JP2017019906A - Thermosetting resin composition, and prepreg, laminate and printed wiring board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition excellent in dielectric property as well as excellent in metal foil adhesion and heat resistance, a prepreg, a laminate and a printed wring board using the same.SOLUTION: A thermosetting resin composition contains: a polyimide curing agent (A) which is a polyimide compound obtained by reacting a maleimide compound (a) having at least 2 N-substituted maleimide compounds in a molecule, an aniline compound (b) having 2 aromatic amino groups in a molecule and an aminophenol compound (c) having an aromatic amino group and at least an aromatic hydroxyl group in a molecule, making the component (a) excess over the components (b) and (c), and has specific weight average molecular weight defined by a concept as binding degree; an epoxy resin (B); and a styrene-maleic acid copolymer (C). The binding degree satisfies the following relationship of binding degree=weight average molecular weight/preparing average molecular weight.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition having excellent dielectric properties and excellent metal foil adhesion and heat resistance, and a prepreg, a laminate and a printed wiring board using the same.

  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. In particular, in copper-clad laminates and interlayer insulation materials, due to the recent demand for higher density, high copper foil adhesion for fine wiring formation and workability when drilling or punching is performed. Is also needed. In recent years, the mounting of electronic components by lead-free solder has required higher heat resistance than conventional ones.

  In addition, mobile communication devices such as mobile phones, their base station devices, network-related electronic devices such as servers and routers, and large computers, etc. transmit and process large amounts of information with low loss and high speed. Is required. When transmitting and processing large volumes of information, electrical signals can be transmitted and processed faster at higher frequencies. However, the electrical signal basically becomes easier to attenuate as the frequency becomes higher. In other words, the output tends to be weak at a shorter transmission distance, and the loss tends to increase. Therefore, in order to satisfy the above-described requirements for low loss and high speed, the dielectric characteristics (relative permittivity, dielectric loss tangent), particularly the high frequency band, in the characteristics of the printed wiring board itself that transmits and processes are installed in equipment. There is a need for improved dielectric properties.

  In order to obtain a printed wiring board with low transmission loss, conventionally, a substrate material using a fluorine-based resin having a low relative dielectric constant and a low 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 as a high-layer printed wiring board used in the above-mentioned communication equipment, network-related electronic equipment, large computers, and the like. There is a problem.

  Therefore, many studies have been made on resin materials for printed wiring boards that can be used for high-frequency applications instead of fluororesins. Among them, many patents using a resin containing a maleimide group having high heat resistance and relatively excellent dielectric properties have been reported. It is known that a bismaleimide containing two maleimide groups in a molecule forms a resin having high heat resistance by self-polymerization between molecules by applying heat.

  Bismaleimide compounds are curing agents for thermosetting resins that have excellent dielectric properties, flame retardancy, and heat resistance, but since known bismaleimide compounds do not have curing reactivity with epoxy resins, epoxy curing systems When used as it is in the thermosetting resin, there is a problem that the heat resistance is insufficient. That is, a case relating to a thermosetting resin in which an adduct of a bismaleimide compound and an aminophenol is produced and used by heat kneading without using an organic solvent (for example, see Patent Document 1 and Patent Document 2) is disclosed. However, the yield of an adduct of a bismaleimide compound and aminophenol is low, and when these are used as a copper clad laminate or an interlayer insulating material, heat resistance, workability, etc. are insufficient.

  Moreover, although the example regarding the thermosetting resin which contains cyanate resin and an aralkyl modified epoxy resin as an essential component is disclosed by patent document 3, patent document 4, etc., cyanate resin which is an essential component is toughness and hardening reactivity. Because it is an inferior resin, the improvement in curing reactivity and toughness of this thermosetting resin is still insufficient, and even when these are used as copper clad laminates or interlayer insulation materials, heat resistance, reliability, processing Sexuality is insufficient.

  Further, Patent Document 5 discloses a case relating to a thermosetting resin using an adduct of a bismaleimide compound and an aminobenzoic acid produced without using an organic solvent, a benzoguanamine formaldehyde condensate, and the like. The temperature is low, and the heat resistance to lead-free solder and the heat resistance with copper are insufficient in recent years.

  Patent Document 6 discloses an example of a reaction product of a bismaleimide compound and an amino compound having an acidic substituent, and a resin composition using a dicyandiamide and a styrene-maleic anhydride copolymer. The solubility with respect to an organic solvent is bad, and there is a large risk that precipitates are generated in the resin composition. In addition, dielectric properties and copper foil adhesion do not satisfy the required properties in the current information and communication field.

Japanese Patent Publication No. 63-34899 JP-A-6-32969 JP 2002-309085 A JP 2002-348469 A Japanese Patent Publication No. 6-8342 JP 2008-111096 A

  In view of the current situation, an object of the present invention is to provide a thermosetting resin composition excellent in metal foil adhesion, heat resistance, flame retardancy, and dielectric properties, and a prepreg, a laminate and a printed wiring board using the same. It is to be.

The present invention relates to the following.
[1] A maleimide compound (a) having at least two N-substituted maleimide groups in one molecule represented by the following general formula (I), and two aromatic compounds in one molecule represented by the following general formula (II) An aniline compound (b) having an amino group, and an aminophenol compound (c) having one aromatic amino group and at least one aromatic hydroxyl group in one molecule represented by the following general formula (III) Used, (a) :( b) :( c) = 4.0: 0.1-1.0: A polyimide curing agent (polyimide curing agent obtained by reacting at a ratio of 0.1 to 1.0 mol ( A), a thermosetting resin composition containing an epoxy resin (B) and a styrene-maleic acid copolymer (C), wherein the polyimide compound has a degree of bond represented by the following formula of 7.0. Polyimide compound obtained by reacting so as not to exceed In it, a thermosetting resin composition.
[Equation 1]
Degree of bond = weight average molecular weight / charge average molecular weight (wherein, the weight average molecular weight is a measured value of the weight average molecular weight of the polyimide compound, and the charge average molecular weight is determined based on the components (a), (b) and (It is a value when the molecular weight of (c) is multiplied by the molar ratio of each component and added, and converted to a molecular weight per mole of charge)

（式中Ａｒ_１は一般式（Ｉ−１）、（Ｉ−２）、（Ｉ−３）又は（Ｉ−４）で表される残基である）

(In the formula, Ar ₁ is a residue represented by the general formula (I-1), (I-2), (I-3) or (I-4)).

（式中、Ｒ_１は水素原子、炭素数１〜５の脂肪族炭化水素基を示し、ｐは０〜４の整数である）

(In the formula, R ₁ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and p is an integer of 0 to 4)

（式中、Ｒ_２及びＲ_３は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基を示し、ｑ、ｒは各々独立に０〜４の整数であり、Ａ_１は炭素数１〜５のアルキレン基、エーテル基、又はスルフォニル基で表される残基である。

(In the formula, R ₂ and R ₃ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, q and r each independently represent an integer of 0 to 4, and A ₁ represents the number of carbon atoms. It is a residue represented by 1-5 alkylene groups, ether groups, or sulfonyl groups.

（式中、ｎは１〜１０の整数である。）

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

（式中、Ａｒ_２は一般式（II−１）、（II−２）に示す残基である。）

(In the formula, Ar ₂ is a residue represented by the general formulas (II-1) and (II-2).)

（式中、Ｒ_４及びＲ_５は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、メトキシ基、水酸基又はハロゲン原子を示し、ｓ、ｔは各々独立に０〜４の整数である。）

Wherein R ₄ and R ₅ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, a hydroxyl group or a halogen atom, and s and t are each independently an integer of 0 to 4 .)

（式中、Ｒ_６、Ｒ_７及びＲ_８は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、メトキシ基、水酸基又はハロゲン原子を示し、ｕ、ｖ、ｗは各々独立に０〜４の整数である。）

(Wherein R ₆ , R ₇ and R ₈ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, a hydroxyl group or a halogen atom, and u, v and w each independently represent It is an integer from 0 to 4.)

（式中、Ａｒ_３は一般式（III−１）で示される残基である。）

(In the formula, Ar ₃ is a residue represented by the general formula (III-1).)

（式中、Ｒ_９は水素原子、炭素数１〜５の脂肪族炭化水素基を示し、ｘは０〜４の整数である）

(Wherein R ₉ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and x is an integer of 0 to 4)

[2] The thermosetting resin composition according to the above [1], which is a polyimide compound obtained by reacting so that the degree of bond is 3.8 to 6.9.
[3] The maleimide compound (a), the aniline compound (b), and the aminophenol compound (c) are converted into (a) :( b) :( c) = 4.0: 0.4 to 1.0. : The thermosetting resin composition according to the above [1] or [2], wherein a polyimide compound is obtained by reacting at a ratio of 0.2 to 0.6.
[4] The thermosetting resin composition according to any one of [1] to [3], wherein the obtained polyimide compound has a weight average molecular weight of 1,000 to 2,500.
[5] The styrene-maleic acid copolymer of component (C) has a weight average molecular weight of 1,000 to 50,000, and is represented by the general formula (IV) with respect to the number of monomer units n2 represented by the general formula (V). The thermosetting resin composition according to any one of [1] to [4], wherein the ratio of the number of monomer units n1 and n1 / n2 is 1.0 to 6.0.

（式中、Ｒ_１０、Ｒ_１１はそれぞれ独立に、水素原子、炭素数１〜５の炭化水素基、フェニル基、又は置換フェニル基を示す。ただし、Ｒ_１０、Ｒ_１１のうち少なくとも１個はフェニル基又は置換フェニル基である。）

(Wherein R ₁₀ and R ₁₁ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. However, at least one of R ₁₀ and R ₁₁ is It is a phenyl group or a substituted phenyl group.)

[6] The thermosetting resin composition according to any one of [1] to [5], further including a curing accelerator (F).

[7] A prepreg using the thermosetting resin composition according to any one of [1] to [6].
[8] A laminate obtained by lamination using the prepreg according to [7].
[9] A printed wiring board manufactured using the laminated board according to [8].

  The thermosetting resin composition of the present invention is excellent in metal foil adhesion, heat resistance, and dielectric properties, has low toxicity, and is excellent in safety and work environment. Therefore, the laminated board obtained by laminate molding using the thermosetting resin composition or a prepreg prepared from the thermosetting resin composition should be suitably used as an electronic component as a printed wiring board. Can do.

  Next, the present invention will be described in detail.

  This invention uses the polyimide compound obtained by making it react by a specific method as a hardening | curing agent, this polyimide hardening | curing agent (A), an epoxy resin (B), and a styrene-maleic acid copolymer (C). It is a thermosetting resin composition to contain.

First, the polyimide curing agent of the polyimide compound obtained by making it react with the specific method of (A) component which comprises a thermosetting resin composition is demonstrated.
The polyimide compound which is a polyimide curing agent includes a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule, an aniline compound (b) having two aromatic amino groups in one molecule, and Each component of the aminophenol compound (c) having one aromatic amino group and at least one hydroxyl group in one molecule is charged in a specific ratio, and “bond” as described later. It is produced by reacting to a weight average molecular weight specified by “degree”.

式中のＡｒ_１は、以下の一般式（Ｉ−１）、（Ｉ−２）、（Ｉ−３）又は（Ｉ−４）で表される残基である。 The maleimide compound of component (a) used for synthesizing the polyimide compound is a compound represented by the general formula (I).

Ar ₁ in the formula is a residue represented by the following general formula (I-1), (I-2), (I-3) or (I-4).

式中のＲ_１は水素原子、炭素数１〜５の脂肪族炭化水素基を示し、ｐは０〜４の整数であり、Ｒ_１としては水素原子もしくは炭素数１〜２の脂肪族炭化水素基で、ｐは０〜１であることが好ましく、Ｒ_１は水素原子であることがさらに好ましい。

In the formula, R ₁ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, p is an integer of 0 to 4, and R ₁ is a hydrogen atom or an aliphatic hydrocarbon having 1 to 2 carbon atoms. In the group, p is preferably 0 to ₁ , and R ₁ is more preferably a hydrogen atom.

式中のＲ_２及びＲ_３は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基を示し、ｑ、ｒは各々独立に０〜４の整数であり、Ａ_１は炭素数１〜５のアルキレン基、エーテル基、又はスルフォニル基で表される残基であり、これらのうちでも、Ｒ_２、Ｒ_３としては水素原子であることが好ましい。また、Ａ_１としては、アルキレン基であることが好ましく、炭素数が１のメチレンであることがさらに好ましい。

In the formula, R ₂ and R ₃ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, q and r are each independently an integer of 0 to 4, and A ₁ has ₁ carbon atom. 5 alkylene group, a residue represented by an ether group, or a sulfonyl group, among them, it is preferred as R _2, R ₃ is a hydrogen atom. A ₁ is preferably an alkylene group, and more preferably methylene having 1 carbon.

式中のｎは１〜１０の整数であり、１〜２であることが好ましい。

N in a formula is an integer of 1-10, and it is preferable that it is 1-2.

  Examples of the maleimide compound (a) having at least two N-substituted maleimide groups in one molecule represented by the above general formula (I) include 4,4′-diphenylmethane bismaleimide and m-phenylene bismaleimide. Bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, polyphenylmethane maleimide, specific Examples of such products include BMI-2000 and BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.

  Among these, 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, and bisphenol A diphenyl ether bismaleimide, which are highly reactive and can be expected to have high heat resistance, are preferable. From the viewpoint of solubility in a solvent, polyphenylmethane maleimide Bisphenol A diphenyl ether bismaleimide is preferred, and 4,4′-diphenylmethane bismaleimide is preferred because it is inexpensive.

式中のＡｒ_２は、一般式（II−１）、（II−２）に示す残基である。 The aniline compound as the component (b) is a compound represented by the general formula (II).

Ar ₂ in the formula is a residue represented by the general formulas (II-1) and (II-2).

式中のＲ_４及びＲ_５は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、メトキシ基、水酸基又はハロゲン原子を示し、ｓ、ｔは各々独立に０〜４の整数であり、Ｒ_４、Ｒ_５としては、水素原子もしくは炭素数１〜２の脂肪族炭化水素基であり、ｓ、ｔは共に０〜１であることが好ましく、Ｒ_４及びＲ_５は、水素原子であることがさらに好ましい。

R ₄ and R ₅ in the formula each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, a hydroxyl group or a halogen atom, and s and t are each independently an integer of 0 to 4. R ₄ and R ₅ are each a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms, s and t are preferably 0 to 1, and R ₄ and R ₅ are each a hydrogen atom. More preferably.

式中のＲ_６、Ｒ_７及びＲ_８は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、メトキシ基、水酸基又はハロゲン原子を示し、ｕ、ｖ、ｗは各々独立に０〜４の整数であり、Ｒ_６、Ｒ_７、Ｒ_８としては、水素原子であることが好ましい。

R ₆ , R ₇ and R ₈ in the formula each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, a hydroxyl group or a halogen atom, and u, v and w are each independently 0 It is an integer of -4, and it is preferable that it is a hydrogen atom as R < ₆ >, R < ₇ >, R < ₈ >.

  Examples of the aniline compound (b) represented by the general formula (II) include 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 1 , 4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like, 4,4′-diaminodiphenyl ether, 1,4-bis [1- (4-aminophenyl) -1- Methylethyl] benzene is preferred because the cured product has a low dielectric loss tangent.

式中のＡｒ_３は、一般式（III−１）で示される残基が挙げられる。 The (c) component aminophenol compound is a compound represented by the general formula (III).

Ar ₃ in the formula includes a residue represented by the general formula (III-1).

式中のＲ_９は、水素原子、炭素数１〜５の脂肪族炭化水素基を示し、ｘは０〜４の整数であり、Ｒ_９としては、水素原子もしくは炭素数１〜２の脂肪族炭化水素基で、ｘは０〜１であることが好ましく、Ｒ_９は水素原子であることがさらに好ましい。

R ₉ in the formula represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, x is an integer of 0 to 4, and R ₉ is a hydrogen atom or an aliphatic group having 1 to 2 carbon atoms. In the hydrocarbon group, x is preferably 0 to 1, and R ₉ is more preferably a hydrogen atom.

  Examples of the aminophenol compound (c) represented by the general formula (III) include p-aminophenol, o-aminophenol, m-aminophenol, 4-amino-3-methylphenol, 4-amino-2,3. -Dimethylphenol etc. are mentioned. Of these, p-aminophenol is preferred because of its high reactivity and low cost.

The polyimide compound used in the present invention obtains a reaction product in which an amino group is added to a maleimide group by reacting the components (a) to (c). In carrying out this reaction, in the present invention, the ratio of the maleimide compound (a) component is increased, and the reaction is stopped in a somewhat reacted state while leaving the starting maleimide compound (a) to some extent, In short, it is necessary to carry out the reaction so as to obtain a reaction product in a state in which the degree of bonding of the polyimide compound does not increase without causing much reaction.
As a result, the polyimide compound obtained can be used as a curing agent for the epoxy group while leaving the self-polymerized group (unsaturated bond of maleimide group) having high heat resistance, and as a result, this polyimide compound The heat resistance, glass transition temperature, and dielectric properties of the thermosetting resin composition using as a curing agent can be improved.

Specifically, the degree of reaction in producing such a polyimide compound can be specified by the “bonding degree” defined by the following formula, and the reaction is performed so that the bonding degree does not exceed 7.0. It is preferable to obtain a polyimide compound, more preferably 6.9 or less, and still more preferably 5.7 or less. The lower limit is greater than 1, but is preferably 3.0 or more, more preferably 3.5 or more, and even more preferably 3.8 or more.
[Equation 2]
Degree of binding = weight average molecular weight / prepared average molecular weight

Here, in the formula, the “weight average molecular weight” of the molecule is the weight average molecular weight of the polyimide compound measured using standard polystyrene by gel permeation chromatography (GPC) as described later.
In addition, the “preparation average molecular weight” of the denominator is obtained by adding the molecular weight of each component (a), (b) and (c) of the raw material at the time of preparation and adding the molar ratio of each component, and adding the molecular weight per mole of the charge. It is the value of molecular weight when converted to.
Specifically, the charged average molecular weight is calculated as follows.
When the molecular weight of each compound of (a), (b) and (c) is MW _a , MW _b and MW _c , respectively, and the charged amounts in the reaction are m _a , _mb and _mc mol, respectively,
Charged average molecular weight = (MW _a × m _a + MW _b × m _b + MW _c × m _c ) / (m _{a +} m _b + m _c )
Is the calculated value.
Even when the preparation is performed in a divided manner, it can be obtained from the total amount of each component in a series of synthesis reactions. In addition, when two or more kinds of compounds are used in each component, each compound is calculated by calculating in the same manner.

  The weight average molecular weight of the polyimide compound obtained by the reaction with respect to the charged average molecular weight calculated in this way is monitored over time by GPC, and the reaction is terminated within a range where the degree of binding does not exceed 7.0. To obtain a polyimide compound. The reaction time cannot be generally specified depending on the reaction scale, reaction conditions, and the like, but in the experimental conditions such as Examples and Comparative Examples, about 2 to 6 hours was preferable.

In synthesizing the polyimide compound used in the present invention, since it is necessary to leave the starting maleimide compound (a) to some extent, the blending amount of each component is also important.
In the synthesis of the polyimide compound, the amount of the aniline compound (b) having two aromatic amino groups in one molecule is the number of moles of the aniline compound (b) when the number of moles of the maleimide compound (a) is 1. Is preferably used in the range of 0.025 to 0.25, and more preferably in the range of 0.1 to 0.25. When the number of moles is 0.025 or less, the storage stability of the polyimide compound may be lowered, and when it is 0.25 or more, the heat resistance and electrical characteristics may be lowered.

  In this synthesis, the amount of the aminophenol compound (c) having one aromatic amino group and at least one aromatic hydroxy group in one molecule is defined so that the number of moles of the maleimide compound (a) is 1. The aminophenol compound (c) is preferably used in the range of 0.025 to 0.25, more preferably in the range of 0.05 to 0.15. When it is 0.025 or less, the reactivity may be lowered, and when it is 0.25 or more, the heat resistance and dielectric properties may be lowered.

In the synthesis of the polyimide compound, the organic solvent to be used is not particularly limited, but for example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, γ -Ester solvents, such as butyrolactone, etc. are mentioned, 1 type or 2 types or more can be mixed and used.
Among these solvents, dimethylformamide, dimethylacetamide, cyclohexanone, γ-butyrolactone, propylene glycol monomethyl ether, methyl cellosolve, butyl cellosolve, etc. are preferable from the viewpoint of solubility, and they are highly volatile and remain in the prepreg production. More preferred are dimethylacetamide and propylene glycol monomethyl ether, which hardly remain as solvents.
The amount of the organic solvent used is preferably 10 to 1,000 parts by mass per 100 parts by mass of the sum of the maleimide compound (a), the aniline compound (b), and the aminophenol compound (c). It is particularly preferable to use parts by mass.

When the reaction temperature is 80 to 130 ° C., the reaction can be easily controlled, and the reaction time can be shortened. The reaction time is preferably 1 to 10 hours from the viewpoint of production cost and ease of reaction control.
In this reaction, a reaction catalyst can be optionally used as necessary. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Can be used in combination.

  The weight average molecular weight of the polyimide compound used in the present invention is preferably about 1,000 to 2,500. When the weight average molecular weight is about 1,000 or more, the solubility in the solvent is not insufficient, and when it is about 2,500 or less, the electrical characteristics are deteriorated and the heat resistance is also deteriorated. Absent. The weight average molecular weight is a value measured by GPC using tetrahydrofuran as an eluent and converted by a standard polystyrene calibration curve.

The thermosetting resin composition of this invention contains the polyimide hardening | curing agent (A) which is said polyimide compound, an epoxy resin (B), and a styrene-maleic acid copolymer (C).
The epoxy resin (B) used in the thermosetting resin composition of the present invention is preferably an epoxy resin having two or more epoxy groups in one molecule from the viewpoint of heat resistance, for example, bisphenol A type Bisphenol F type, biphenyl type, novolak type, polyfunctional phenol type, naphthalene type, alicyclic type and alcohol type glycidyl ether, glycidyl amine type and glycidyl ester type epoxy resin, etc. The above can be mixed and used.
Among these, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin and the like from the viewpoint of dielectric properties, heat resistance, moisture resistance and copper foil adhesion A cresol novolac type epoxy resin or the like is preferable.

  The component (C) of the styrene-maleic acid copolymer used in the thermosetting resin composition of the present invention includes a monomer unit represented by the general formula (IV) and a copolymer comprising the monomer unit represented by the general formula (V). Resin.

式中、Ｒ_１0、Ｒ_１1はそれぞれ独立に、水素原子、炭素数１〜５の炭化水素基、フェニル基、又は置換フェニル基を示す。ただし、Ｒ_１0、Ｒ_１1のいずれかは、フェニル基又は置換フェニル基である。また、このフェニル基に対する置換基としては、炭素数１〜５のアルキル基、ハロゲン等が挙げられる。

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. However, either R ₁₀ or R ₁₁ is a phenyl group or a substituted phenyl group. Moreover, as a substituent with respect to this phenyl group, a C1-C5 alkyl group, a halogen, etc. are mentioned.

Examples of the monomer constituting the monomer unit represented by the general formula (IV) include styrene compounds such as styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, and bromostyrene. The monomer unit represented by the general formula (V) is obtained from maleic anhydride.
When the number of monomer units shown in the general formula (IV) is n1, and the number of monomer units in the general formula (V) is n2, the monomer ratio (n1 / n2) in the copolymer of the component (C) is a dielectric property or Considering the balance between the glass transition temperature, the moisture and heat resistance, and the adhesiveness, 1.0 to 6.0 is preferable, and 3.0 to 5.0 is more preferable. Further, the weight average molecular weight of the copolymer of component (C) is preferably 1,000 to 50,000, considering the balance between heat resistance and mechanical strength and moldability, and 9,000 to 12 More preferably, it is 1,000. The weight average molecular weight is a value measured by GPC using tetrahydrofuran as an eluent and converted by a standard polystyrene calibration curve.
Moreover, in addition to said monomer, the styrene-maleic acid copolymer of (C) component may be copolymerized with monomers of vinyl compounds such as ethylene, propylene and isobutylene.

  In addition to the above components (A) to (C), the thermosetting resin composition of the present invention can contain an inorganic filler (D). Examples of the inorganic filler (D) that can be used in the thermosetting resin composition of the present invention include silica, alumina, mica, talc, short glass fiber or fine powder, hollow glass, calcium carbonate, quartz powder, and the like. Among these, silica, alumina, mica, talc and the like are preferable from the viewpoint of copper foil adhesion, heat resistance, and flame retardancy, and silica and alumina are particularly preferable from the viewpoint of high heat dissipation.

Moreover, a flame retardant (E) can also be contained in the thermosetting resin composition of the present invention for the purpose of improving flame retardancy. By using an appropriate flame retardant in combination, it is possible to impart high flame retardancy with little reduction in various properties such as heat resistance, copper foil adhesion, high elastic modulus, and low thermal expansion.
Examples of the flame retardant include metal hydrates such as aluminum hydroxide and magnesium hydroxide having a thermal decomposition temperature of less than 300 ° C., triphenyl phosphate, tricresyl phosphate, 1,3-phenylenebis (di-2,6-xylate). Nyl phosphate), phosphoric acid ester compounds, phosphazenes, phosphorous flame retardants such as red phosphorus, and inorganic flame retardant aids such as antimony trioxide and zinc molybdate. Halogen-containing flame retardants containing bromine and chlorine are not suitable for the purpose of the present invention due to recent environmental problems. Metal hydrates such as aluminum hydroxide and magnesium hydroxide, and triphenyl phosphate and 1,3-phenylenebis (di-2,6-xylenyl phosphate) can exhibit high glass transition temperature and dielectric properties. Possible and desirable.

  Furthermore, the thermosetting resin composition of the present invention can contain a curing accelerator (F). Examples of the curing accelerator (F) used in the thermosetting resin composition of the present invention include imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts. Among them, imidazoles and derivatives thereof are preferable from the viewpoints of heat resistance, flame retardancy, copper foil adhesion, and the like.

The thermosetting resin composition of the present invention can be prepared by mixing the above components (A) to (C) and, if necessary, the components (D) to (F) by known means. When mixing, it can also be diluted and mixed using a solvent. In preparation, various additives such as thermoplastic resins, elastomers, organic fillers, ultraviolet absorbers, and antioxidants can be added as components other than the above components.
In addition, when preparing the prepreg etc., it is easy to handle and use the thermosetting resin composition of this invention in the form of a varnish with a solid content density | concentration of about 40-90 mass%.

The prepreg of the present invention is obtained by impregnating or coating the thermosetting resin composition of the present invention on a sheet-like reinforcing base material and forming a B-stage. This prepreg can be produced by impregnating or coating the above-mentioned thermosetting resin composition on a sheet-like reinforcing substrate and semi-curing (B-stage) by heating or the like. The well-known thing used for the laminated board for various electrical insulation materials can be used as a sheet-like reinforcement base material of a prepreg. Examples of the material 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 base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined.
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 was given is suitable from the surface of heat resistance, moisture resistance, and workability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.

The laminate of the present invention is obtained by laminate molding using the aforementioned thermosetting resin composition or prepreg. For example, it can be manufactured by stacking 1 to 20 prepregs and laminate-molding them with a configuration in which a metal foil such as copper and aluminum is disposed on one or both sides thereof.
The metal foil is not particularly limited as long as it is used for electrical insulating material applications. The molding conditions can be applied to a laminate for an electrical insulating material and a multilayer board, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. It can be molded in a range of 10 MPa and a heating time of 0.1 to 5 hours.
Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.

  The printed wiring board of the present invention uses the laminated board of the present invention. The metal foil arrange | positioned on the single side | surface or both surfaces of the insulating resin layer in the laminated board of this invention can be manufactured by circuit-processing. For example, the conductor layer of the laminate of the present invention is subjected to wiring processing by a normal etching method, a plurality of laminates processed by wiring through the above-described prepreg are laminated, and then multilayered by heating press processing, A multilayer printed wiring board can also 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.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these description. In addition, the copper clad laminated board obtained by each Example and the comparative example measured and evaluated the performance with the following method.

(1) Measurement of weight average molecular weight The weight average molecular weight of the polyimide compound was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). A peak with a retention time of 5-11 minutes was utilized. The calibration curve was approximated by a cubic equation using a standard polystyrene kit (PStQuick Kit-L [trade name] manufactured by Tosoh Corporation). The conditions for GPC are as follows.
Measuring condition apparatus: HLC-8320GPC (trade name, manufactured by Tosoh Corporation)
Column: TSKgel SuperHZ2000 + TSKgel SuperHZ
3000 (two in total) (trade name, manufactured by Tosoh Corporation)
Column size: 4.6 mm I.D. D x 150mm
Guard column: TSK guard column Super HZ-L
Guard column size: 4.6 mm I.D. D x 20mm
Eluent: Tetrahydrofuran Sample concentration: 10 mg / 1.3 mL
<Pump>
Sample-side pump upper limit pressure: 70 MPa
Sample side pump lower limit pressure: 0.1 MPa
Sample side flow rate: 0.35 mL / min
Reference side pump upper limit pressure: 70MPa
Reference side pump lower limit pressure: 0.1 MPa
Reference flow rate ratio: 1x <sampler>
Tube volume: 112 μL
Injection volume: 10 μL
Pre-suction volume: 150μL
Sampling rate: 5 μL / sec
Air volume: 1μL
Loop volume: 100 μL
<Oven>
Column oven control temperature: 40 ° C
Column oven gas sensor level: 300mV
Pump oven control temperature: 40 ° C
Pump oven gas sensor level: 300mV
<Differential refraction detector>
Balance value: 0.00mV
Response: 0.50sec
Temperature control temperature: 40 ° C
Polarity: +
Range: 256μRIU / FS

(2) Copper foil adhesion (copper foil peel strength)
By immersing the copper-clad laminate in a copper etching solution, a copper foil having a width of 5 mm is formed to produce an evaluation substrate, and using a tensile tester, copper foil adhesion (copper foil peel strength (90 °)) Was measured.

(3) Solder heat resistance A copper clad laminate cut to a 25 mm square was floated on a solder bath at 288 ° C., and the time until the substrate expanded was measured (maximum 30 minutes, 30 minutes in the table being “30:00” And time display).

(4) Dielectric characteristics (dielectric constant Dk, dielectric loss tangent Df)
A 2 mm × 85 mm evaluation substrate was prepared from a resin plate prepared as described below. The substrate was measured for relative dielectric constant Dk and dielectric loss tangent Df at 1 GHz by a cavity resonator perturbation method using a network analyzer E8364B manufactured by Agilent Technologies.

(Production Examples 1-8)
Production Example 1: Production of polyimide compound (A-1) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, 4,4′-diphenylmethane bismaleimide: 350 g, 4 , 4′-diaminodiphenyl ether: 36.7 g, p-aminophenol: 13.3 g and ethylene glycol monomethyl ether: 171.4 g were added and reacted for 2 hours while refluxing to obtain a solution of the polyimide compound (A-1). It was. The weight average molecular weight was 1180.

Production Example 2: Production of polyimide compound (A-2) 4,4'-diphenylmethane bismaleimide: 350 g, 4 mL in a reaction vessel having a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. , 4′-diaminodiphenyl ether: 36.7 g, p-aminophenol: 13.3 g and ethylene glycol monomethyl ether: 171.4 g were added and reacted for 4 hours while refluxing to obtain a solution of the polyimide compound (A-2). It was. The weight average molecular weight was 1770.

Production Example 3: Production of polyimide compound (A-3) 4,4′-diphenylmethane bismaleimide: 350 g, 4 mL in a reaction vessel having a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser. , 4′-diaminodiphenyl ether: 36.7 g, p-aminophenol: 13.3 g and ethylene glycol monomethyl ether: 171.4 g were added and reacted for 6 hours while refluxing to obtain a solution of the polyimide compound (A-3). It was. The weight average molecular weight was 2150.

Production Example 4: Production of polyimide compound (A-4) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, 4,4′-diphenylmethane bismaleimide: 350 g, 1 , 4-bis [1- (4-aminophenyl) -1-methylethyl] benzene: 63.2 g, p-aminophenol: 13.3 g and ethylene glycol monomethyl ether: 171.4 g, and refluxed for 2 hours It was made to react and the solution of the polyimide compound (A-4) was obtained. The weight average molecular weight was 1270.

Production Example 5 Production of Polyimide Compound (A-5) In a reaction vessel having a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a reflux condenser, 4,4′-diphenylmethane bismaleimide: 350 g, 1 , 4-bis [1- (4-aminophenyl) -1-methylethyl] benzene: 63.2 g, p-aminophenol: 13.3 g and ethylene glycol monomethyl ether: 171.4 g, and refluxed for 4 hours. It was made to react and the solution of the polyimide compound (A-5) was obtained. The weight average molecular weight was 1910.

Production Example 6 Production of Polyimide Compound (A-6) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, 4,4′-diphenylmethane bismaleimide: 350 g, 1 , 4-bis [1- (4-aminophenyl) -1-methylethyl] benzene: 63.2 g, p-aminophenol: 13.3 g and ethylene glycol monomethyl ether: 171.4 g, and refluxed for 6 hours It was made to react and the solution of the polyimide compound (A-6) was obtained. The weight average molecular weight was 2290.

Production Example 7: Production of polyimide compound (A-7) BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd., commercial product) in a 2 liter reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume Name, maleimide compound represented by formula (I-3), n = 1-3, average molecular weight, 424): 350 g, 4,4′-diaminodiphenyl ether: 18.6 g, p-amino Phenol: 11.3 g and ethylene glycol monomethyl ether: 98.0 g were added and reacted for 4 hours while refluxing to obtain a solution of the polyimide compound (A-7). The weight average molecular weight was 1850.

Production Example 8: Production of polyimide compound (A-8) BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd. Name): 350 g, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene: 32.0 g, p-aminophenol: 11.3 g and ethylene glycol monomethyl ether: 98.0 g The solution was reacted for 4 hours while refluxing to obtain a solution of the polyimide compound (A-8). The weight average molecular weight was 2230.

(Comparative Production Examples 1-6)
Comparative production example 1: Production of polyimide compound (A-9) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, 4,4′-diphenylmethane bismaleimide: 350 g, 4,4′-Diaminodiphenyl ether: 22.0 g, p-aminophenol: 13.3 g and ethylene glycol monomethyl ether: 171.4 g were added and reacted for 1 hour while refluxing to obtain a solution of the polyimide compound (A-9). Obtained. The weight average molecular weight was 650. After cooling to room temperature, a precipitate was generated in the polyimide compound (A-9).

Comparative production example 2: Production of polyimide compound (A-10) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, 4,4'-diphenylmethane bismaleimide: 350 g, 1,4-Bis [1- (4-aminophenyl) -1-methylethyl] benzene: 37.9 g, p-aminophenol: 13.3 g, and ethylene glycol monomethyl ether: 171.4 g were added while refluxing. It was made to react for time and the solution of the polyimide compound (A-10) was obtained. The weight average molecular weight was 850. After cooling to room temperature, a precipitate was generated in the polyimide compound (A-10).

Comparative Production Example 3 Production of Polyimide Compound (A-11) 4,4′-diphenylmethanebis was placed in a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Maleimide: 350 g, 4,4′-diaminodiphenyl ether: 61.78 g, p-aminophenol: 11.3 g and ethylene glycol monomethyl ether: 171.4 g were added and reacted for 6 hours while refluxing to obtain a polyimide compound (A-11 ) Was obtained. The weight average molecular weight was 2620.

Comparative Production Example 4: Production of Polyimide Compound (A-12) BMI-2300 (Daiwa Kasei Kogyo Co., Ltd.) was added to a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Product name): 350 g, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene: 105.28 g, p-aminophenol: 11.3 g and ethylene glycol monomethyl ether: 171.4 was added and reacted for 6 hours while refluxing to obtain a polyimide compound (A-12) solution. The weight average molecular weight was 3140.

Comparative Production Example 5: Production of polyimide compound (A-13) BMI-2300 (Daiwa Kasei Kogyo Co., Ltd.) was added to a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Product name: 350 g, Jeffamine D-230 (manufactured by HUNTSMAN, product name, polyoxypropylene-based diamine, average molecular weight, 230): 42.2 g, p-aminophenol: 13.3 g and ethylene Glycol monomethyl ether: 173.8 g was added and reacted for 30 minutes while refluxing to obtain a solution of polyimide compound (A-13). The weight average molecular weight was 1980.

Comparative Production Example 6: Production of polyimide compound (A-14) BMI-2300 (Daiwa Kasei Kogyo Co., Ltd.) was added to a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Co., Ltd., trade name): 350 g, Jeffamine D-400 (manufactured by HUNTSMAN, trade name, polyoxypropylene diamine, average molecular weight, 400): 73.3 g, p-aminophenol: 13.3 g and ethylene Glycol monomethyl ether: 173.8 g was added and reacted for 30 minutes while refluxing to obtain a solution of polyimide compound (A-14). The weight average molecular weight was 2290.

The production of the polyimide compound is shown in Table 1 together with the “degree of bonding” defined in the present invention.

(Examples 1-8, Comparative Examples 3-6)
Composition ratios shown in Tables 2 and 3 using the synthesized polyimide compound (A), epoxy resin (B), styrene-maleic acid copolymer (C), curing accelerator (F), and methyl ethyl ketone as a diluent solvent ( To obtain a uniform varnish having a resin content of 60% by mass. Next, the varnish was impregnated and coated on an E glass cloth having a thickness of 0.1 mm and dried by heating at 140 ° C. for 3 to 4 minutes to produce a prepreg having a resin content of 54 ± 2% by mass. Further, three of these prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 1.5 MPa and a temperature of 230 ° C. for 60 minutes to produce a copper clad laminate. Further, the produced prepreg was crushed in a plastic bag, and resin powder was collected. An electrolytic copper foil having a thickness of 18 μm was disposed on both surfaces of the resin powder, and pressing was performed at a pressure of 1.5 MPa and a temperature of 230 ° C. for 60 minutes to prepare a resin plate sandwiched between the electrolytic copper foils. Next, the electrolytic copper foil on the surface was peeled off from the resin plate sandwiched between the electrolytic copper foils to obtain a resin plate having a thickness of 1 mm.
Using the copper-clad laminate or resin plate thus obtained, copper foil adhesion (copper foil peel strength (90 °)), solder heat resistance, and dielectric properties [relative permittivity (Dk ) And dielectric loss tangent (Df)]. The results are shown in Tables 2 and 3.
In addition, in the polyimide compounds (A-9) and (A-10) produced in Comparative Production Examples 1 and 2, since the polyimide compound was precipitated at room temperature, the varnish cannot be produced using this polyimide compound. Evaluation (comparative examples 1 and 2) as a thermosetting resin composition was not performed.
However, although the above comparative production example is a case where ethylene glycol monomethyl ether is used as a solvent, by using other solvents, precipitation can also be suppressed and a varnish can be produced, so that a polyimide compound is precipitated. Therefore, the degree of coupling is not specified to be 2.6 or more.

The materials shown in Tables 2 and 3 are as follows.
Epoxy resin (B)
Dicyclopentadiene type epoxy resin: HP-7200H (manufactured by DIC Corporation, trade name)
Styrene-maleic acid copolymer (C)
SMA-EF40 (manufactured by Elf Atchem, trade name, styrene / maleic anhydride ratio = 4/1, average molecular weight 11,000)
Curing accelerator (F)
-Imidazoles: P200-H50 (Mitsubishi Chemical Corporation, trade name, 2-phenylimidazole addition reactant solution to bisphenol A type epoxy resin)

  As is apparent from Tables 2 and 3, in the examples of the present invention, a laminated board and a resin board having excellent dielectric characteristics and excellent copper foil adhesion and heat resistance are obtained. On the other hand, in the comparative example, the polyimide compound was precipitated, and the solder heat resistance and dielectric properties were inferior to those of the examples.

  According to the present invention, a thermosetting resin composition having excellent dielectric properties and excellent balance of copper foil adhesion and heat resistance can be obtained. Using this thermosetting resin composition, a prepreg and a laminated board can be provided, and it is suitably used for an electronic device or the like as a multilayer printed wiring board.

Claims (9)

A maleimide compound (a) having at least two N-substituted maleimide groups in one molecule represented by the following general formula (I), and two aromatic amino groups in one molecule represented by the following general formula (II) Using an aniline compound (b) having, and an aminophenol compound (c) having one aromatic amino group and at least one aromatic hydroxyl group in one molecule represented by the following general formula (III): a) :( b) :( c) = polyimide curing agent (A), which is a polyimide compound obtained by reacting at a ratio of 4.0: 0.1 to 1.0: 0.1 to 1.0 mol, A thermosetting resin composition containing an epoxy resin (B) and a styrene-maleic acid copolymer (C), wherein the polyimide compound has a degree of bond represented by the following formula of not more than 7.0. It is a polyimide compound obtained by reacting , A thermosetting resin composition.
[Equation 1]
Degree of bond = weight average molecular weight / charge average molecular weight (wherein, the weight average molecular weight is a measured value of the weight average molecular weight of the polyimide compound, and the charge average molecular weight is determined based on the components (a), (b) and (It is a value when the molecular weight of (c) is multiplied by the molar ratio of each component and added, and converted to a molecular weight per mole of charge)

(In the formula, Ar ₁ is a residue represented by the general formula (I-1), (I-2), (I-3) or (I-4)).

(In the formula, R ₁ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and p is an integer of 0 to 4)

(In the formula, R ₂ and R ₃ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, q and r each independently represent an integer of 0 to 4, and A ₁ represents the number of carbon atoms. It is a residue represented by 1-5 alkylene groups, ether groups, or sulfonyl groups.

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

(In the formula, Ar ₂ is a residue represented by the general formulas (II-1) and (II-2).)

Wherein R ₄ and R ₅ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, a hydroxyl group or a halogen atom, and s and t are each independently an integer of 0 to 4 .)

(Wherein R ₆ , R ₇ and R ₈ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, a hydroxyl group or a halogen atom, and u, v and w each independently represent It is an integer from 0 to 4.)

(In the formula, Ar ₃ is a residue represented by the general formula (III-1).)

(Wherein R ₉ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and x is an integer of 0 to 4)   The thermosetting resin composition according to claim 1, which is a polyimide compound obtained by reacting so that the degree of bonding is 3.8 to 6.9.   The maleimide compound (a), the aniline compound (b), and the aminophenol compound (c) are converted into (a) :( b) :( c) = 4.0: 0.4 to 1.0: 0. The thermosetting resin composition according to claim 1 or 2, wherein a polyimide compound is obtained by reacting at a ratio of 2 to 0.6.   The thermosetting resin composition according to any one of claims 1 to 3, wherein the obtained polyimide compound has a weight average molecular weight of 1,000 to 2,500. The weight average molecular weight of the component (C) styrene-maleic acid copolymer is 1,000 to 50,000, and is represented by the general formula (IV) with respect to the number of monomer units n2 represented by the general formula (V). The thermosetting resin composition according to any one of claims 1 to 4, wherein the ratio of the number of monomer units n1 and n1 / n2 is 1.0 to 6.0.

(Wherein R ₁₀ and R ₁₁ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. However, at least one of R ₁₀ and R ₁₁ is It is a phenyl group or a substituted phenyl group.)

  Furthermore, the thermosetting resin composition in any one of Claims 1-5 containing a hardening accelerator (F).   The prepreg using the thermosetting resin composition in any one of Claims 1-6.   A laminate formed by using the prepreg according to claim 7.   The printed wiring board manufactured using the laminated board of Claim 8.