JP2016060780A - Thermosetting resin composition, prepreg, laminate and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which has adequate copper foil adhesiveness, glass transition temperature, moisture solder heat resistance, low thermal expansion, flame retardance and dielectric characteristics; and a prepreg; a laminate; and a printed wiring board.SOLUTION: A thermosetting resin composition contains: a compound which is obtained by reacting a maleimide compound having at least two N-substituted maleimide groups in one molecule and an amine compound that is represented by formula (a2-1) and has an acidic substituent, and has the acidic substituent and the N-substituted maleimide group in a molecular structure; and a compound which is obtained by reacting a siloxane resin having a carboxyl group in a molecule terminal and an epoxy compound having at least two epoxy groups in one molecule, and has a hydroxyl group and the epoxy group in a molecular structure. In the formula (a2-1), Ris an acidic substituent of a hydroxyl group, a carboxyl group or a sulfonic acid group; Ris an alkyl group or a halogen atom; x is an integer of 1 to 5; and y is an integer of 0 to 4.SELECTED DRAWING: None

Description

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

  Thermosetting resin compositions have a cross-linked structure and exhibit high heat resistance and dimensional stability, and thus are widely used in the field of electronic components and the like. In particular, a laminate (for example, copper-clad laminate) formed from a prepreg impregnated or coated with a thermosetting resin composition on a substrate, or a conductor pattern is formed on the surface or surface of this laminate and the inside thereof. In printed wiring boards and interlayer insulating materials, high copper foil adhesion and heat resistance, and good low thermal expansion are required due to recent demands for higher density and higher reliability.

  A bismaleimide compound having thermosetting properties is a resin excellent in dielectric properties, flame retardancy and heat resistance. However, when a known bismaleimide compound having no curing reactivity with an epoxy resin is used as it is as an epoxy-curable thermosetting resin, there is a problem that heat resistance and toughness are insufficient. Therefore, a thermosetting resin containing an adduct of a bismaleimide compound and aminophenol has been proposed (see Patent Documents 1 and 2). A thermosetting resin composition containing an adduct of a bismaleimide compound and aminobenzoic acid produced without using an organic solvent and a benzoguanamine formaldehyde condensate has also been proposed (see Patent Document 3). .

Japanese Patent Publication No. 63-34899 JP-A-6-32969 Japanese Patent Publication No. 6-8342

However, even when the thermosetting resin compositions of Patent Documents 1 and 2 are used as a copper clad laminate or an interlayer insulating material, the curing reactivity and toughness are still insufficient, and the heat resistance, reliability and workability Etc. are also insufficient. In addition, the thermosetting resin composition of Patent Document 3 has a low thermal decomposition temperature, and lacks the heat resistance to lead-free solder that has recently been required.
Therefore, the object of the present invention is to provide a thermosetting resin composition having good copper foil adhesion, glass transition temperature, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy and dielectric properties, as well as prepregs, laminates and prints. It is to provide a wiring board.

  As a result of earnest research to solve the above-mentioned problems, the present inventors have obtained by reacting a specific maleimide compound with a specific amine compound having an acidic substituent, “an acidic substituent in the molecular structure and It is obtained by esterifying a compound having a N-substituted maleimide group (A), a siloxane resin having a carboxyl group at the molecular end and a specific epoxy compound, and having “a hydroxyl group and an epoxy group in the molecular structure”. The present inventors have found that a thermosetting resin composition containing “compound (B)” at a specific ratio can achieve the above-mentioned object, and has completed the present invention. The present invention has been completed based on such knowledge. The present invention includes the following contents.

（式中、Ｒ¹は、水酸基、カルボキシ基及びスルホン酸基から選択される酸性置換基を示す。Ｒ²は、炭素数１〜５のアルキル基又はハロゲン原子を示す。ｘは１〜５の整数、ｙは０〜４の整数であり、且つ、１≦ｘ＋ｙ≦５を満たす。但し、ｘが２〜５の整数の場合、複数のＲ¹は同一であってもよいし、異なっていてもよい。また、ｙが２〜４の整数の場合、複数のＲ²は同一であってもよいし、異なっていてもよい。）
［２］一般式（ａ２−１）中、Ｒ¹が水酸基である、上記［１］に記載の熱硬化性樹脂組成物。
［３］前記シロキサン樹脂（ｂ１）が下記一般式（ｂ１−１）で表されるシロキサン樹脂である、上記［１］又は［２］に記載の熱硬化性樹脂組成物。

（式中、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、各々独立に、炭素数１〜５のアルキル基、フェニル基又は置換フェニル基を示す。ｍは、５〜１００の整数である。複数のＲ³は、それぞれ同一であってもよいし、異なっていてもよい。また、複数のＲ⁴は、それぞれ同一であってもよいし、異なっていてもよい。また、Ｘ¹及びＸ²は、各々独立に、炭素数１〜５の飽和炭化水素基を示す。）
［４］前記エポキシ化合物（ｂ２）が、下記式（ｂ２−１−１）で表される構造単位と下記式（ｂ２−１−２）で表される構造単位とを有するナフトールアラルキルクレゾール共重合ノボラック型エポキシ樹脂である、上記［１］〜［３］のいずれか１つに記載の熱硬化性樹脂組成物。

［５］さらに、ジアミン化合物、無機充填剤、難燃剤及び硬化促進剤から選択される少なくとも１種を含有する、上記［１］〜［４］のいずれか１つに記載の熱硬化性樹脂組成物。
［６］上記［１］〜［５］のいずれか１つに記載の熱硬化性樹脂組成物を、基材に含浸又は塗工してなるプリプレグ。
［７］上記［６］に記載のプリプレグを用いて形成された積層板。
［８］上記［７］に記載の積層板に配線パターンを形成して得られるプリント配線板。 [1] A reaction between a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a2) having an acidic substituent represented by the following general formula (a2-1) And a compound (A) having an acidic substituent and an N-substituted maleimide group in the molecular structure, a siloxane resin (b1) having a carboxyl group at the molecular end, and at least two epoxies in one molecule. Compound (B) having a hydroxyl group and an epoxy group in the molecular structure obtained by reacting with an epoxy compound (b2) having a group
A heat-curable resin composition comprising the compound (A), wherein the content of the compound (A) is 30 to 90 parts by mass with respect to 100 parts by mass of the total of the compounds (A) and (B). Curable resin composition.

(In the formula, R ¹ represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ² represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. X represents 1 to 5) An integer, y is an integer of 0 to 4, and satisfies 1 ≦ x + y ≦ 5, provided that when x is an integer of 2 to 5, a plurality of R ¹ may be the same or different. In addition, when y is an integer of 2 to 4, a plurality of R ² may be the same or different.
[2] The thermosetting resin composition according to [1], wherein R ¹ is a hydroxyl group in the general formula (a2-1).
[3] The thermosetting resin composition according to the above [1] or [2], wherein the siloxane resin (b1) is a siloxane resin represented by the following general formula (b1-1).

^{(Wherein, R 3, R 4, R} 5 and R ⁶ are each independently, .m represents an alkyl group, a phenyl group or a substituted phenyl group having 1 to 5 carbon atoms, an integer of 5 to 100. The plurality of R ³ may be the same or different, and the plurality of R ⁴ may be the same or different, and X ¹ and X ² each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms.)
[4] Naphthol aralkylcresol copolymer in which the epoxy compound (b2) has a structural unit represented by the following formula (b2-1-1) and a structural unit represented by the following formula (b2-1-2) The thermosetting resin composition according to any one of [1] to [3], which is a novolac type epoxy resin.

[5] The thermosetting resin composition according to any one of [1] to [4], further including at least one selected from a diamine compound, an inorganic filler, a flame retardant, and a curing accelerator. object.
[6] A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition according to any one of [1] to [5].
[7] A laminate formed using the prepreg according to [6] above.
[8] A printed wiring board obtained by forming a wiring pattern on the laminated board according to [7].

  The thermosetting resin composition of the present invention has good copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. According to the present invention, a prepreg impregnated or coated with the thermosetting resin composition, a laminate formed using the prepreg, and a printed wiring board obtained by forming a wiring pattern on the laminate are obtained. It is done.

Hereinafter, embodiments of the present invention will be described in detail.
[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule and an acidic substituent represented by the general formula (a2-1) described later. A compound (A) having an acidic substituent and an N-substituted maleimide group in the molecular structure, and a siloxane resin (b1) having a carboxyl group at the molecular end, obtained by reacting with an amine compound (a2) having Compound (B) having a hydroxyl group and an epoxy group in its molecular structure, obtained by reacting an epoxy compound (b2) having at least two epoxy groups in one molecule
A heat-curable resin composition comprising the compound (A), wherein the content of the compound (A) is 30 to 90 parts by mass with respect to 100 parts by mass of the total of the compounds (A) and (B). It is a curable resin composition.
Hereinafter, each component contained in the thermosetting resin composition of the present invention will be described in detail.

<Compound (A)>
Compound (A) is a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule [hereinafter abbreviated as maleimide compound (a1)] and a general formula (a2-1) described later. A compound having an acidic substituent and an N-substituted maleimide group in its molecular structure, obtained by reacting with an amine compound (a2) having an acidic substituent [hereinafter abbreviated as amine compound (a2)] It is.

(Maleimide compound (a1))
The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups in one molecule.
As the maleimide compound (a1), a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups among a plurality of maleimide groups [hereinafter referred to as an aromatic hydrocarbon group-containing maleimide] preferable. 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 (a1) includes 2 to 5 N-substituted maleimides per molecule from the viewpoints of copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. A maleimide compound having a group is preferable, and a maleimide compound having two N-substituted maleimide groups in one molecule is more preferable. Moreover, as a maleimide compound (a1), from the viewpoint of copper foil adhesiveness, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion property, flame retardancy, and dielectric properties, the following general formulas (a1-1) to (a1- 4) It is more preferable that it is an aromatic hydrocarbon group-containing maleimide represented by any one of the following, and the aromatic carbonization represented by the following general formula (a1-1), (a1-2) or (a1-4) More preferably, it is a hydrogen group-containing maleimide.

In said formula, R < ¹¹ > -R < ¹³ > shows a C1-C5 aliphatic hydrocarbon group each independently. X ¹¹ represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, —O— or a sulfonyl group. p, q, and r are each independently an integer of 0-4. n is an integer of 0-10.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^{11 to} R ¹³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, An n-pentyl group and the like can be mentioned. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms from the viewpoint of copper foil adhesion, glass transition temperature, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. And more preferably a methyl group or an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by X ¹¹ 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. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, more preferably from the viewpoint of copper foil adhesion, glass transition temperature, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. A methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ¹¹ 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 copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties.
X ¹¹ is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
p, q and r are each independently an integer of 0 to 4, and from the viewpoints of copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy and dielectric properties, Preferably it is an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
n is an integer of 0 to 10, and is preferably 0 to 5 and more preferably 0 to 3 from the viewpoint of availability. In particular, the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (a1-3) is preferably a mixture of n = 0 to 3.

Examples of the maleimide compound (a1) include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5, 5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, etc. It is done. Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4 from the viewpoint of high reaction rate and higher heat resistance. , 4-diphenylmethane bismaleimide and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane are preferred, and 2,2-bis [4- (4-maleimidophenoxy) phenyl from the viewpoint of dielectric properties. Propane is more preferred.
As the maleimide compound (a1), one type may be used alone, or two or more types may be used in combination.

(Amine compound (a2))
The amine compound (a2) is an amine compound having an acidic substituent represented by the following general formula (a2-1).

In the general formula (a2-1), R ¹ represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ² represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. x is an integer of 1 to 5, y is an integer of 0 to 4, and 1 ≦ x + y ≦ 5 is satisfied. However, when x is integer of 2 to 5, to a plurality of R ¹ may be the same or different. Further, if y is 2 to 4 integer, to a plurality of R ² may be the same or different.
The acidic substituent represented by R ¹ is preferably a hydroxyl group or a carboxyl group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
x is an integer of 1 to 5, and preferably an integer of 1 to 3, more preferably 1 from the viewpoint of copper foil adhesion, glass transition temperature, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy and dielectric properties. Or 2, more preferably 1.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ² 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. Can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the halogen atom represented by R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
y is an integer of 0 to 4, and preferably an integer of 0 to 3, more preferably 0, from the viewpoints of copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. An integer of ˜2, more preferably 0 or 1, particularly preferably 0.
The amine compound (a2) is more preferably the following general formula (a2-2) or (a2) from the viewpoints of copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. -3), more preferably an amine compound represented by the following general formula (a2-2). However, R ¹ , R ² and y in the general formulas (a2-2) and (a2-3) are the same as those in the general formula (a2-1), and preferable ones are also the same.

Examples of the amine compound (a2) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and reactivity, and o-aminophenol from the viewpoint of heat resistance. , M-aminophenol and p-aminophenol are preferable, and p-aminophenol is more preferable in consideration of dielectric properties, low thermal expansibility and production cost.
The amine compound (a2) may be used alone or in combination of two or more.

(Use amount of maleimide compound (a1) and amine compound (a2))
In the reaction of the maleimide compound (a1) and the amine compound (a2), the amount of both used is the primary amino group equivalent [denoted as —NH ₂ group equivalent] of the amine compound (a2) and the maleimide compound (a1). ) Of the maleimide group equivalent preferably satisfies the following formula.
2 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalent] ≦ 11
By setting [maleimide group equivalent] / [-NH ₂ group equivalent total] to 2 or more, gelation and hygroscopic solder heat resistance do not decrease, and by setting it to 11 or less, Since solubility and moisture absorption solder heat resistance do not fall, it is preferable.
From the same viewpoint, more preferably,
3 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalent] ≦ 11
More preferably,
3 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalent] ≦ 10.5 is satisfied.

(Organic solvent)
The reaction between the maleimide compound (a1) and the amine compound (a2) is preferably performed in an organic solvent. Moreover, it is preferable to implement by stirring for 0.1 to 10 hours suitably heating and heat retention.
The organic solvent is not particularly limited as long as it does not adversely affect the reaction between the maleimide compound (a1) and the amine compound (a2). For example, alcohols such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether Solvents: Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene and mesitylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone A nitrogen atom-containing solvent including a system solvent; a sulfur atom-containing solvent including a sulfoxide-based solvent such as dimethyl sulfoxide; and an ester solvent such as γ-butyrolactone. Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, ester solvents are preferable, and from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve are more preferable, and high volatility, Considering that it is difficult to remain as a residual solvent during the production of the prepreg, propylene glycol monomethyl ether is more 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, Preferably it is 10-1000 mass parts with respect to a total of 100 mass parts of a maleimide compound (a1) and an amine compound (a2). Preferably it may be 20 to 500 parts by mass, more preferably 50 to 250 parts by mass. By setting it as 10 mass parts or more, solubility can be ensured, and by setting it as 1000 mass parts or less, the fall of reaction efficiency can be prevented.

(Reaction catalyst)
You may implement reaction of a maleimide compound (a1) and an amine compound (a2) in presence of a reaction catalyst as needed. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine, and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine.
A reaction catalyst 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 a reaction catalyst, Preferably it is 0-0.5 mol with respect to 1 mol of maleimide groups which a maleimide compound (a1) has, More preferably, it is 0-0.3 mol, More preferably, it is 0. ~ 0.1 mol.
(Reaction temperature)
The reaction between the maleimide compound (a1) and the amine compound (a2) is preferably carried out at 70 to 150 ° C, more preferably 90 to 140 ° C, and further preferably 100 to 130 ° C.

A compound in which the carbon-carbon double bond in the maleimide group of the maleimide compound (a1) reacts with the primary amino group of the amine compound (a2) by the reaction of the maleimide compound (a1) and the amine compound (a2). Thus, a compound (A) having an acidic substituent and an N-substituted maleimide group is obtained. As a compound (A), the compound represented by either of the following general formula (A1)-(A4) is mentioned, for example. In the following general formulas (A1) to (A4), R ¹ , R ² , R ^{11 to} R ¹³ , X ¹¹ , n, p, q, r, x and y are the same as those in the general formula (a1-1). To (a1-4) or the same as those described in the general formula (a2-1), and preferable ones are also the same.

<Compound (B)>
The compound (B) includes a siloxane resin (b1) having a carboxyl group at the molecular terminal [hereinafter abbreviated as siloxane resin (b1)] and an epoxy compound (b2) having at least two epoxy groups in one molecule [ Hereinafter, it is a compound having a hydroxyl group and an epoxy group in the molecular structure obtained by reacting with an abbreviated epoxy compound (b2).
When the siloxane resin (b1) and the epoxy compound (b2) are reacted, a secondary alcohol is generated by an esterification reaction between the carboxyl group of the siloxane resin (b1) and the epoxy group of the epoxy compound (b2). .

(Siloxane resin (b1))
The siloxane resin (b1) is not particularly limited as long as it is a siloxane resin having a carboxyl group at the molecular end. The siloxane resin (b1) preferably has a carboxyl group at both molecular ends from the viewpoints of copper foil adhesion, glass transition temperature, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. It is more preferable to have one carboxyl group at each end of the molecule. From the same viewpoint, the siloxane resin (b1) preferably has a structural unit represented by the following general formula (1) and has a carboxyl group at the molecular end. Further, the carboxyl group equivalent of the siloxane resin (b1) is preferably 600 to 3000 g / eq, more preferably 700 to 2500 g / eq, still more preferably 700 to 1500 g / eq, and particularly preferably 700 to 1100 g / eq.

In the general formula (1), R ³ and R ⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
Examples of the substituent of the substituted phenyl group represented by R ³ and R ⁴ include an alkyl group having 1 to 5 carbon atoms and an alkoxyl group having 1 to 5 carbon atoms. Examples of the alkyl group include the same alkyl groups as described above, and preferred ones are also the same. Examples of the alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and an n-pentyloxy group. The alkoxyl group is preferably an alkoxyl group having 1 to 3 carbon atoms.
R ³ and R ⁴ are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably as described above.

Moreover, it is preferable that the siloxane resin (b1) has 5 to 100 structural units represented by the general formula (1), and more preferably 5 to 50 structural units. At this time, the plurality of R ³ may be the same or different. Further, the plurality of R ⁴ may be the same or different.
As the siloxane resin (b1), a siloxane resin represented by the following general formula (b1-1) from the viewpoint of copper foil adhesion, glass transition temperature, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties It is preferable that

In the general formula ^{(b1-1), R 3, R} 4, R 5 and R ⁶ each independently represents an alkyl group, a phenyl group or a substituted phenyl group having 1 to 5 carbon atoms. m is an integer of 5-100. A plurality of R ³ may be the same or different. Further, the plurality of R ⁴ may be the same or different. X ¹ and X ² each independently represent a saturated hydrocarbon group having 1 to 5 carbon atoms.
R ^{3 to} R ⁶ are described in the same manner as R ¹ and R ² in the general formula (1), and preferred ones are also the same.
m is preferably an integer of 5 to 50. Depending on the value of m, the carboxyl group equivalent of the siloxane resin represented by the general formula (b1-1) is preferably 600 to 3000 g / eq, more preferably 700 to 2500 g / eq, still more preferably 700 to 1500 g / eq, Particularly preferably, it is 700 to 1100 g / eq.
Examples of the saturated hydrocarbon group having 1 to 5 carbon atoms represented by X ¹ and X ² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and 1,5. -A pentamethylene group etc. are mentioned.

From the above, the siloxane resin (b1) is represented by the following general formula (b1-2) from the viewpoints of copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. A siloxane resin is preferable.

In the general formula (b1-2), m, X ¹ and X ² are the same as those in the general formula (b1-1), and preferable ones are also the same.
The siloxane resin represented by the general formula (b1-1) or (b1-2) can be obtained commercially from Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd., or the like.
As the siloxane resin (b1), from the viewpoint of moisture absorption solder heat resistance, low thermal expansion and solvent solubility, trade name “X-22-162A” (carboxyl group equivalent: 865 g / eq) manufactured by Shin-Etsu Chemical Co., Ltd. The trade name “X-22-162B” (carboxyl group equivalent: 1500 g / eq) and the trade name “X-22-162C” (carboxyl group equivalent: 2330 g / eq) are preferable.
A siloxane resin (b1) may be used individually by 1 type, and may use 2 or more types together.

<Epoxy compound (b2)>
Examples of the epoxy compound (b2) include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among these, a glycidyl ether type epoxy resin is preferable.
Epoxy resins are classified into various epoxy resins depending on the difference in the main skeleton. In each of the above types of epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are also included. Epoxy resin; biphenylaralkylphenol type epoxy resin; phenol novolac type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolac type epoxy resin, naphthol alkylphenol copolymer novolak type epoxy resin, naphthol aralkyl cresol copolymer novolak type epoxy resin, bisphenol A novolak Type epoxy resin, novolak type epoxy resin such as bisphenol F novolak type epoxy resin; stilbene type epoxy resin ; Triazine skeleton containing epoxy resin; fluorene skeleton containing epoxy resin; naphthalene type epoxy resin; triphenylmethane type epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylylene type epoxy resin; dicyclopentadiene type epoxy resin, etc. Classified as cyclic epoxy resin. Furthermore, the phosphorus containing epoxy resin which introduce | transduced the phosphorus compound to at least 1 sort (s) of these is also mentioned.
Among these, from the viewpoints of copper foil adhesion, glass transition temperature, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties, biphenyl aralkyl phenol type epoxy resin, naphthol aralkyl cresol copolymer novolak type epoxy resin, biphenyl Type epoxy resin is preferred.
An epoxy compound (b2) may be used individually by 1 type, and may use 2 or more types together.

  Furthermore, it has a structural unit represented by the following formula (b2-1-1) and a structural unit represented by the following formula (b2-1-2) from the viewpoint of moldability when the multilayer material is press-molded. A naphthol aralkylcresol copolymer novolak type epoxy resin, a biphenyl type epoxy compound represented by the following general formula (b2-2), and a biphenylaralkylphenol type epoxy resin having a structural unit represented by the following formula (b2-3) are preferable. More preferably, it is a naphthol aralkyl cresol copolymer novolak type epoxy resin having a structural unit represented by the following formula (b2-1-1) and a structural unit represented by the following formula (b2-1-2). .

（式中、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰は、各々独立に、水素原子又はメチル基である）

^{(Wherein, R 7, R 8, R} 9 and R ¹⁰ are each independently a hydrogen atom or a methyl group)

The structural unit represented by the above formula (b2-1-1) is preferably a structural unit represented by the following formula (b2-1-1 ′). The structural unit represented by the formula (b2-1-2) is preferably a structural unit represented by the following formula (b2-1-2 ′).

Epoxy equivalent of naphthol aralkylcresol copolymer novolak type epoxy resin having a structural unit represented by the above formula (b2-1) and biphenylaralkylphenol type epoxy resin having a structural unit represented by the above formula (b2-3) Are preferably 100 to 500 g / eq, more preferably 120 to 400 g / eq, and still more preferably 140 to 300 g / eq.
Here, the epoxy equivalent is the mass of the resin per epoxy group (g / eq), and can be measured according to the method defined in JIS K 7236. Specifically, using an automatic titration apparatus “GT-200 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd., weigh 2 g of epoxy resin in a 200 ml beaker, drop 90 ml of methyl ethyl ketone, dissolve in an ultrasonic cleaner, and then dissolve glacial acetic acid. It is obtained by adding 10 ml and 1.5 g of cetyltrimethylammonium bromide and titrating with a 0.1 mol / L perchloric acid / acetic acid solution.
As a commercially available product of the epoxy compound (b2), a biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation; trade name “YX-4000”, epoxy equivalent: 186 g / eq), naphthol aralkyl cresol copolymer novolak type epoxy resin (Nipponization) Made by Yakuhin Co., Ltd .; trade name “NC-7000L”, epoxy equivalent; 230 g / eq), naphthalene type epoxy resin (Mitsubishi Chemical Corporation; trade name “HP-4032”, epoxy equivalent; 152 g / eq), dicyclo Examples thereof include pentadiene type epoxy resins (manufactured by Mitsubishi Chemical Corporation; trade name “HP-7200H”, epoxy equivalent: 280 g / eq). The epoxy equivalent described next to the product name is a value described in the catalog of the product manufacturer.

(Use amount of siloxane resin (b1) and epoxy compound (b2))
In the reaction of the siloxane resin (b1) and the epoxy compound (b2), the amount of each raw material used is preferably as follows. That is, the number of epoxy groups [epoxy compound (b2) used / epoxy group equivalent of epoxy compound (b2)] of the epoxy compound (b2) is the number of carboxyl groups of the siloxane resin (b1) [used amount of siloxane resin (b1) / The carboxyl group equivalent of the siloxane resin (b1) is preferably 1.5 to 10 times, and more preferably 2 to 10 times. If it is 1.5 times or more, gelation of the siloxane resin (b1) and the epoxy compound (b2) during the reaction can be suppressed. Moreover, the fall of the moisture resistance of the laminated board produced using the compound (B) obtained by reacting a siloxane resin (b1) and an epoxy compound (b2) can be prevented. Moreover, if it is 10 times or less, the fall of the solubility with respect to an organic solvent and the fall of a cure rate can be prevented.

(Organic solvent)
The reaction of the siloxane resin (b1) and the epoxy compound (b2) is preferably carried out in the presence of an organic solvent.
The organic solvent is not particularly limited as long as it does not adversely affect the reaction between the siloxane resin (b1) and the epoxy compound (b2). For example, aromatic solvents such as toluene, xylene, mesitylene; methyl ethyl ketone, methyl isobutyl ketone, Examples thereof include ketone solvents such as cyclohexanone; ether solvents such as tetrahydrofuran; sulfur atom-containing solvents including sulfoxide solvents such as dimethyl sulfoxide; ester solvents such as γ-butyrolactone. Among these, aromatic solvents are preferable from the viewpoints of high solubility and volatility and hardly remaining at the time of manufacturing the prepreg, and copper foil adhesiveness, hygroscopic solder heat resistance and dielectric properties of the obtained laminate, and toluene. Is more preferable.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
The amount of the organic solvent used is preferably 40 to 1000 parts by mass, more preferably 40 to 500 parts by mass with respect to 100 parts by mass of the total of the siloxane resin (b1) and the epoxy compound (b2). It is more preferable to set it as 40-200 mass parts, and it is especially preferable to set it as 40-150 mass parts. When the blending amount of the organic solvent is 40 parts by mass or more, the solubility of the raw material is sufficiently obtained, and the inability to synthesize due to thickening can be prevented. Further, if it is 1000 parts by mass or less, an appropriate synthesis time can be obtained, and an unnecessary increase in manufacturing cost can be avoided.

(Reaction catalyst)
A reaction catalyst may be used for the reaction between the siloxane resin (b1) and the epoxy compound (b2). The reaction catalyst is not particularly limited. Examples of reaction catalysts include amine compounds such as triethylamine and tributylamine; nitrogen-containing aromatic heterocyclic compounds such as pyridine; imidazole compounds such as methylimidazole and phenylimidazole; and phosphorus-based catalysts containing triarylphosphine such as triphenylphosphine. Etc. A reaction catalyst may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of copper foil adhesiveness and moisture-absorbing solder heat resistance, a phosphorus-based catalyst is preferable, triarylphosphine is more preferable, and triphenylphosphine is more preferable.
A reaction catalyst 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 a reaction catalyst, Preferably it is 0-0.5 mol with respect to 1 mol of carboxyl groups which siloxane resin (b1) has, More preferably, it is 0-0.2 mol, More preferably, it is 0. ~ 0.1 mol.

(Reaction temperature)
The reaction of the siloxane resin (b1) and the epoxy compound (b2) is preferably carried out by stirring for 0.1 to 10 hours while appropriately heating or keeping warm.
The reaction temperature in the reaction of the siloxane resin (b1) and the epoxy compound (b2) is preferably 25 to 200 ° C, more preferably 50 to 150 ° C, and further preferably 70 to 130 ° C. When the reaction temperature is 25 ° C. or higher, an appropriate reaction rate can be obtained, and when the reaction temperature is 200 ° C. or lower, a high boiling point organic solvent is not required. A decrease in heat resistance due to the residue can be prevented.
In addition, confirmation of the end point of the reaction and confirmation of the formation of compound (B) are obtained by taking out a small amount of sample and measuring the acid value by neutralization titration, and confirming the decrease of the carboxyl group in the siloxane resin (b1) as the raw material. Can be determined. The acid value measurement method by neutralization titration conforms to the method according to JIS standards. For example, a method of adding phenolphthalein as an indicator to a small sample taken and titrating it with a methanolic potassium hydroxide solution to confirm the neutralization point is preferred. The acid value at the end of the reaction is preferably 1/5 or less of the acid value at the beginning of the reaction, more preferably 0 mgKOH / g. By setting the acid value at the end point to 1/5 or less of the acid value at the beginning of the reaction, the amount of the compound (B) having a hydroxyl group and an epoxy group in the molecular structure becomes sufficient, and the phase with the compound (A) A highly tolerable one is obtained.

（式中、Ｒ³〜Ｒ⁶、Ｘ¹、Ｘ²及びｍは、前記定義の通りである。ｓ及びｔは、１以上の整数である。） As an example of the compound (B) obtained by the reaction of the siloxane resin (b1) and the epoxy compound (b2), a compound represented by the following general formula (B1) [a siloxane resin represented by the general formula (b1-1) and A reactive organism with a naphthol aralkylcresol copolymer novolak type epoxy resin having a structural unit represented by the formula (b2-1)].

(In the formula, R ^{3 to} R ⁶ , X ¹ , X ² and m are as defined above. S and t are integers of 1 or more.)

[Thermosetting resin composition]
The thermosetting resin composition of the present invention contains the compound (A) and the compound (B). The content of the compound (A) with respect to 100 parts by mass of the total of the compound (A) and the compound (B) is the viewpoint of copper foil adhesiveness, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy and dielectric properties. From 30 to 90 parts by mass, preferably from 50 to 80 parts by mass. When the content of the compound (A) is within the above range, the copper foil adhesiveness, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy and dielectric properties tend to be good.

The thermosetting resin composition of the present invention can contain a thermoplastic resin, an elastomer, an additive, an organic solvent, and the like as necessary within a range not impairing the effects of the present invention. These may contain 1 type independently, and may contain 2 or more types.
(Thermoplastic resin)
Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether, phenoxy resin, polycarbonate, polyester, polyamide, polyimide, xylene resin, petroleum resin, and silicone resin. These may be used individually by 1 type and may use 2 or more types together.

(Elastomer)
Examples of the elastomer include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. Among these, styrene elastomers and olefin elastomers are preferable, and styrene elastomers are more preferable. The styrene elastomer may be unhydrogenated, but is more preferably a hydrogenated styrene elastomer.
One type of elastomer may be used alone, or two or more types may be used in combination.
Examples of the styrene elastomer (including hydrogenated styrene elastomer) include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer ( SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and the like. In addition to styrene, which is a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and the like can be used.
Moreover, maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2.2.1] -5-heptene-2,3- Dicarboxylic acids and the like, and anhydrides, esters, amides and imides of these dicarboxylic acids; so-called carboxylic acid modifications modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like and esters of these monocarboxylic acids Styrenic elastomers can also be preferably used.
Commercially available products can be used as the styrenic elastomer. Specifically, “Tufprene (registered trademark)”, “Asaprene (registered trademark) T”, “Tuftec (registered trademark)” (above, Asahi Kasei Chemicals Corporation) "Elastomer AR" (manufactured by Aron Kasei Co., Ltd.), "Clayton (registered trademark) G" (manufactured by Shell Japan Ltd.), "JSR-TR", "TSR-SIS", "Dynalon (registered trademark)" (Made by JSR Co., Ltd.), “DENKA (registered trademark) STR” (manufactured by Denki Kagaku Kogyo Co., Ltd.), “QUINTAC (registered trademark)” (manufactured by ZEON CORPORATION), “ESPOLEX (registered trademark) SB "Series (manufactured by Sumitomo Chemical Co., Ltd.)", "Lavalon (registered trademark)" (manufactured by Mitsubishi Chemical Corporation), "Septon (registered trademark)", "Hibler (registered trademark)" ( On, manufactured by Kuraray Co., Ltd.), "Sumi flex" (Sumitomo Bakelite Co., Ltd.), "Reosutoma (registered trademark)", "Activision mer (registered trademark)" (or more, include the Riken Technos Co., Ltd.), and the like.

  The olefin elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, for example, an ethylene-propylene copolymer (EPR). ), Ethylene-propylene-diene copolymer (EPDM) and the like. Further, non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, and α-olefin copolymers are also included. Furthermore, examples of the olefin elastomer include carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, and phenol-modified polybutadiene. Specific examples of olefin elastomers include ethylene-α-olefin copolymer rubber, ethylene-α-olefin / non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer. Examples thereof include polymer rubber. Commercially available products can be used as the olefin-based elastomer. Specifically, “Miralastomer (registered trademark)” (manufactured by Mitsui Chemicals), “EXACT (registered trademark)” (manufactured by ExxonMobil Corporation), “ENGAGE” (Registered trademark) "(manufactured by Sadau Chemical Company), hydrogenated styrene-butadiene rubber" DYNABON HSBR "(manufactured by JSR Corporation), butadiene-acrylonitrile copolymer" NBR series "(manufactured by JSR Corporation), Examples thereof include “XER series” (manufactured by JSR Corporation) and the like of both end carboxyl group-modified butadiene-acrylonitrile copolymers.

  The content of the thermoplastic resin or elastomer in the thermosetting resin composition of the present invention is 100 parts by mass of the total of the compound (A) and the compound (B), respectively, provided that the compound (A) and the compound (B) are added to the solution. When used in a state, it is preferably 0 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, still more preferably 1 to 20 parts by mass, particularly preferably 100 parts by mass in terms of solid content]. 5 to 15 parts by mass.

(Additive)
Examples of the additive include a diamine compound, an inorganic filler, a flame retardant, a curing accelerator, an antioxidant, an ultraviolet absorber, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and an organic filler. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to contain at least one selected from diamine compounds, inorganic fillers, flame retardants and curing accelerators, and all of diamine compounds, inorganic fillers, flame retardants and curing accelerators are contained. More preferably.

(Diamine compound)
From the viewpoint of further improving the glass transition temperature, moisture-absorbing solder heat resistance and low thermal expansion property of the thermosetting resin composition of the present invention, a diamine compound may be contained.
Examples of the diamine compound include aromatic diamine compounds such as m-phenylenediamine, p-phenylene, and 3,3′-diethyl-4,4′-diaminodiphenylmethane; 1,3-bis (aminomethyl) cyclohexane, 1 , 2-cyclohexanediamine, aliphatic diamine compounds such as 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane; siloxane resins having amino groups, and the like. A diamine compound may be used individually by 1 type, and may use 2 or more types together. Among these, 3,3′-diethyl-4,4′-diaminodiphenylmethane is preferable from the viewpoint of copper foil adhesion and moisture absorption solder heat resistance, and siloxane having an amino group from the viewpoint of low thermal expansion. It is preferable to use a resin. The siloxane resin having an amino group is preferably, for example, a siloxane resin represented by the following general formula (2).

In said general formula (2), R < ⁷ >, R <^8> , R < ⁹ > and R < ¹⁰ > show a C1-C5 alkyl group, a phenyl group, or a substituted phenyl group each independently. u is an integer of 5 to 100. A plurality of R ⁷ may be the same or different. The plurality of R ⁸ may be the same or different. X ³ and X ⁴ each independently represent a saturated hydrocarbon group having 1 to 5 carbon atoms.
The siloxane resin represented by the general formula (2) is preferably a siloxane resin represented by the following general formula (2 ′).

上記一般式（２'）中、Ｘ³、Ｘ⁴及びｕは、前記一般式（２）中のものと同じである。

In the general formula (2 ′), X ³ , X ⁴ and u are the same as those in the general formula (2).

The thermosetting resin composition of the present invention may further contain an inorganic filler, and preferably contains it. By containing the inorganic filler, the coefficient of thermal expansion can be reduced, the elastic modulus can be increased, and the heat resistance and flame retardancy can be improved.
Examples of the inorganic filler include silica, alumina, mica, talc, short glass fiber, fine glass powder, hollow glass, calcium carbonate, and quartz powder. Among these, silica, alumina, mica, and talc are preferable from the viewpoint of heat resistance, flame retardancy, and dielectric properties, and silica and alumina are more preferable, and silica is more preferable from the viewpoint of high heat dissipation. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. , Crushed silica, fumed silica, fused silica (fused spherical silica) and the like. As the inorganic filler, fused silica is preferable.

  When fused silica is used as the inorganic filler, the average particle size is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm. By making the average particle size of the fused silica 0.1 μm or more, it is possible to maintain good fluidity when it is highly filled, and if it is 10 μm or less, it is fine when forming a circuit pattern on the insulating layer. There is a tendency that the pattern can be stably formed. Here, the average particle size is a particle size at a point corresponding to a volume of 50% when a 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 inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent from the viewpoint of improving dispersibility in the resin composition. Although it does not specifically limit as this surface treating agent, An aminosilane coupling agent, a vinyl silane coupling agent, an epoxy silane coupling agent, a styryl silane coupling agent, a methacryl silane coupling agent, a silicone oligomer coupling agent, etc. are mentioned. Of these, aminosilane coupling agents are preferred.
The aminosilane coupling agent is a silane having one or two amino groups and one silicon atom, preferably a silane having one amino group and one silicon atom. Examples of commercially available silica surface-treated with an aminosilane coupling agent include “SC-2050KNK” (average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.).
An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

  The content of the inorganic filler in the thermosetting resin composition of the present invention varies depending on the characteristics of the thermosetting resin composition and the desired function in the present invention, but the total of the compound (A) and the compound (B) is 100. Preferably 0 to 400 parts by mass, more preferably 20 to 300 parts by mass with respect to mass parts [however, when compound (A) and compound (B) are used in the form of a solution, 100 parts by mass in terms of solid content). Part by mass, more preferably 50 to 300 parts by mass, particularly preferably 100 to 300 parts by mass, and most preferably 150 to 250 parts by mass.

(Flame retardants)
Examples of the flame retardant include, for example, molybdenum compounds such as zinc molybdate, magnesium molybdate, calcium molybdate, and sodium molybdate, inorganic flame retardant aids such as antimony trioxide; boehmite type aluminum hydroxide (AlOOH), gibbsite type water Compounds such as aluminum oxide (Al (OH) ₃ ), etc., in which the thermal decomposition temperature of a metal hydrate is adjusted to 300 ° C. or higher by heat treatment; metals having a thermal decomposition temperature of less than 300 ° C. such as aluminum hydroxide and magnesium hydroxide Hydrates; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl-2,6-xylenyl phosphate, 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (di-2 , 6-Xylenyl phosphate), bisphenol A bi Phosphoric ester compounds such as su (diphenyl phosphate); Phosphazenes; Phosphorus flame retardants such as red phosphorus. The flame retardant is preferably a non-halogen flame retardant containing no halogen such as bromine or chlorine from the viewpoint of environmental problems in recent years.
From the viewpoint of heat resistance, the flame retardant is preferably an inorganic flame retardant aid, a compound having a thermal decomposition temperature adjusted to 300 ° C. or more, more preferably a molybdenum compound or boehmite aluminum hydroxide (AlOOH), and a molybdenum compound is further included. Zinc molybdate is preferred and particularly preferred. The molybdenum compound may be used by being supported on a carrier such as talc. For example, a compound in which zinc molybdate is supported on talc may be referred to as zinc molybdate-treated talc.
A flame retardant may be used individually by 1 type, and may use 2 or more types together.
The content of the flame retardant in the thermosetting resin composition of the present invention is from the viewpoint of improving flame retardancy without impairing copper foil adhesion, glass transition temperature, hygroscopic solder heat resistance, low thermal expansion and dielectric properties. The solid content of the thermosetting resin composition is preferably 0 to 50 parts by mass, more preferably 1 to 30 parts by mass, still more preferably 3 to 20 parts by mass, and particularly preferably 5 to 20 parts by mass. Part by mass.

(Curing accelerator)
Examples of curing accelerators include, for example, zinc metal naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), imidazole compounds, and the like. Examples thereof include organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Among these, an organic phosphorus compound is preferable from the viewpoints of copper foil adhesiveness, heat resistance, and flame retardancy.
Examples of organophosphorus compounds include, for example, ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine. , Triphenylphosphine / triphenylborane complex, tetraphenylphosphonium tetraphenylborate, addition reaction product of p-benzoquinone and tri-n-butylphosphine, and the like. Among these, an addition reaction product of p-benzoquinone and tri-n-butylphosphine is preferable.
A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
The content of the curing accelerator in the thermosetting resin composition of the present invention is 100 parts by mass of the total of compound (A) and compound (B) from the viewpoints of copper foil adhesiveness, heat resistance and flame retardancy [however, When the compound (A) and the compound (B) are used in the form of a solution, it is preferably 0 to 7 parts by mass, more preferably 0 to 5 parts by mass, and still more preferably 100 parts by mass in terms of solid content]. Is 0.001 to 3 parts by mass, particularly preferably 0.011 to 1 part by mass.

(Ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent brightener, adhesion improver, organic filler)
Examples of the ultraviolet absorber include benzotriazole compounds. Examples of the antioxidant include hindered phenol antioxidants and styrenated phenol antioxidants. Examples of the photopolymerization initiator include benzophenone photopolymerization initiators, benzyl ketal photopolymerization initiators, and thioxanthone photopolymerization initiators. Examples of the fluorescent brightener include stilbene derivatives. Examples of the adhesion improver include urea compounds such as urea silane, silane coupling agents, and the like. Examples of the organic filler include powders of organic substances such as silicone, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.
These may be used individually by 1 type and may use 2 or more types together.

(Organic solvent)
The thermosetting resin composition of the present invention may be made into a varnish state by adding an organic solvent from the viewpoint of facilitating handling by dilution and easy manufacture of a prepreg described later. A varnish is preferred.
Examples of the organic solvent include, but are not limited to, 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; tetrahydrofuran Ether solvents such as toluene; aromatic solvents such as toluene, xylene and mesitylene; nitrogen-containing solvents including amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; including sulfoxide solvents such as dimethyl sulfoxide Sulfur atom-containing solvents; ester solvents containing lactone solvents such as γ-butyrolactone.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are more preferable, and methyl ethyl ketone and methyl isobutyl ketone are preferable. More preferred is methyl ethyl ketone.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
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. If there is no particular limitation, the solid content concentration (concentration of components other than the organic solvent) derived from the thermosetting resin composition is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably 40. It is made to become -70 mass%, Most preferably, it will be 50-70 mass%.

(Method for preparing thermosetting resin composition)
In the preparation of the thermosetting resin composition of the present invention, first, a compound (A) having an acidic substituent and an N-substituted maleimide group in the molecular structure and a compound (B) having a hydroxyl group and an epoxy group in the molecular structure. Are reacted in the organic solvent by stirring for 0.1 to 10 hours while heating and holding as necessary. The end point of the reaction can be confirmed by the solution casting method. A small amount of the reaction solution is taken in an aluminum cup and heated and dried at 25 to 200 ° C. for 0.1 to 1 hour to volatilize the organic solvent and form a resin film on the aluminum cup. At this time, the resin film is preferably transparent from the viewpoint of the heat resistance of the laminate. If the resin film is opaque, the resins are not compatible with each other, and the resins are separated, so that the heat resistance may be significantly reduced.
If the end point of reaction is confirmed, the said reaction will be complete | finished and the thermosetting resin composition of this invention will be obtained by mixing the obtained solution and said other component as needed.

[Prepreg]
The prepreg of the present invention is obtained by impregnating or coating the base material with 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. Examples of the material for the sheet-like reinforcing base include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like reinforcement base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, or a surfacing mat, for example. 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 varnish is prepared by adding an organic solvent to the thermosetting resin composition, a sheet-like reinforcing base material is immersed in the varnish, and the sheet-like reinforcing base material is impregnated, 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. The adhesion amount of the thermosetting resin composition to the substrate is such that the resin content of the prepreg after drying (that is, the solid content derived from the thermosetting resin composition) is 20 to 90% by mass. After impregnating or coating the material, it is usually heat-dried at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.
As the prepreg, one sheet is used, or preferably 2 to 20 sheets are overlapped.

[Laminated board]
The laminated board of this invention is formed using the said prepreg. For example, it can be manufactured by using one sheet of the prepreg, or stacking 2 to 20 sheets, and laminating and forming the metal foil on one or both sides thereof.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, preferably copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, Iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferable, copper and amylnium are more preferable, and copper is more preferable.
As the molding conditions of the laminated plate, a known molding method of a laminated plate for an electrical insulating material and a multilayer plate can be applied, for example, using 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 metal foil, According to the use etc. of a printed wiring board, it can select suitably. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 10 to 50 μm, and particularly preferably 1 to 30 μm.

In addition, it is also preferable to form a plating layer by plating metal 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.

  The printed wiring board of the present invention is obtained by forming a wiring pattern on the laminated board. The method for forming the wiring pattern is not particularly limited. For example, a subtractive method, a full additive method, a semi-additive process (SAP) or a modified semi-additive method (m-SAP) is used. The wiring pattern can be formed by a known method such as Process. In other words, the metal foil of the laminated plate is processed by a known etching method, a plurality of laminated plates processed by wiring through the above-described prepreg are stacked, and multilayered by heating and pressing. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.

  Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention 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. Evaluation of copper foil adhesion (copper foil peel strength)>
The adhesiveness of the copper foil was evaluated by peel strength. The copper-clad laminate produced in each example was dipped in a copper etching solution to form a 1 cm wide copper foil to produce an evaluation substrate, and the peel strength of the copper foil was measured using a tensile tester. It shows that it is excellent in copper foil adhesiveness, so that a value is large.

<2. Measurement of 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 “TMA2940” was prepared. ”(Manufactured by DuPont Co., Ltd.), the thermal expansion characteristics at 40 to 350 ° C. in the surface direction (Z direction) of the evaluation substrate were observed, and the inflection point of the expansion amount was defined as the glass transition temperature. It shows that it is excellent in heat resistance, so that a value is large.

<3. Evaluation of heat resistance of hygroscopic solder>
A copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to prepare a 5 cm square evaluation board from which a pressure cooker test apparatus “ Using PTU-305VIII (manufactured by Hirayama Seisakusho Co., Ltd.), pressure cooker treatment was performed for 4 hours at 121 ° C. and 2 atm. The evaluation substrate after the treatment was immersed in a solder bath having a temperature of 288 ° C. for 20 seconds, and the hygroscopic solder heat resistance was evaluated according to the following evaluation criteria.
Good: No change is seen on the evaluation substrate by visual inspection.
Swelling: Swelling of the evaluation substrate is confirmed by visual inspection.

<4. Evaluation of low thermal expansion>
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 “TMA2940” was prepared. ”(Manufactured by DuPont) was used to measure the thermal expansion coefficient (linear expansion coefficient) in the surface direction of the evaluation substrate. In addition, in order to remove the influence of the thermal strain of the sample, the temperature rising / cooling cycle was repeated twice, and the coefficient of thermal expansion [ppm / ° C.] of 30 ° C. to 100 ° C. of the second temperature displacement chart was measured, An index of low thermal expansion was used. The smaller the value, the better the low thermal expansion.
Measurement conditions 1 ^st Run: room temperature → 350 ° C. (temperature increase rate 10 ° C./min)
^{2 nd Run: 0 ℃ → 350} ℃ ( heating 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 desired that the prepreg warp during heat treatment be small. In order to reduce the warpage, it is effective that the coefficient of thermal expansion in the surface direction of the substrate is small.

<5. Flame retardant evaluation>
The test of 127 mm in length and 12.7 mm in width from the evaluation board which removed the copper foil by immersing the copper clad laminated board manufactured in each example in copper etching liquid "Ammonium persulfate (APS)" (made by ADEKA Corporation). A piece was cut out, and the flame retardancy was tested and evaluated using the test piece according to the UL94 test method (Method V).
That is, flame contact for 10 seconds with a 20 mm flame was performed twice on the lower end of the test piece held vertically. Evaluation was performed in accordance with UL94 V method standards. In addition, when combustion did not stop even 30 seconds after flame contact, it described as "combustion."

<6. Evaluation of dielectric properties (measurement of relative dielectric constant Dk and dielectric loss tangent Df)>
An 80 mm × 2 mm evaluation substrate was prepared from the evaluation substrate from which the copper foil was removed by immersing the copper clad laminate produced in each example in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA Corporation). Using a relative dielectric constant measuring device “HP4291B” (manufactured by Hewlett Packard), the relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured and used as indices of dielectric characteristics.
The smaller the relative dielectric constant and the smaller the dielectric loss tangent, the better.

[Production Example 1] Compound (A) -1 having acidic substituent and unsaturated maleimide group
In a 2 L reaction vessel equipped with a thermometer, a stirrer and a moisture quantifier with a reflux condenser, can be heated and cooled, and 358.0 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane 34.2 g of p-aminophenol [(maleimide group equivalent) / (— NH ₂ group equivalent) = 4.0] and 392.2 g of propylene glycol monomethyl ether as an organic solvent were mixed and reacted for 5 hours while refluxing. A solution containing a compound having an acidic substituent represented by the following formula (A) -1 and an unsaturated maleimide group was obtained. As a result of analyzing the obtained solution by gel permeation chromatography (GPC) measurement (polystyrene conversion, eluent: tetrahydrofuran), the peak of p-aminophenol which should appear at about 19 minutes elution time has disappeared. The completion of the reaction was confirmed.
The conditions for the GPC measurement were as follows. Autosampler “AS-8020” (manufactured by Tosoh Corporation), column oven “860-C0” (manufactured by JASCO Corporation), RI detector “830-RI” (manufactured by JASCO Corporation), UV / VIS detector “870-UV” (manufactured by JASCO Corporation), HPLC pump “880-PU” (manufactured by JASCO Corporation). The column used was TSKgel Super HZ2000 (one) and Super HZ2300 (one) manufactured by Tosoh Corporation, connected in series, with a measurement temperature of 40 ° C., a flow rate of 0.5 ml / min, and a solvent THF. there were.

[Production Example 2] Compound (A) -2 having acidic substituent and unsaturated maleimide group
Into a reaction vessel having a volume of 2 L, which can be heated and cooled, equipped with a thermometer, a stirrer and a moisture quantifier with a reflux condenser, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide 442. 0 g and 54.5 g of p-aminophenol [(maleimide group equivalent) / (-NH ₂ group equivalent) = 4.0] and 496.5 g of propylene glycol monomethyl ether as an organic solvent were reacted for 5 hours while refluxing. And a solution containing a compound having an acidic substituent represented by the following formula (A) -2 and an unsaturated maleimide group was obtained.

[Production Example 3] Compound (A) -3 having acidic substituent and unsaturated maleimide group
In a 2 L reaction vessel equipped with a thermometer, a stirrer and a moisture quantifier with a reflux condenser, can be heated and cooled in a volume of 2 L, and 358.0 g of bis (4-maleimidophenyl) methane and 54.5 g of p-aminophenol [( Maleimide group equivalent) / (— NH ₂ group equivalent) = 4.0], and 412.5 g of propylene glycol monomethyl ether as an organic solvent were mixed, reacted at 120 ° C. for 2 hours, and represented by the following compound (A) -3. A solution containing a compound having an acidic substituent and an unsaturated maleimide group was obtained.

[Production Example 4] Compound (A) -4 having acidic substituent and unsaturated maleimide group
In a 2 L reaction vessel equipped with a thermometer, a stirrer and a moisture quantifier with a reflux condenser, can be heated and cooled, and 358.0 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane p-aminobenzoic acid 17.2 g [(maleimide group equivalent) / (-NH ₂ group equivalent) = 10.0], and 375.2 g of N, N-dimethylacetamide as an organic solvent were mixed at 160 ° C. The solution was reacted for 5 hours to obtain a solution containing a compound having an acidic substituent represented by the following formula (A) -4 and an unsaturated maleimide group.

[Production Example 5] Compound (A) -5 having acidic substituent and unsaturated maleimide group
In a 2 L reaction vessel equipped with a thermometer, a stirrer and a moisture quantifier with a reflux condenser, can be heated and cooled, and 358.0 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane M-aminophenol 34.2 g [(maleimide group equivalent) / (-NH ₂ group equivalent) = 4.0] and 392.2 g of propylene glycol monomethyl ether as an organic solvent were mixed and reacted for 5 hours while refluxing. Thus, a solution containing a compound having an acidic substituent represented by the following formula (A) -5 and an unsaturated maleimide group was obtained.

[Production Example 6] Compound (B) -1 having hydroxyl group and epoxy group
In a reaction vessel with a volume of 2 L that can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, a siloxane resin “X-22- having a carboxyl group at the molecular end represented by the above formula (b1-2)”. 162A "(manufactured by Shin-Etsu Chemical Co., Ltd., carboxyl group equivalent = 865 g / eq) 313.4 g and a naphthol aralkylcresol copolymer novolak type epoxy resin having a structural unit represented by the above formula (b2-1)" NC- 7000L "(Nippon Kayaku Co., Ltd., epoxy equivalent = 230 g / eq) 686.6 g, 1000.0 g of toluene as the organic solvent, and 1.96 g of triphenylphosphine as the reaction catalyst (based on 1 mol of the carboxyl group of the siloxane resin) 0.02 mol). The equivalent ratio of the reaction is (epoxy group number) / (carboxyl group number) = 8.0.
Next, the reaction was performed at about 100 ° C. with stirring, sampling was performed every hour, and the acid value was measured by neutralization titration. Three hours later, when the acid value reached 0 mgKOH / g, the reaction was considered to be completed, and the reaction solution was cooled to room temperature to obtain a solution of the compound (B) -1 having a hydroxyl group and an epoxy group.

[Production Example 7] Compound (B) -2 having hydroxyl group and epoxy group
In a reaction vessel with a volume of 2 L that can be heated and cooled, equipped with a thermometer, a stirrer, and a reflux condenser, a siloxane resin “X-22- having a carboxyl group at the molecular end represented by the above formula (b1-2)”. 162AS "(manufactured by Shin-Etsu Chemical Co., Ltd., carboxyl group equivalent = 420 g / eq) 313.4 g, and a naphthol aralkylcresol copolymer novolak type epoxy resin having a structural unit represented by the above formula (b2-1)" NC- 7000L "(Nippon Kayaku Co., Ltd., epoxy equivalent = 230 g / eq) 686.6 g, 1000.0 g of toluene as the organic solvent, and 1.96 g of triphenylphosphine as the reaction catalyst (based on 1 mol of the carboxyl group of the siloxane resin) 0.02 mol). The equivalent ratio of the reaction is (number of epoxy groups) / (number of carboxyl groups) = 4.0.
Next, the reaction was performed at about 100 ° C. with stirring, sampling was performed every hour, and the acid value was measured by neutralization titration. After 3 hours, when the acid value reached 0 mgKOH / g, the reaction was regarded as completed, and the reaction solution was cooled to room temperature to obtain a solution of compound (B) -2 having a hydroxyl group and an epoxy group.

[Examples 1 to 8]
First, in a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, which can be heated and cooled, a solution of the compounds (A) -1 to (A) -5 obtained in Production Examples 1 to 5 and production The solutions of the compounds (B) -1 to (B) -2 obtained in Examples 6 to 7 were mixed so that the mass ratio of the solid content was as shown in Table 1, and stirred at 115 ° C. for 4 hours. As a result, a thermosetting resin solution was obtained. A small amount of the obtained solution was taken out on an aluminum cup and dried by heating at 170 ° C. for 15 minutes. As a result, it was confirmed that the obtained resin film was transparent.
Next, the obtained thermosetting resin solution and the remaining components shown in Table 1 were mixed at a mass ratio shown in Table 1, and methyl ethyl ketone was used as the organic solvent, so that the solid content concentration was 65% by mass. A thermosetting resin composition (varnish) was obtained.
The obtained varnish was impregnated and applied to an S glass cloth having a thickness of 0.1 mm, and then dried by heating at 160 ° C. for 10 minutes, so that the solid content derived from the thermosetting resin composition (that is, S glass cloth was included). No) was obtained. Next, four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 25 kg / cm ² and a temperature of 185 ° C. for 90 minutes to produce a copper clad laminate.
Using the obtained copper-clad laminate, copper foil adhesiveness (copper foil peel strength), glass transition temperature, hygroscopic solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties were measured and evaluated by the above methods. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, a thermosetting resin solution was obtained in the same manner except that the maleimide compound (a1) shown in Table 2 was used instead of the compound (A) -1, and a copper-clad laminate was prepared. Measured and evaluated. The results are shown in Table 2.

[Comparative Examples 2 to 4]
In Example 1, a thermosetting resin solution was obtained in the same manner except that the siloxane resin (b1) and / or the epoxy compound (b2) shown in Table 2 was used instead of the compound (B) -1. And the copper clad laminated board was produced, and it measured and evaluated. The results are shown in Table 2.

[Comparative Examples 5-6]
In Example 1, a thermosetting resin solution was obtained in the same manner except that the amounts of the compounds (A) and (B) used were changed as shown in Table 2, and a copper-clad laminate was produced. Measured and evaluated. The results are shown in Table 2.

The numbers in the table are indicated by mass parts of solid content.
The description of each component is as follows.
* 1: "Tuftec (registered trademark) M1913", carboxylic acid-modified hydrogenated styrene elastomer (carboxylic acid-modified SEBS), manufactured by Asahi Kasei Corporation * 2: 3,3'-diethyl-4,4'-diaminodiphenylmethane "KAYAHARD" (Registered trademark) AA ”, amino group equivalent = 127 g / eq, manufactured by Nippon Kayaku Co., Ltd. * 3:“ X-22-161B ”, both-end amine-modified siloxane resin, amino group equivalent = 1500 g / eq, Shin-Etsu * 4: “SC-2050KNK”, fused silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Admatechs Co., Ltd., dilution solvent; methyl isobutyl ketone)
* 5: “KEMGARD2200”, zinc molybdate-treated talc, manufactured by Sherwin Williams * 6: “TBP2”, p-benzoquinone and tri-n-butylphosphine addition reaction product, manufactured by Kurokin Kasei Co., Ltd. * 7: “BMI-” 4000 ”, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, manufactured by Daiwa Kasei Kogyo Co., Ltd. * 8:“ X-22-162A ”, carboxylic acid-modified siloxane resin at both ends, Shin-Etsu Chemical Co., Ltd. Company equivalent, carboxyl group equivalent = 865 g / eq
* 9: “NC-7000L”, naphthol aralkylcresol copolymer novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy group equivalent = 230 g / eq

From Tables 1 and 2, by using the thermosetting resin composition and the prepreg produced in the examples, a laminated board having good copper foil adhesion, hygroscopic solder heat resistance, low thermal expansion, flame retardancy and dielectric properties It can be seen that It can also be said that the glass transition temperature is high and the heat resistance is excellent.
On the other hand, when the thermosetting resin composition and the prepreg produced in the comparative example are used, at least one selected from copper foil adhesiveness, hygroscopic solder heat resistance, low thermal expansion, flame retardancy and dielectric properties is inferior. As a result. Specifically, Comparative Examples 1 and 4 are inferior in moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy, and dielectric properties. In Comparative Example 2, the copper foil adhesion, moisture-absorbing solder heat resistance, flame retardancy and dielectric properties are inferior. In Comparative Example 3, the low thermal expansion property is inferior. In Comparative Example 5, the low thermal expansibility and flame retardancy are poor. In Comparative Example 6, all of copper foil adhesion, moisture-absorbing solder heat resistance, low thermal expansion, flame retardancy and dielectric properties are inferior. Further, in Comparative Examples 1, 2, 4, and 6, the glass transition temperature is also low, and it can be said that the heat resistance is poor.

  A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention, and a laminate formed using the prepreg are copper foil adhesiveness, glass transition temperature, moisture absorption solder heat resistance, Since it is excellent in low thermal expansion, flame retardancy and dielectric properties, it is useful as a printed wiring board for electronic equipment.

Claims (8)

By reacting a maleimide compound (a1) having at least two N-substituted maleimide groups in one molecule with an amine compound (a2) having an acidic substituent represented by the following general formula (a2-1) The resulting compound (A) having an acidic substituent and an N-substituted maleimide group in the molecular structure, and a siloxane resin (b1) having a carboxyl group at the molecular end and at least two epoxy groups in one molecule Compound (B) having a hydroxyl group and an epoxy group in the molecular structure, obtained by reacting with epoxy compound (b2)
A heat-curable resin composition comprising the compound (A), wherein the content of the compound (A) is 30 to 90 parts by mass with respect to 100 parts by mass of the total of the compounds (A) and (B). Curable resin composition.

(In the formula, R ¹ represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ² represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. X represents 1 to 5) An integer, y is an integer of 0 to 4, and satisfies 1 ≦ x + y ≦ 5, provided that when x is an integer of 2 to 5, a plurality of R ¹ may be the same or different. In addition, when y is an integer of 2 to 4, a plurality of R ² may be the same or different. The thermosetting resin composition of Claim ¹ whose R < ¹ > is a hydroxyl group in general formula (a2-1). The thermosetting resin composition according to claim 1 or 2, wherein the siloxane resin (b1) is a siloxane resin represented by the following general formula (b1-1).

^{(Wherein, R 3, R 4, R} 5 and R ⁶ are each independently, .m represents an alkyl group, a phenyl group or a substituted phenyl group having 1 to 5 carbon atoms, an integer of 5 to 100. The plurality of R ³ may be the same or different, and the plurality of R ⁴ may be the same or different, and X ¹ and X ² each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms.) The epoxy compound (b2) has a structural unit represented by the following formula (b2-1-1) and a structural unit represented by the following formula (b2-1-2). The thermosetting resin composition according to any one of claims 1 to 3, which is a resin.

  Furthermore, the thermosetting resin composition of any one of Claims 1-4 containing at least 1 sort (s) selected from a diamine compound, an inorganic filler, a flame retardant, and a hardening accelerator.   A prepreg formed by impregnating or coating the base material with the thermosetting resin composition according to any one of claims 1 to 5.   A laminate formed using the prepreg according to claim 6.   A printed wiring board obtained by forming a wiring pattern on the laminated board according to claim 7.