JP5736944B2 - Thermosetting resin composition, prepreg and laminate - Google Patents

Description

  The present invention relates to a thermosetting resin composition, and has excellent low thermal expansibility, high glass transition temperature, good copper foil adhesion, solder heat resistance, heat resistance with copper, flame resistance, drill workability, In particular, the present invention relates to a thermosetting resin composition, a prepreg, and a laminate that are excellent in low water absorption and desmear resistance, have low toxicity and are excellent in safety and work environment, and are suitable for electronic parts and the like.

Thermosetting resins are widely used in the field of electronic components and the like because the cross-linked structure unique to thermosetting resins exhibits high heat resistance and dimensional stability. In particular, in copper-clad laminates and interlayer insulation materials, characteristics such as high copper foil adhesion, heat resistance (high glass transition temperature), and good low thermal expansion properties have been demanded in recent years for higher density and higher reliability. Is strongly demanded.
Moreover, due to recent environmental problems, mounting of electronic parts using lead-free solder and flame resistance using halogen-free are required, and therefore higher heat resistance and flame resistance than conventional ones are required.
Furthermore, in order to improve the safety of the product and the working environment, there is a demand for a thermosetting resin that includes only low-toxic components and does not generate toxic gases.

  In this respect, the liquid crystalline polymer is a thermosetting resin that has excellent dielectric properties, low thermal expansion, flame retardancy, etc., but is polyester, polyamide, polycarbonate, polythiol, or polyether. When a known liquid crystal polymer such as polyazomethine is used as it is in a thermosetting resin, the melting temperature is too high, and the processability and moldability are insufficient, and the solubility in organic solvents is insufficient, making it difficult to handle. There was a problem.

  Among these liquid crystalline polymers, since GFD'Alelio found polyazomethine (see Non-Patent Document 1), which is a liquid crystalline oligomer, many patent cases relating to resins using polyazomethine have been reported ( For example, see Patent Documents 1 to 7).

Patent Document 1 discloses various polyazomethines, and Patent Documents 2 to 7 disclose polyazomethines having specific structures. Patent Document 8 discloses thermosetting polyazomethine resins containing unsaturated groups, and describes that these resins exhibit high heat resistance.
However, the polyazomethines described in Patent Documents 1 to 7 are different from thermosetting resins that are three-dimensionally cross-linked and infusible and insolubilized. When used as a copper-clad laminate or an interlayer insulating material, heat resistance and moldability May be insufficient.
Further, the thermosetting polyazomethine resin described in Patent Document 8 still lacks improvement in heat resistance and toughness, and even when these are used as a copper clad laminate or an interlayer insulating material that has recently been required, In some cases, the reliability, reliability, workability and the like are insufficient.

As described above, the laminated board material is required to have high copper foil adhesiveness, heat resistance, good low thermal expansion property, and the like due to the recent demand for higher density and higher reliability. For example, it is desired that the copper foil peel strength is 1.0 kN / m or more, particularly 1.2 kN / m or more as the copper foil adhesion for forming fine wiring.
In addition, as the density increases, the base material tends to be thinner, and the warp of the base material during heat treatment needs to be small. In order to reduce warpage, it is effective that the base material has low thermal expansion, and it is desired that the thermal expansion coefficient is 25 ppm / ° C. or less, particularly 20 ppm / ° C. or less. It is necessary to increase the number of layers using a build-up material to increase the density, and high reflow heat resistance is required, but heat resistance with copper (T-300), which is a guideline for reflow heat resistance evaluation It is desired that no blistering occurs for 30 minutes or more.
Furthermore, as the density increases, the base material is in a direction that requires more reliability, and the inner wall roughness of the drill hole during drilling is required to be small. The evaluation of the inner wall roughness of the drill hole is evaluated based on the penetration property of the plated copper, and it is desired that the maximum plating penetration length is 20 μm or less, particularly 15 μm or less.
The demand for high-speed response continues to increase, and it is desired that the relative dielectric constant of the substrate is 5.0 or less and the dielectric loss tangent is 0.020 or less.

JP 51-138800 A JP-A-60-181127 JP-A-60-101123 JP 2003-073470 A JP-A-63-193925 Japanese Patent Laid-Open No. 01-069631 Japanese Patent Laid-Open No. 01-079233 Japanese Patent Laid-Open No. 05-140067

Polymer Sci. Tech., Wiley-Interscience, NewYork, 1969, Vol.10, pp.659-670

  In view of the current situation, the object of the present invention has excellent low thermal expansibility, high glass transition temperature, low dielectric property, copper foil adhesion, solder heat resistance, heat resistance with copper, flame retardancy, and drill workability. In particular, it is to provide a thermosetting resin composition, a prepreg, and a laminate which are excellent in low water absorption, desmear resistance, low toxicity and excellent in safety and work environment, and suitable for electronic parts and the like.

As a result of diligent research in the situation where the laminated plate material has various characteristics as described above, the present inventors have found that a bismaleimide derivative (A) and an epoxy resin (B) having a polyazomethine having a specific chemical formula. It has been found that a resin composition suitable for the above-mentioned purpose can be obtained by the inclusion, and the present invention has been completed.
That is, the present invention provides the following thermosetting resin composition, prepreg and laminate.

1. A thermosetting resin comprising a bismaleimide derivative (A) having polyazomethine represented by the following general formula (I) and an epoxy resin (B) having at least two epoxy groups in one molecule Resin composition.

（式中、Ａr₁は独立に一般式（I−１）、（I−２）、（I−３）又は（I−４）で表される残基であり、Ａr₂は下記一般式（I−５）又は（I−６）で示される残基であり、複数あるＡr₂は同一でも異なっていても良い。ｎは０〜１０である。）

(In the formula, Ar ₁ is independently a residue represented by general formula (I-1), (I-2), (I-3) or (I-4), and Ar ₂ is represented by the following general formula ( I-5) or a residue represented by (I-6), and a plurality of Ar ₂ may be the same or different. N is 0 to 10.)

（式中、Ｒ₁は炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｐは０〜４の整数である）

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

（式中、Ｒ₂及びＲ₃は各々独立に炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｑ、ｒは各々独立に０〜４の整数であり、Ａ₁は炭素数１〜５のアルキレン基、アルキリデン基、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 an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, q and r are each independently an integer of 0 to 4, and A ₁ represents the number of carbon atoms. It is a residue represented by an alkylene group of 1 to 5, an alkylidene group, an ether group, or a sulfonyl group.)

（式中、ｍは１〜１０の整数である。）

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

（式中、Ｒ₆及びＲ₇は各々独立に炭素数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、Ａ₂は単結合、炭素数１〜５のアルキレン基、アルキリデン基、エーテル基、スルフォニル基、ケトン基、フルオレン基、又はフェニレンジオキシ基で表される残基である。）

(Wherein R ₆ and R ₇ each independently represents 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, A ₂ is a residue represented by a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group, an ether group, a sulfonyl group, a ketone group, a fluorene group, or a phenylenedioxy group.

（式中、Ａ₃は、単結合、炭素数１〜５のアルキレン基、イソプロピリデン基、エーテル基、又はスルフォニル基である。）

(In the formula, A ₃ is a single bond, an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, or a sulfonyl group.)

2. Furthermore, said 1 thermosetting resin composition containing a hardening accelerator (C).
3. Furthermore, the said 1 or 2 thermosetting resin composition containing an inorganic filler (D).
4). Furthermore, the thermosetting resin composition in any one of said 1-3 containing a flame retardant (E).
5. Furthermore, said 4 thermosetting resin composition containing a flame retardant adjuvant (F).
6). Prepreg, characterized in that either of the thermosetting resin composition of the 1-5 are free immersion or coating in the sheet-shaped reinforcing substrate.
7). An insulating resin layer is formed using the thermosetting resin composition according to any one of 1 to 5 or the prepreg according to 6 above.

  The thermosetting resin composition of the present invention has excellent low thermal expansion, high glass transition temperature, low dielectric property, copper foil adhesion, solder heat resistance, heat resistance with copper, flame resistance, and drill workability. In particular, it has excellent low water absorption and desmear resistance, is low in toxicity and excellent in safety and work environment, and can be suitably used for electronic parts and the like.

2 is an FT-IR measurement chart of a polyazomethine compound having a primary amino group at the terminal obtained in Production Example 1. 2 is an FT-IR measurement chart of a bismaleimide derivative (A-1) having polyazomethine obtained in Production Example 1. 10 is an FT-IR measurement chart of a prepreg obtained in Example 9. 6 is an FT-IR measurement chart of a prepreg obtained in Example 11. FIG.

（式中、Ａr₁は独立に下記一般式（I−１）、（I−２）、（I−３）又は（I−４）で表される残基であり、Ａr₂は下記一般式（I−５）又は（I−６）で示される残基であり、複数あるＡr₂は同一でも異なっていても良い。ｎは０〜１０である。） First, the bismaleimide derivative (A) having polyazomethine will be described. The bismaleimide derivative having polyazomethine as the component (A) is a compound represented by the following general formula (I).

(In the formula, Ar ₁ is independently a residue represented by the following general formula (I-1), (I-2), (I-3) or (I-4), and Ar ₂ is represented by the following general formula: (It is a residue represented by (I-5) or (I-6), and a plurality of Ar ₂ may be the same or different. N is 0 to 10.)

（式中、Ｒ₁は炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｐは０〜４の整数である）

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

（式中、Ｒ₂及びＲ₃は各々独立に炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｑ、ｒは各々独立に０〜４の整数であり、Ａ₁は炭素数１〜５のアルキレン基、アルキリデン基、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 an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, q and r are each independently an integer of 0 to 4, and A ₁ represents the number of carbon atoms. It is a residue represented by an alkylene group of 1 to 5, an alkylidene group, an ether group, or a sulfonyl group.)

（式中、ｍは１〜１０の整数である。）

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

（式中、Ｒ₆及びＲ₇は各々独立に炭素数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、Ａ₂は単結合、炭素数１〜５のアルキレン基、アルキリデン基、エーテル基、スルフォニル基、ケトン基、フルオレン基、又はフェニレンジオキシ基で表される残基である。）

(Wherein R ₆ and R ₇ each independently represents 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, A ₂ is a residue represented by a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group, an ether group, a sulfonyl group, a ketone group, a fluorene group, or a phenylenedioxy group.

（式中、Ａ₃は、単結合、炭素数１〜５のアルキレン基、イソプロピリデン基、エーテル基、又はスルフォニル基である。）

(In the formula, A ₃ is a single bond, an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, or a sulfonyl group.)

Examples of the bismaleimide derivative (A) having the polyazomethine as the component (A) include bismaleimide derivatives represented by the following formula (II).

Next, the manufacturing method of the bismaleimide derivative (A) which has polyazomethine is demonstrated. As a method for producing the bismaleimide derivative (A) having polyazomethine, there are the following three methods (Production Methods A, B, and C).
Production method A: An amino compound (a) having two primary amino groups in one molecule represented by the following general formula (III), and two aldehydes in one molecule represented by the following general formula (IV) A polyazomethine compound (c) having a primary amino group at the terminal represented by the following general formula (V) is produced by dehydration condensation reaction with an aldehyde compound (b) having a group in an organic solvent, and then the compound ( bismaleimide having polyazomethine by c) and Michael addition reaction of maleimide compound (d) having at least two N-substituted maleimide groups in one molecule represented by the following general formula (VI) in an organic solvent A derivative is produced.

（式中、Ａr₂は一般式（I）のものと同様である。）

(In the formula, Ar ₂ is the same as that of the general formula (I).)

（式中、Ａr₂及びｎは一般式（I）のものと同様である。）

(In the formula, Ar ₂ and n are the same as those in formula (I).)

（式中、Ａr₁は一般式（I）のものと同様である。）

(In the formula, Ar ₁ is the same as that of the general formula (I).)

Production method B: An amino compound (a ₁ ) having two primary amino groups in one molecule represented by the general formula (III) and at least two N— in one molecule represented by the general formula (VI) The maleimide compound (d) having a substituted maleimide group is subjected to Michael addition reaction in an organic solvent to produce a maleimide derivative (e) having a primary amino group represented by the following general formula (VII), and then this compound (e ) And an aldehyde compound (b) having two aldehyde groups in one molecule represented by general formula (IV), or an aldehyde compound (b) having two aldehyde groups in one molecule represented by general formula (IV) (b) ) And an amino compound (a ₂ ) having two primary amino groups in one molecule represented by the general formula (III) are subjected to a dehydration condensation reaction in an organic solvent to thereby produce a bismaleimide derivative having polyazomethine (A ).

（式中、Ａr₁は一般式（I）のものと同様である。）

(In the formula, Ar ₁ is the same as that of the general formula (I).)

Production method C: Compound (a ₁ ) having two primary amino groups in one molecule represented by general formula (III), and at least two N-substituted maleimides in one molecule represented by general formula (VI) The maleimide compound (d) having a group is subjected to Michael addition reaction in an organic solvent to produce a maleimide derivative (e) having a primary amino group in the molecule represented by the general formula (VII), and then the maleimide derivative (e ) And an aldehyde compound (b) having two aldehyde groups in one molecule represented by general formula (IV), or an aldehyde compound (b) having two aldehyde groups in one molecule represented by general formula (IV) (b) ) And an amino compound (a ₂ ) having two primary amino groups in one molecule represented by the general formula (III) is prepared in an organic solvent, and this mixed resin solution is Heat treatment at 100-200 ° C. A bismaleimide derivative (A) having polyazomethine is produced by dehydrating condensation reaction.
Bismaleimide derivatives having (A) component polyazomethine may be produced by any of the production methods of A, B, and C described above, and production method A and production method B have the feature that the end point of the synthesis is particularly easy to manage. The production method C is a production method particularly effective when the solvent solubility of the bismaleimide derivative (A) having the polyazomethine of the present invention is insufficient.

  First, the production method A will be described in detail. In production method A, first, two amino compounds (a) having two primary amino groups in one molecule represented by the general formula (III) are contained in one molecule represented by the general formula (IV). A polyazomethine compound (c) having a primary amino group at the terminal represented by the general formula (V) is produced by a dehydration condensation reaction with an aldehyde compound (b) having an aldehyde group in an organic solvent. By subjecting the azomethine compound (c) and the maleimide compound (d) having at least two N-substituted maleimide groups in one molecule represented by the general formula (VI) to Michael addition reaction in an organic solvent, the general formula (I The bismaleimide derivative (A) having a polyazomethine represented by

  The amino compound (a) may be independent or the same, for example, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3-methyl-1,4-diaminobenzene, 2,5-dimethyl- 1,4-diaminobenzene, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2 , 2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis (3-a No-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- ( 4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4, 4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9,9-bis (4-aminophenyl) ) Aromatic amines such as fluorene.

  Among these, the amino compound (a) has a high reaction rate at the time of synthesis, and 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, which can have higher heat resistance. , 4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- ( 4-aminophenoxy) phenyl) propane and the like are more preferable and 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4 in view of low cost and solubility in a solvent. , 4′-diamino-3,3′-diethyl-diphenylmethane and bis (4- (4-aminophenoxy) phenyl) propane are preferred, and 3,3 ′ is preferred from the viewpoint of low thermal expansion and dielectric properties. Dimethyl-4,4'-diamino biphenyl, bis (4- (4-aminophenoxy) phenyl) propane is particularly preferred. Moreover, since it is a high elastic modulus, p-phenylenediamine, m-phenylenediamine, 3-methyl-1,4-diaminobenzene, and 2,5-dimethyl-1,4-diaminobenzene are particularly preferable.

Examples of the aldehyde compound (b) include terephthalaldehyde, isophthalaldehyde, and o-phthalaldehyde. Among these, terephthalaldehyde, which can be further reduced in thermal expansion, has a high reaction rate during synthesis, is excellent in solvent solubility, and is easily available commercially, is particularly preferable.
Here, the amount of amino compound (a) and aldehyde compound (b) used is the number of primary amino groups of amino compound (a) [the amount of amino compound (a) used / the amount of primary amino group equivalent of amino compound (a)]. The number of aldehyde groups of the aldehyde compound (b) [desired amount of aldehyde compound (b) / equivalent aldehyde group of aldehyde compound (b)] is preferably used. If the number of primary amino groups in the amino compound (a) is less than or equal to the number of aldehyde groups in the aldehyde compound (b), the synthesis yield is significantly reduced, gelation or insolubilization occurs during the synthesis, The heat resistance of the bismaleimide derivative obtained may be reduced.

  The organic solvent used in the dehydration condensation reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, γ- Examples thereof include ester solvents such as butyrolactone, and one or two or more of them can be used in combination. Among these, dimethylformamide, dimethylacetamide, cyclohexanone, γ-butyrolactone and the like are preferable from the viewpoint of solubility, and dimethylacetamide and propylene glycol monomethyl ether, which are highly volatile and hardly remain as residual solvents during the production of prepreg, are more preferable. Since this synthesis reaction is a dehydration condensation reaction, water is produced as a by-product. It is particularly preferable to use an aromatic solvent such as toluene, xylene, mesitylene or the like for the purpose of removing this by-product water, while removing the by-product water by azeotropy with the aromatic solvent. It is desirable to synthesize.

The amount of the organic solvent used is preferably 25 to 2000 parts by mass, more preferably 40 to 1000 parts by mass, based on 100 parts by mass of the total amount of the amino compound (a) and the aldehyde compound (b). It is especially preferable to set it as -500 mass parts. When the amount of the organic solvent used is less than 25 parts by mass, the solubility is insufficient, and when it is more than 2000 parts by mass, the synthesis takes a long time and the production cost increases.
In the dehydration condensation reaction, a reaction catalyst can be optionally used as necessary, and the catalyst is not particularly limited. Examples of reaction catalysts include acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. 1 type (s) or 2 or more types can be mixed and used. An acidic catalyst such as p-toluenesulfonic acid is particularly preferred in order to allow the dehydration condensation reaction to proceed efficiently.

The above raw materials, organic solvent and, if necessary, a reaction catalyst are charged into a synthesis kettle, and if necessary, stirred for 0.1 to 10 hours with heating and heat retention to cause a dehydration condensation reaction. A polyazomethine compound (c) having a primary amino group is produced.
The reaction temperature is preferably 25 to 200 ° C. When the temperature is lower than 25 ° C, the reaction rate becomes slow. When the temperature is higher than 200 ° C, a high boiling point solvent is required as the reaction solvent. It may be easy to leave a solvent and heat resistance may decrease. It is desirable to react with dimethylformamide, dimethylacetamide, cyclohexanone and the like having excellent solubility in combination with an aromatic solvent such as toluene and xylene while removing water as a by-product by azeotropy, and the reaction temperature is 120 to 200 ° C. is particularly preferred.

The polyazomethine compound (c) obtained by the dehydration condensation reaction can be confirmed by taking out a small amount of sample and performing IR measurement on the sample purified by reprecipitation. 1700 cm ^-1, and 2750 cm ^-1 due to the aldehyde group of the aldehyde compound is a synthetic material by IR measurement (b), the peak of 2800 cm ^-1 disappeared, due to Schiff base (-N = CH-) 1620cm ^- Ensure ^that the ^first peak appears, also, by the peak around at 3,440 cm ^-1, and 3370cm ^-1 due to primary amino groups to make sure that there, better synthesis reaction proceeds to the desired It can be confirmed that the compound is produced.

The bismaleimide derivative (A) having the polyazomethine of the present invention represented by the general formula (I) is prepared by heating the polyazomethine compound (c) produced as described above and the maleimide compound (d) in an organic solvent as necessary. -Manufactured by stirring for 0.1 to 10 hours while keeping the temperature to allow Michael addition reaction.
As the maleimide compound (d), for example, bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide represented by the following general formula (VIII), 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 and the like.

（式中、ｍは１〜１０の整数である。）

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

  Among these, as the maleimide compound (d), bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5 having a high reaction rate and higher heat resistance can be obtained. -Diethyl-4,4-diphenylmethane bismaleimide and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred. From the viewpoint of solubility in a solvent, 3,3-dimethyl-5,5- Diethyl-4,4-diphenylmethane bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred because it is inexpensive.

In the Michael addition reaction, the amount of polyazomethine compound (c) and maleimide compound (d) used is the number of maleimide groups of maleimide compound (d) [the amount of maleimide compound (d) used / maleimide group equivalent of maleimide compound (d)]. Is preferably in the range of 2 to 10 times the number of primary amino groups of polyazomethine compound (c) [amount of polyazomethine compound (c) used / equivalent primary amino group of polyazomethine compound (c)]. If it exceeds 10 times, the solubility in an organic solvent may be insufficient or the heat resistance of the thermosetting resin may be reduced. If it is less than 2 times, gelation may occur or the heat resistance of the thermosetting resin may be reduced. There is a case. Moreover, it is preferable that the usage-amount of an organic solvent shall be 25-2000 mass parts per 100 mass parts of total amounts (solid content) of a maleimide compound (d) and an amino compound (a), and shall be 40-1000 mass parts. It is more preferable to set it as 40-500 mass parts. When the amount of the organic solvent is less than 40 parts by mass, the solubility is insufficient, and when it is more than 500 parts by mass, the synthesis takes a long time and the production cost increases.
As the organic solvent used in the Michael addition reaction, the same solvent as in the dehydration condensation reaction is used. Moreover, the reaction catalyst similar to the above-mentioned dehydration condensation reaction can be arbitrarily used for the Michael addition reaction.

By adding the above polyazomethine compound (c), maleimide compound (d), an organic solvent, and a reaction catalyst to a synthesis kettle if necessary, and stirring for 0.1 to 10 hours while heating and keeping heat as necessary to cause a Michael addition reaction, A bismaleimide derivative (A) having polyazomethine is produced.
The reaction temperature of the Michael addition reaction is preferably 25 to 200 ° C, particularly preferably 100 to 160 ° C. When the reaction temperature is lower than 25 ° C, the reaction rate is slow, and when the reaction temperature is higher than 200 ° C, gelation tends to occur.
The obtained bismaleimide derivative (A) having polyazomethine can be confirmed by taking out a small amount of sample and performing GPC measurement and IR measurement of the sample purified by reprecipitation. It was confirmed that the peak of the bismaleimide derivative synthesized by GPC measurement appeared, and by IR measurement, 1710 cm ⁻¹ due to the imide group of bismaleimide and 1620 cm due to the Schiff base (—N═CH—) By confirming that the peak of ⁻¹ appears, it can be confirmed that the Michael addition reaction proceeds well and a desired compound is produced.

Next, the production method B will be described in detail.
In production method B, a maleimide derivative (e) having a primary amino group in the molecular structure is first produced by Michael addition reaction of amino compound (a ₁ ) and maleimide compound (d) in an organic solvent. Then, this maleimide derivative (e), the aldehyde compound (b), or the aldehyde compound (b) and the amino compound (a ₂ ) are subjected to a dehydration condensation reaction in an organic solvent, whereby a bismaleimide derivative (A) having polyazomethine is obtained. Is manufactured.
In the production method B, the amino compound (a ₁ ) and the amino compound (a ₂ ) are the same as the amino compound (a) in the production method A, and the maleimide compound (d), the aldehyde compound (b) and the organic solvent are the production methods. Same as A.

In the production method B, first, the amino compound (a ₁ ) and the maleimide compound (d) are stirred in the organic solvent for 0.1 to 10 hours while heating and holding as necessary, and subjected to a Michael addition reaction. A maleimide derivative (e) having a primary amino group is obtained.
In this Michael addition reaction, the amount of maleimide compound (d) and amine compound (a ₁ ) used is the number of maleimide groups in maleimide compound (d) [the amount of maleimide compound (d) used / maleimide group in maleimide compound (d). Equivalent)] is in the range of 2.0 to 10.0 times the number of primary amino groups of amine compound (a ₁ ) [amount of amine compound (a) / primary amino group equivalent of amine compound (a ₁ )]. It is desirable to use it. If it exceeds 10.0 times, the solubility in the solvent may be insufficient or the heat resistance of the thermosetting resin may decrease, and if it is less than 2.0 times, gelation may occur or the heat resistance of the thermosetting resin may decrease. May decrease.

The amount of the organic solvent, the total amount (solid content) 100 parts by weight per amine compounds (a ₁₎ and maleimide compound (d), preferably to 25 to 2000 parts by weight, and 40 to 1000 parts by weight It is more preferable to set it to 40 to 500 parts by mass. When the amount of the organic solvent is less than 25 parts by mass, the solubility is insufficient, and when it is more than 2000 parts by mass, the Michael addition reaction takes a long time and the production cost is increased. In the Michael addition reaction, the same reaction catalyst as in Production Method A can be optionally used as necessary.
Amine compound (a ₁ ), maleimide compound (d), organic solvent, and if necessary, a reaction catalyst is added to the synthesis kettle, and if necessary, stirred for 0.1 to 10 hours while heating and keeping warm, and subjected to Michael addition reaction. A maleimide derivative (e) having a primary amino group represented by the formula (VII) is produced.
The temperature of the Michael addition reaction is preferably 80 to 200 ° C, particularly preferably 100 to 160 ° C. When the temperature is lower than 80 ° C, the reaction rate is slow, and when the temperature is higher than 200 ° C, gelation is likely to occur. The obtained maleimide derivative (e) having a primary amino group can be confirmed by taking a small sample and performing GPC measurement. By confirming that the peak of the maleimide derivative synthesized by GPC measurement appears, it can be confirmed that the synthesis reaction proceeds well and the desired compound is produced.

Next, the obtained maleimide derivative (e) and the aldehyde compound (b), or the aldehyde compound (b) and the amino compound (a ₂ ) are subjected to a dehydration condensation reaction in an organic solvent, whereby the polyazomethine of the present invention is obtained. The bismaleimide derivative (A) having is produced.
Here, the amount of the aldehyde compound (b) and the amino compound (a ₂ ) used is the number of primary amino groups of the maleimide derivative (e) [the amount of maleimide derivative (e) used / the primary amino group equivalent of the maleimide derivative (e)] When amino compound primary amino groups of (a ₂₎ the sum of [the amino compound usage / amino compound (a ₂₎ (a ₂₎ primary amino group equivalent of], aldehyde groups [aldehyde compound of the aldehyde compound (b) It is desirable that the amount used is in a range of 0.1 to 4.0 times the amount of (b) used / aldehyde group equivalent of aldehyde compound (b). If it exceeds 4.0 times, the solubility in the solvent may be insufficient, or the heat resistance of the thermosetting resin and the copper foil adhesion may be reduced. If it is less than 0.1 times, gelation may occur, The heat resistance and heat insulation properties of the curable resin may be reduced.
The amount of the organic solvent used is preferably 25 to 2000 parts by mass per 100 parts by mass of the total amount of the amine compound (a ₁ ), maleimide compound (d), aldehyde compound (b) and amino compound (a ₂ ). 40 to 1000 parts by mass, more preferably 40 to 500 parts by mass. When the amount of the organic solvent used is less than 25 parts by mass, the solubility is insufficient, and when it is more than 2000 parts by mass, the synthesis takes a long time and the production cost increases. The organic solvent used is the same as in production method A. In addition, the same reaction catalyst as in production method A can be arbitrarily used for this dehydration condensation reaction.

A maleimide derivative (e), an aldehyde compound (b), an amino compound (a ₂ ) and an organic solvent, if necessary, a reaction catalyst are charged into the synthesis kettle, and the reaction catalyst is heated for 0.1 hours to 10 minutes, if necessary. The bismaleimide derivative (A) having the polyazomethine of the present invention is produced by stirring for a period of time and causing a dehydration condensation reaction.
The dehydration condensation reaction temperature is preferably 25 to 200 ° C. When the reaction temperature is lower than 25 ° C, the reaction rate becomes slow. When the reaction temperature is higher than 200 ° C., a high-boiling solvent is required as a solvent for the dehydration condensation reaction. Therefore, when the prepreg is produced, the residual solvent tends to remain and heat resistance may be lowered. As an organic solvent, dimethylformamide, dimethylacetamide, cyclohexanone with excellent solubility, and aromatic solvents such as toluene and xylene can be used together, and dehydration condensation reaction can be performed while removing water as a by-product by azeotropy. Desirably, the reaction temperature is particularly preferably 120 to 200 ° C.
The bismaleimide derivative (A) having polyazomethine obtained by the production method B can be confirmed by the same method as the production method A so that the dehydration condensation reaction proceeds well and the desired compound is produced.

Next, the production method C will be described in detail.
In the production method C, first, a maleimide derivative (e) having a primary amino group is produced by Michael addition reaction of an amino compound (a ₁ ) and a maleimide compound (d) in an organic solvent, and then the maleimide derivative A mixed resin solution prepared by dissolving (e), an aldehyde compound (b), or an aldehyde compound (b) and an amino compound (a ₂ ) in an organic solvent, and then applying the mixed resin solution to 100 to 200 A bismaleimide derivative (A) having polyazomethine is produced by a dehydration condensation reaction by heat treatment at ° C.
In production method C, amino compound (a ₁ ) and amino compound (a ₂ ) are the same as amino compound (a) in production method A, and maleimide compound (d), aldehyde compound (b) and the organic solvent are It is the same as that of production method A.

In the production method C, first, a method for producing a maleimide derivative (e) having a primary amino group in a molecular structure by subjecting an amino compound (a ₁ ) and a maleimide compound (d) to a Michael addition reaction in an organic solvent. Is the same as in the case of production method B.
Subsequently, the obtained maleimide derivative (e) and the aldehyde compound (b) or the aldehyde compound (b) and the amino compound (a ₂ ) are dissolved in an organic solvent to produce a mixed resin solution, and then this mixed resin solution The bismaleimide derivative (A) having the polyazomethine of the present invention is produced by heat-treating the material coated with bismuth and causing a dehydration condensation reaction.
Here, the use amount of the aldehyde compound (b) and the amino compound (a ₂ ), the organic solvent and the use amount thereof, and the reaction catalyst are the same as in the case of the production method B.

The compound kettle is charged with maleimide derivative (e), aldehyde compound (b), amino compound (a ₂ ), if necessary, an organic solvent, and a reaction catalyst if necessary, and is heated and kept at 20-100 ° C. if necessary. By stirring and dissolving for 1 to 10 hours, a uniformly dissolved mixed resin solution can be obtained. Although the mixed resin solution may become cloudy after being uniformly dissolved, there is no particular problem as long as it is uniformly dispersed.
Next, dehydration condensation is performed by heat-treating the mixed resin solution applied by casting on a support such as impregnation coating or film using a glass substrate at 100 to 200 ° C. in a dryer. Thus, the bismaleimide derivative (A) having the polyazomethine of the present invention can be produced.
This production method C is particularly effective when the bismaleimide derivative (A) itself having polyazomethine according to the present invention is produced in a dry process, and therefore the bismaleimide derivative (A) itself having polyazomethine is insufficient in solvent solubility. It is a simple manufacturing method.
If the temperature of the dryer is less than 100 ° C., the dehydration condensation reaction may be insufficient or the residual solvent may increase, resulting in a decrease in heat resistance and elastic modulus. Moreover, when the temperature of a dryer exceeds 200 degreeC, gelatinization will advance by superposition | polymerization of bismaleimide, etc., and a moldability may fall.
The bismaleimide derivative (A) having polyazomethine obtained by the production method C can confirm that the dehydration-condensation reaction proceeds well and the desired compound is produced in the same manner as in the production method A.

Next, the epoxy resin (B) having at least two epoxy groups in one molecule will be described. The epoxy resin having at least two epoxy groups in one molecule of the component (B) is not particularly limited as long as it is an epoxy resin having at least two epoxy groups in one molecule. For example, bisphenol A, bisphenol F-type, biphenyl-type, novolak-type, polyfunctional phenol-type, naphthalene-type, alicyclic epoxy resin and glycidyl ether of alcohol-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, etc. Or 2 or more types can be mixed and used.
Among these, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion, Biphenyl aralkyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc. are preferable, and naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin from the viewpoint of having good low thermal expansion and high glass transition temperature Biphenyl aralkyl type epoxy resins and phenol novolac type epoxy resins are more preferred.
In the thermosetting resin composition of the present invention, the use amount of the component (A) is preferably 20 to 95 parts by mass per 100 parts by mass of the total amount of the component (A) and the component (B) in terms of solid content. 40 to 90 parts by mass is more preferable. When the blending amount of the component (A) is 20 parts by mass or more, flame retardancy, heat resistance, adhesiveness, and dielectric characteristics are improved.

In the thermosetting resin composition of the present invention, a flame retardant (E) such as a curing accelerator (C), an inorganic filler (D), or a metal hydrate may be used in combination as necessary. Various properties can be further improved by appropriately using these materials together.
By using an appropriate curing accelerator (C) in combination with the thermosetting resin composition of the present invention, low temperature curability at a molding temperature of 250 ° C. or less can be imparted, and further, high elasticity and flame retardancy. Property, copper foil adhesiveness, etc. can be improved.
Examples of the curing accelerator (C) 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 high elastic modulus, flame retardancy, copper foil adhesion, and the like.
Further, a compound in which an imidazole group represented by the following general formula (IX) is substituted by an epoxy resin, or a compound substituted by an isocyanate resin represented by the following general formula (X) at a relatively low temperature of 200 ° C. or less. It is more preferable because it has excellent curing moldability and aging stability of varnish and prepreg. The compound represented by the following general formula (XI) or (XII) may be used in a small amount, and is also commercially inexpensive. This is particularly preferable.

（式中、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉は各々独立に水素原子、又は炭素数１〜５の脂肪族炭化水素基、フェニル基を示し、Ｂは単結合、又はアルキレン基、アルキリデン基、エーテル基、スルフォニル基のいずれかである。）

(Wherein R ₆ , R ₇ , R ₈ and R ₉ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and B represents a single bond, an alkylene group or an alkylidene group) A group, an ether group, or a sulfonyl group.)

（式中、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉は各々独立に水素原子、又は炭素数１〜５の脂肪族炭化水素基、フェニル基を示し、Ｄはアルキレン基、芳香族炭化水素基等のイソシアネート樹脂の残基である）

(In the formula, R ₆ , R ₇ , R ₈ and R ₉ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a phenyl group, and D represents an alkylene group or an aromatic hydrocarbon group. Is a residue of isocyanate resin, etc.)

In addition, the thermosetting resin composition of the present invention may optionally contain an inorganic filler (D) for the purpose of improving low thermal expansion property, high elastic modulus, heat resistance, and flame retardancy. Can do.
Examples of the inorganic filler (D) include silica, alumina, mica, talc, short glass fiber or fine powder, and hollow glass, calcium carbonate, quartz powder, etc. Among them, copper foil adhesiveness, heat resistance Silica, alumina, mica, talc and the like are preferable from the viewpoint of flame retardancy, and silica and alumina are particularly preferable from the viewpoint of high heat dissipation.

Furthermore, a flame retardant (E) can 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 flame retardants (E) include metal hydrates such as aluminum hydroxide and magnesium hydroxide, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, phosphazenes, red phosphorus, etc. Examples thereof include inorganic flame retardant aids such as phosphorus-based flame retardants, 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.
Among these flame retardants, metal hydrates such as aluminum hydroxide and magnesium hydroxide can express high glass transition temperature and copper foil adhesiveness, and do not contain phosphorus, so safety and environment It is preferable because it is highly adaptable.
Among metal hydrates, boehmite-type aluminum hydroxide (AlOOH) or gibbsite-type aluminum hydroxide [Al (OH) 3] is prepared by heat treatment to have a thermal decomposition temperature of 300 ° C. or higher, such as magnesium hydroxide. A metal hydrate having a thermal decomposition temperature of 300 ° C. or higher is more preferable because it has excellent heat resistance. In particular, boehmite-type aluminum hydroxide (AlOOH) has a particularly high thermal decomposition temperature of 350 ° C. or higher, so that both flame retardancy and particularly high heat resistance are compatible, chemical resistance such as acid resistance, and low water absorption. Since it is excellent in efficiency etc., it is especially preferable.

When the curing accelerator (C) is contained in the thermosetting resin composition of the present invention, the amount used is 0.000 per 100 parts by mass of the total amount of the components (A) and (B) in terms of solid content. It is preferable to set it as 1-10 mass parts, and it is more preferable to set it as 0.1-5 mass parts. If the amount of the curing accelerator used is less than 0.1 parts by mass, heat resistance, flame retardancy, copper foil adhesiveness, etc. may be insufficient, and if it exceeds 10 parts by mass, the heat resistance and aging stability will decrease. Sometimes.
Similarly, when the inorganic filler (D) is contained, the amount used is preferably 10 to 300 parts by mass per 100 parts by mass of the total amount of the components (A) and (B) in terms of solid content. 10 to 250 parts by mass, more preferably 20 to 200 parts by mass, and particularly preferably 30 to 200 parts by mass. If the content of the inorganic filler (C) exceeds 300 parts by mass, chemical resistance such as plating solution resistance and moldability may be deteriorated.

Similarly, when the flame retardant (E) is contained, the amount used is, when the flame retardant is a metal hydrate, per 100 parts by mass of the total amount of the component (A) and the component (B) in terms of solid content. 10 to 300 parts by mass, more preferably 10 to 250 parts by mass, and particularly preferably 50 to 200 parts by mass. If it is less than 10 parts by mass, the flame retardancy may be insufficient, and if it exceeds 300 parts by mass, chemical resistance such as plating solution resistance may be lowered.
When the flame retardant (E) is a phosphorus flame retardant, the content of phosphorus atoms is 0.1 to 10.0 parts by mass per 100 parts by mass of the bismaleimide derivative (A) having polyazomethine in terms of solid content. It is preferable to mix | blend, it is more preferable to mix | blend so that it may become 1.0-10.0 mass part, and it is especially preferable to mix | blend so that it may become 1.0-8.0 mass%. If it is less than 0.1% by mass, the flame retardancy may be insufficient, and if it exceeds 10.0 parts by mass, chemical resistance such as plating solution resistance, heat resistance, and copper foil adhesion may be deteriorated. .
Moreover, a flame retardant adjuvant (F) can be used for a flame retardant (E). As the flame retardant aid, inorganic flame retardant aids such as antimony trioxide and zinc molybdate can be used. The amount used is preferably 0.1 to 20 parts by mass, and preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total amount of components (A) and (B) in terms of solid content. More preferred. When the flame retardant aid (F) exceeds 20 parts by mass, chemical resistance such as plating solution resistance may be lowered.

The thermosetting resin composition of the present invention can optionally contain a known thermoplastic resin, elastomer, flame retardant, organic filler and the like.
Examples of the thermoplastic resin include tetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.
Examples of the organic filler include organic powders such as silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  The thermosetting resin composition of the present invention can optionally contain an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like. Examples of these include UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescence such as stilbene derivatives. Examples include brighteners, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.

  In addition, the organic solvent is used for the thermosetting resin composition of this invention on the handling. The organic solvent to be used is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, etc. Ether solvents, 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 dimethylsulfoxide, and ester systems such as γ-butyrolactone A solvent etc. are mentioned, 1 type (s) or 2 or more types can be mixed and used. Among these, dimethylformamide, dimethylacetamide, cyclohexanone, γ-butyrolactone, propylene glycol monomethyl ether, etc. are preferable from the viewpoint of solubility, and dimethyl dimethyl which has high volatility and hardly remains as a residual solvent at the time of producing a prepreg. Acetamide and propylene glycol monomethyl ether are more preferred.

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. The prepreg of the present invention can be produced by impregnating and coating the above thermosetting resin composition on a sheet-like reinforcing base material 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.

In the laminated board of the present invention, the insulating resin layer is formed using the above-mentioned 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., at a temperature of 100 to 250 ° C., a pressure of 0.2 to 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.

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

(1) Copper foil adhesion (copper foil peel strength)
A 1 cm wide copper foil was formed by immersing the copper clad laminate in a copper etching solution to produce an evaluation substrate, and the adhesion (peel strength) of the copper foil was measured using a tensile tester.

(2) Glass transition temperature (Tg)
A 5 mm square evaluation board from which the copper foil was removed by immersing the copper-clad laminate in a copper etching solution was prepared, and a TMA test apparatus (manufactured by DuPont, TMA2940) was used in the thickness direction (Z direction) of the evaluation board. Measured from thermal expansion characteristics.

(3) Coefficient of linear thermal expansion A 5 mm square evaluation board from which the copper foil has been removed by immersing a copper clad laminate in a copper etching solution is prepared, and a TMA test apparatus (manufactured by DuPont, TMA2940) is used. The linear thermal expansion coefficient of 30 to 100 ° C. in the thickness direction (Z direction) was measured.

(4) Solder heat resistance A 5 cm square evaluation board from which the copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and 121 ° C. using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. After performing the pressure cooker treatment for 4 hours under the condition of 0.2 MPa, the evaluation substrate was immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance. (If there is a blister on the exterior, mark it “blister”.)

(5) Evaluation of water absorption rate A 5-cm square evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and the pressure cooker test apparatus manufactured by Hirayama Mfg. Co., Ltd. was used. After performing moisture absorption treatment for 4 hours under the conditions of ° C and 0.2 MPa, the difference in mass of the substrate before and after moisture absorption treatment was measured, and the increase in mass was calculated as a percentage.

(6) Flame retardance A test piece cut out to a length of 127 mm and a width of 12.7 mm was prepared from an evaluation substrate from which a copper foil was removed by immersing a copper-clad laminate in a copper etching solution. Evaluation was made according to V method.

(7) Heat resistance with copper (T-300)
A 5 mm square evaluation board was produced from the copper clad laminate, and evaluation was performed by measuring the time until the evaluation board swells at 300 ° C. using a TMA test apparatus (manufactured by DuPont, TMA2940). (Things that were blistered when the temperature was raised are referred to as “bulges when the temperature is raised.”)

(8) Dielectric properties (dielectric constant and dielectric loss tangent)
An evaluation board from which copper foil is removed by immersing a copper clad laminate in a copper etching solution is prepared, and a relative dielectric constant at a frequency of 1 GHz is measured using a relative dielectric constant measuring apparatus (product name: HP4291B) manufactured by Hewllet Packerd. The rate and dielectric loss tangent were measured.

(9) Drill workability Using a drill with a diameter of 0.105 mm (Union Tool MV J676), drilling was performed under the conditions of rotation speed: 160000 rpm, feed rate: 0.8 m / min, number of stacked sheets: 6000 hits Thus, an evaluation substrate was produced, and the inner wall roughness of the drill hole was evaluated. The inner wall roughness was evaluated by performing electroless copper plating (plating thickness: 15 μm) and measuring the maximum value of the plating penetration length into the hole wall.

(10) Desmear resistance Desmear treatment is performed by swelling a test piece that has been entirely etched (70 ° C., 5 minutes), washing with running water (room temperature, 2 minutes), roughening (80 ° C., 10 minutes), drag-out (50 ° C., 2 minutes), neutralization (40 ° C., 5 minutes), washing with running water (room temperature, 2 minutes). The test solution used was a solution prepared by adjusting the swelling properties, desmear solution, and neutralization solution made by Atotech to predetermined liquid properties and concentrations.
The test piece size was 50 mm × 50 mm, and the test piece size was three. The mass change after drying (125 ° C., 1 hour) treatment and desmear treatment of the test piece was measured, and the average mass loss per unit area of the three test pieces [mass reduction amount (g) / test piece surface area ( dm ² )] was calculated.

Production Example 1: Production of bismaleimide derivative (A-1) having polyazomethine In a reaction vessel having a volume of 3 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, terephthalaldehyde was added. : 134.0 g, 3,3′-dimethyl-4,4′-diaminobiphenyl: 424.0 g, propylene glycol monomethyl ether: 405.7 g, and toluene: 278.0 g, and the mixture was heated while stirring. After a reflux dehydration reaction at 115 to 125 ° C. for 4 hours, the mixture was cooled to room temperature to obtain a polyazomethine compound solution having a primary amino group at the terminal.
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, terephthalaldehyde, which is a synthetic raw material whose elution time appears around 13.7 minutes, and around 12.8 minutes The peak derived from 3,3′-dimethyl-4,4′-diaminobiphenyl appearing in FIG.
Further, the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) to cause reprecipitation, whereby the purified solid content was taken out and subjected to FT-IR measurement. The measurement results are shown in FIG.
According to Figure 1, around 1700 cm ^-1 due to the aldehyde group of the compound having an aldehyde group, and 2750 cm ^-1, the peak around 2800 cm ^-1 is not observed, also, the Schiff base (-N = CH-) at 3,440 cm ^-1 due to the strong peaks, and a primary amino group at around 1620 cm ^-1 due to, and 3370cm ^-1 confirmed peaks around, the compound of the following formula (XIII) was confirmed that it is prepared .

Next, 716.0 g of bis (4-maleimidophenyl) methane: was added to the above reaction solution, and the mixture was refluxed at about 120 ° C. for 2 hours with stirring, then heated to 130 ° C. and concentrated at normal pressure. Next, after cooling to 100 ° C., 770.1 g of cyclohexanone was added and cooled to room temperature to obtain a solution of bismaleimide derivative (A-1) having polyazomethine.
A small amount of this reaction solution was taken out, dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated to take out the purified solid, and FT-IR measurement was performed. The measurement results are shown in FIG.
According to FIG. 2, near 1715 cm ^-1 due to the imide group bismaleimide, and confirmed peak around 1620 cm ^-1 due to Schiff base (-N = CH-), poly represented by the following Formula (XIV) It was confirmed that a bismaleimide derivative having azomethine was produced.
In Production Example 1, the number of primary amino groups of 3,3′-dimethyl-4,4′-diaminobiphenyl is 4.0, and the number of aldehyde groups of terephthalaldehyde is 2.0. The number of maleimide groups in bis (4-maleimidophenyl) methane is 2.0 times the number of primary amino groups in the polyazomethine compound (XIV) having a primary amino group at the terminal.

Production Example 2: Production of bismaleimide derivative (A-2) having polyazomethine In a reaction vessel having a volume of 5 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, terephthalaldehyde : 134.0 g, p-phenylenediamine: 108.0 g, N, N-dimethylacetamide: 601.6 g and toluene: 396.6 g were mixed, and the temperature was increased while stirring. A reflux dehydration reaction was performed for a period of time.
Subsequently, 4,4′-diaminodiphenylmethane: 396.0 g was added, the temperature was increased while stirring, and the reflux dehydration reaction was further performed at about 115 to 125 ° C. for 4 hours. A solution of a polyazomethine compound having an amino group was obtained.
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, terephthalaldehyde, which is a synthetic raw material that appears at about 13.7 minutes, and about 13.2 minutes The peak derived from p-phenylenediamine appearing at 4 and 4,4′-diaminodiphenylmethane appearing around 12.8 minutes had disappeared.
Furthermore, when the reaction solution taken out in a small amount was dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1) and reprecipitated, the purified solid content was taken out and subjected to FT-IR measurement. around 1700 cm ^-1 due to the aldehyde group of the compound having an aldehyde group, and 2750 cm ^-1, the peak around 2800 cm ^-1 is not observed, also, around 1620 cm ^-1 due to Schiff base (-N = CH-) due to strong peaks, and the primary amino group of at 3,440 cm ^-1, and 3370cm peak around ^-1 confirmed, the compound of the following formula (XV) was confirmed that it is manufactured.

Next, propylene glycol monomethyl ether: 1064.1 g and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 1140.0 g were added to the reaction solution, and the mixture was stirred at about 120 ° C. for 2 hours. After keeping the temperature, the solution was cooled to room temperature to obtain a solution of a bismaleimide derivative (A-2) having polyazomethine.
A small amount of this reaction solution was taken out, dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1), and reprecipitated to take out the purified solid and subjected to FT-IR measurement. around 1715 cm ^-1 due to the imide group and a peak around 1620 cm ^-1 due to Schiff base (-N = CH-) to check, bismaleimide derivative having the polyazomethine of the following formula (XVI) is prepared Confirmed that.
In Production Example 2, the total number of primary amino groups of p-phenylenediamine and 4,4′-diaminodiphenylmethane is 4.0, and the number of aldehyde groups of terephthalaldehyde is 2.0. The number of maleimide groups in 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is 2.0 times the number of primary amino groups in the polyazomethine compound (XVI) having a primary amino group at the terminal.

Production Example 3: Production of bismaleimide derivative (B-1) having polyazomethine In a reaction vessel having a volume of 5 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 2-bis (4- (4-maleimidophenoxy) phenyl) propane: 1140.0 g, 4,4′-diamino-3,3′-dimethyl-diphenylmethane: 226.0 g, and propylene glycol monomethyl ether: 540.5 g And toluene: 328.9 g were mixed and refluxed at 115 to 125 ° C. for 2 hours with stirring.
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, 4,4′-diamino-3,3′-dimethyl-diphenylmethane appeared at an elution time of about 12.8 minutes. In addition, a peak different from the synthetic raw material appeared at an elution time of about 11.3 minutes, and it was confirmed that the compound of the following chemical formula (XVII) was produced.

Next, 67.0 g of terephthalaldehyde was added, and reflux dehydration reaction was performed at about 115 to 125 ° C. for 4 hours. Next, after heating up to 130 ° C. and concentrating at normal pressure, cooling, adding 841.0 g of cyclohexanone at 100 ° C., cooling to room temperature with stirring, and bismaleimide derivative (B-1) having polyazomethine Solution was obtained.
A small amount of this reaction solution was taken out, dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1), and reprecipitated to take out the purified solid and subjected to FT-IR measurement. around 1715 cm ^-1 due to the imide group and a peak around 1620 cm ^-1 due to Schiff base (-N = CH-) to check, bismaleimide derivative having the polyazomethine of the following formula (XIII) are prepared Confirmed that.
In Production Example 3, the number of maleimide groups of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is the number of primary amino groups of 4,4′-diamino-3,3′-dimethyl-diphenylmethane. The number of aldehyde groups of terephthalaldehyde is 1.0 times the number of primary amino groups of the compound of formula (XVIII).

Production Example 4: Production of bismaleimide derivative (B-2) having polyazomethine In a reaction vessel having a volume of 5 liters capable of being heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide: 1768.0 g, bis (4- (4-aminophenoxy) phenyl) propane: 410.0 g, and propylene glycol monomethyl ether: 842.2 g And toluene: 514.5 g were mixed and refluxed at 115 to 125 ° C. for 2 hours with stirring.
When a small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran), it was derived from bis (4- (4-aminophenoxy) phenyl) propane that appeared at around 12.0 minutes. In addition, a peak different from the synthetic raw material appeared at an elution time of about 11.0 minutes, and it was confirmed that the compound of the following chemical formula (XIX) was produced.

Next, 67.0 g of terephthalaldehyde was added, and reflux dehydration reaction was performed at about 115 to 125 ° C. for 4 hours. Next, after heating to 130 ° C. and concentrating at normal pressure, cooling, adding cyclohexanone: 1318.8 g at 100 ° C., cooling to room temperature with stirring, and bismaleimide derivative (B-2) having polyazomethine Solution was obtained.
A small amount of this reaction solution was taken out, dropped into a mixed solvent of methanol and benzene (mixing mass ratio 1: 1), and reprecipitated to take out the purified solid and subjected to FT-IR measurement. around 1715 cm ^-1 due to the imide group, and Schiff base (-N = CH-) to confirmed peak around 1620 cm ^-1 due bismaleimide derivative having the polyazomethine of the following formula (XX) is prepared Confirmed that.
In Production Example 4, the number of maleimide groups of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is the number of primary amino groups of 4,4′-diamino-3,3′-dimethyl-diphenylmethane. The number of aldehyde groups of terephthalaldehyde is 1.0 times the number of primary amino groups of the compound of formula (XX).

Production Example 5 Production of Maleimide Derivative (C-1) Bis (4-maleimidophenyl) was added to a reaction vessel having a volume of 5 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Methane: 716.0 g, bis (4- (4-aminophenoxy) phenyl) propane: 410.0 g, propylene glycol monomethyl ether: 842.2 g and toluene: 514.5 g were blended, and 115-125 while stirring. Reflux at 2 ° C. for 2 hours. Next, the temperature was raised to 130 ° C. and concentrated at normal pressure, followed by cooling, adding cyclohexanone: 1318.8 g at 100 ° C., and cooling to room temperature with stirring to obtain a solution of the bismaleimide derivative (C-1). It was.
When a small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran), it was derived from bis (4- (4-aminophenoxy) phenyl) propane that appeared at around 12.0 minutes. That the peak that differs from the synthetic raw material appears at an elution time of about 11.1 minutes, and the compound of the following chemical formula (XXI) [maleimide derivative (C-1)] has been produced. confirmed.
In Production Example 5, the number of maleimide groups in bis (4-maleimidophenyl) methane is 2.0 times the number of primary amino groups in bis (4- (4-aminophenoxy) phenyl) propane. The maleimide derivative (C-1) is dissolved in an organic solvent together with terephthalaldehyde in Example 9 and Example 10, and subjected to a dehydration condensation reaction by heat treatment to be a bismaleimide derivative (A) having polyazomethine.

Production Example 6 Production of Maleimide Derivative (C-2) Bis (4-maleimidophenyl) was added to a reaction vessel having a volume of 5 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Methane: 716.0 g, 3,3′-dimethyl-4,4′-diaminobiphenyl: 106.0 g, and propylene glycol monomethyl ether: 325.6 g and toluene: 191.3 g were blended, while stirring, Reflux at 125 ° C. for 2 hours. Next, the temperature was raised to 130 ° C. and the solution was concentrated at normal pressure, then cooled, cyclohexanone: 477.7 g was added at 100 ° C., and the mixture was cooled to room temperature with stirring to obtain a solution of the maleimide derivative (C-2). .
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). As a result, 3,3′-dimethyl-4,4′-diaminobiphenyl, which appeared at an elution time of about 12.8 minutes, was obtained. The derived peak disappears, and a peak different from the synthetic raw material appears at an elution time of about 11.1 minutes, and the compound of the following chemical formula (XXII) [maleimide derivative (C-2)] has been produced. It was confirmed.
In Production Example 6, the number of maleimide groups of bis (4-maleimidophenyl) methane is 4.0 times the number of primary amino groups of 3,3′-dimethyl-4,4′-diaminobiphenyl. The maleimide derivative (C-2) is dissolved in an organic solvent together with terephthalaldehyde in Example 11 and Example 12, and subjected to a dehydration condensation reaction by heat treatment to be a bismaleimide derivative (A) having polyazomethine.

Examples 1-12, Comparative Examples 1-3
Bismaleimide derivatives A-1, A-2, B-1, B-2 having the polyazomethine obtained in Production Examples 1 to 4 as component (A) using methyl ethyl ketone as a diluent solvent, Production Example 5 And 6, maleimide derivatives C-1, C-2 and aldehyde compounds, or bismaleimide derivatives used in comparative examples, an epoxy resin (B) having at least two epoxy groups in one molecule, and a curing accelerator (C), inorganic filler (D) flame retardant (E) and flame retardant aid (F) are mixed at the blending ratio (parts by mass) shown in Tables 1 and 2 to give a resin content of 60% by mass. Uniform varnish was obtained.
Next, the varnish was impregnated and applied to an E glass cloth having a thickness of 0.2 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by mass.
Furthermore, four of these prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 230 ° C. for 120 minutes to obtain a copper-clad laminate.
Using the copper-clad laminate thus obtained, copper foil adhesion (copper foil peel strength), glass transition temperature (Tg), thermal expansion coefficient, solder heat resistance, water absorption, flame retardancy, with copper Heat resistance, dielectric properties [relative permittivity (1 GHz), dielectric loss tangent (1 GHz)], drilling workability and desmear resistance were measured and evaluated by the methods described above. The results are shown in Tables 1, 2 and 3.

In addition, the epoxy resin (B), curing accelerator (C), inorganic filler (D), flame retardant (E), flame retardant auxiliary (F) and bismaleimide in Table 1, Table 2 and Table 3 Derivatives (used in comparative examples) are as follows.
(1) Epoxy resin (B)
・ EP806 [manufactured by Japan Epoxy Resin Co., Ltd .: trade name, bisphenol F type epoxy resin],
N-770 [Dainippon Ink Chemical Co., Ltd .: trade name, phenol novolac type epoxy resin],
-HP-4032D [Dainippon Ink Chemical Co., Ltd .: trade name, bifunctional naphthalene type epoxy resin],
ESN-175 [manufactured by Toto Kasei Co., Ltd .: trade name, naphthol aralkyl type epoxy resin],
ESN-375 [manufactured by Toto Kasei Co., Ltd .: trade name, bifunctional naphthalene aralkyl type epoxy resin],
・ YX-4000 [manufactured by Japan Epoxy Resin Co., Ltd .: trade name, biphenyl type epoxy resin],
NC-3000-H [manufactured by Nippon Kayaku Co., Ltd .: trade name, biphenyl aralkyl type epoxy resin],
YX-8800 [Japan Epoxy Resin Co., Ltd., trade name, anthracene type epoxy resin],

(2) Curing accelerator (C)
・ P-200 (made by Japan Epoxy Resin Co., Ltd .: trade name, epoxy mask imidazole represented by the formula (XI))
G-8809L (Daiichi Kogyo Seiyaku Co., Ltd .: trade name, isocyanate mask imidazole represented by the formula (XII))
(3) Inorganic filler (D)
・ Fused silica (manufactured by Admatechs: trade name SO-25R)
(4) Flame retardant (E)
AlOOH: Boehmite type aluminum hydroxide (manufactured by Kawai Lime Co., Ltd .: trade name BMT-3L, thermal decomposition temperature: 400 ° C.)
Mg (OH) ₂ : Magnesium hydroxide (Kanto Chemical Co., Inc., thermal decomposition temperature: 350 ° C.)
(5) Flame retardant aid (F)
KG1100: Zinc molybdate-treated talc (manufactured by Sherwin Williams)
(6) Bismaleimide derivative / BMI (manufactured by Keisei Kasei Co., Ltd .: trade name, bis (4-maleimidophenyl) methane, maleimide equivalent 179)
BMI-80 (manufactured by Keisei Kasei Co., Ltd .: trade name, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, maleimide equivalent 285)

In addition, about Example 9 and Example 11, the FT-IR measurement of the prepreg was performed. The results are shown in FIGS.
In addition, the number of aldehyde groups of terephthalaldehyde in Example 9 and Example 10 is 2.0 times the number of primary amino groups of maleimide derivative (C-1).
Moreover, the number of aldehyde groups of terephthalaldehyde in Example 11 and Example 12 is 1.0 times the number of primary amino groups of the bismaleimide derivative (C-2).
3 and 4, around 1715 cm ^-1 due to the imide group of the bismaleimide, and confirmed peak around 1620 cm ^-1 due to Schiff base (-N = CH-), bismaleimide derivative having polyazomethine Is confirmed to be manufactured.

As is apparent from Tables 1 and 2, in the examples of the present invention containing the bismaleimide derivative (A) having polyazomethine and the epoxy resin (B) having at least two epoxy groups in one molecule, Adhesion of copper foil (copper foil peel strength), high glass transition temperature, low thermal expansion, solder heat resistance, low water absorption, heat resistance with copper, flame resistance, low dielectric properties, drill workability, desmear resistance Pre-pregs and laminates excellent in balance are obtained for all.
On the other hand, as apparent from Table 3, bismaleimide derivatives (A) having polyazomethine and other bismaleimides without containing an epoxy resin (B) having at least two epoxy groups in one molecule In Comparative Examples 1 to 3 using a derivative, copper foil adhesion, high glass transition temperature, low thermal expansion, solder heat resistance, low water absorption, heat resistance with copper, flame resistance, low dielectric properties, drill workability, Only prepregs and laminates that are inferior to the examples in all properties of desmear resistance are obtained.

  According to the present invention, by using a resin composition containing a bismaleimide derivative (A) having polyazomethine and an epoxy resin (B) having at least two epoxy groups in one molecule, copper foil adhesion, high glass Excellent balance in transition temperature, low thermal expansion, solder heat resistance, low water absorption, heat resistance with copper, flame resistance, low dielectric properties, drilling workability, desmear resistance, low toxicity and safety and work A thermosetting resin composition excellent in environment and suitable for electronic parts and the like can be obtained, and it becomes possible to provide a prepreg and a laminate using the composition, and it is advantageously used for electronic devices as a multilayer printed wiring board. .

Claims (9)

A thermosetting resin comprising a bismaleimide derivative (A) having polyazomethine represented by the following general formula (I) and an epoxy resin (B) having at least two epoxy groups in one molecule Resin composition.

(In the formula, Ar ₁ is independently a residue represented by general formula (I-1), (I-2), (I-3) or (I-4), and Ar ₂ is represented by the following general formula ( I-5) or a residue represented by (I-6), and a plurality of Ar ₂ may be the same or different. N is 0 to 10.)

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

(In the formula, R ₂ and R ₃ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, 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 an alkylene group of 1 to 5, an alkylidene group, an ether group, or a sulfonyl group.)

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

(Wherein R ₆ and R ₇ each independently represent 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, A ₂ is a residue represented by a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group, an ether group, a sulfonyl group, a ketone group, a fluorene group, or a phenylenedioxy group.

(In the formula, A ₃ is a single bond, an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, or a sulfonyl group.) The epoxy resin (B) is bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolak type epoxy resin, cresol The thermosetting resin composition of Claim 1 which is 1 or more types chosen from a novolak-type epoxy resin . The usage-amount of the said bismaleimide derivative (A) is 20-90 mass parts per 100 mass parts in total of the said bismaleimide derivative (A) and said epoxy resin (B) of solid content conversion. The thermosetting resin composition described in 1 . Furthermore, the thermosetting resin composition in any one of Claims 1-3 containing a hardening accelerator (C). Furthermore, the thermosetting resin composition in any one of Claims 1-4 containing an inorganic filler (D). Furthermore, the thermosetting resin composition in any one of Claims 1-5 containing a flame retardant (E). Furthermore, the thermosetting resin composition in any one of Claims 1-6 containing a flame retardant adjuvant (F). Prepreg wherein the thermosetting resin composition according to any one of claims 1 to 7 is free immersion or coating in the sheet-shaped reinforcing substrate. A laminated board, wherein the insulating resin layer is formed using the thermosetting resin composition according to any one of claims 1 to 7 or the prepreg according to claim 8 .

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