copper foil was further lowered and the heat resistance was also lowered. And in Comparative Examples 9-12 which used an epoxy resin instead of (B) component, since a dielectric characteristic deteriorates, a thermal expansion coefficient increases, Furthermore, since the compounding quantity of an epoxy resin is a small amount, The adhesiveness of was not sufficient.

  The thermosetting resin composition of the present invention and the prepreg formed using the thermosetting resin composition have high adhesion to copper foil, high heat resistance, excellent dielectric properties, high glass transition temperature, low thermal expansion. Since it has a coefficient and good moldability, it is useful as a copper-clad laminate and printed wiring board for electronic equipment.

Claims (11)

(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 having a hydroxyl group, and (C) a maleimide compound,
A thermosetting resin composition comprising: The component (A) includes 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 copolymer resin.

(In the formula, R ^A1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^A2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 6 to 20 carbon atoms. An aryl group, a hydroxyl group or a (meth) acryloyl group, wherein x is an integer of 0 to 3. However, when x is 2 or 3, a plurality of R ^A2 may be the same or different. May be.)   In the component (A), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [the structural unit derived from the aromatic vinyl compound / the structural unit derived from maleic anhydride] (mole The thermosetting resin composition according to claim 1 or 2, wherein the ratio is 2-9. The thermosetting resin composition according to any one of claims 1 to 3, wherein the component (B) is an epoxy-modified polybutadiene represented by the following general formula (B).

(In the formula, a, b and c each represent a ratio of structural units in parentheses, a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.30. 0.80, and a + b + c = 1.00 and (a + c)> b are satisfied, and y represents the number of structural units in parentheses and is an integer of 10 to 250.)   The thermosetting resin composition according to any one of claims 1 to 4, wherein the component (C) is a maleimide compound having at least two N-substituted maleimide groups in one molecule. The maleimide compound (c1) in which the component (C) is represented by any one of the following general formulas (c1-1) to (c1-5) is a monoamine compound (c2) and a diamine compound (c3) having an acidic substituent. The thermosetting resin composition according to any one of claims 1 to 5, which is a maleimide compound modified with (1).

(Wherein R ^{C1 to} R ^C3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^C1 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. An alkylidene group, -O-, -C (= O)-, -S-, -SS- or a sulfonyl group, wherein p, q and r are each independently an integer of 0 to 4; s is an integer of 0-10.) The monoamine compound (c2) having the acidic substituent is represented by the following general formula (c2-1), and the diamine compound (c3) is represented by any one of the following general formulas (c3-1) to (c3-3). The thermosetting resin composition according to claim 6.

(Wherein R ^C4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ^C5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. T represents 1 to 5) Integer, u is an integer of 0 to 4 and satisfies 1 ≦ t + u ≦ 5, provided that when t is an integer of 2 to 5, a plurality of R ^C4 may be the same or different. In addition, when u is an integer of 2 to 4, a plurality of R ^C5 may be the same or different.

(X ^C2 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 group. R ^C6 and R ^C7 each independently represent 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, and v and w are each Independently, it is an integer of 0-4.
X ^C3 and X ^C4 are each independently a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O- or a sulfonyl group. )   Furthermore, it contains at least one selected from the group consisting of (D) radical reaction initiator, (E) curing accelerator, (F) flame retardant and (G) inorganic filler. The thermosetting resin composition according to any one of the above.   The prepreg containing the thermosetting resin composition of any one of Claims 1-8.   A copper-clad laminate obtained by laminating the prepreg according to claim 9 and a copper foil.   A printed wiring board using the copper-clad laminate according to claim 10.