JP5589470B2 - Bismaleimide derivative and method for producing the same, thermosetting resin composition, prepreg and laminate - Google Patents

Description

  The present invention relates to a bismaleimide derivative and a method for producing the same, and a thermosetting resin composition, a prepreg, and a laminate, and in particular, has copper foil adhesion, low thermal expansion, high glass transition temperature, and low dielectric constant. Heat resistance, solder heat resistance, heat resistance with copper, flame retardancy, drilling workability, low toxicity and excellent safety and work environment, thermosetting resin composition suitable for electronic parts, prepreg and lamination The present invention relates to a plate, a bismaleimide derivative used in the resin composition, and a method for producing the same.

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.

Cyanate compound is a thermosetting resin with excellent dielectric properties and flame retardancy, but when this cyanate compound is used as it is in an epoxy curable thermosetting resin, heat resistance and toughness are insufficient. There is a problem of low thermal expansion that is compatible with next-generation insulating materials.
Examples of the resin exhibiting low thermal expansion include a resin composition containing a cyanate compound and an inorganic filler (see, for example, Patent Document 1), and a resin composition containing a cyanate compound, an inorganic filler, and an epoxy resin (eg, a patent). Reference 2), a resin composition containing a cyanate compound, an inorganic filler, an epoxy resin, and a phenol resin (see, for example, Patent Document 3), a thermosetting resin containing cyanate resin and an aralkyl-modified epoxy resin as essential components ( For example, see Patent Documents 4 and 5).

However, the resin composition described in Patent Documents 1 to 3 described above has a large amount of the inorganic filler used for expressing low thermal expansibility as 30 to 80% by mass of the entire resin composition, and is a copper-clad laminate. When used as an interlayer insulating material, drill workability and formability may be insufficient.
In addition, the thermosetting resins described in Patent Documents 4 and 5 are resins in which the cyanate resin, which is an essential component, is inferior in toughness and curing reactivity, and the curing reactivity and toughness of this thermosetting resin are still insufficient. Even when these are used as a copper clad laminate or an interlayer insulating material, heat resistance, reliability, workability, etc. may be insufficient.

As described above, the laminated plate material is required to have high copper foil adhesiveness, high glass transition temperature, good low thermal expansion, and the like due to the recent demand for higher density and higher reliability.
For example, as the copper foil adhesiveness for forming fine wiring, it is desired that the peel strength of the copper foil is 1.0 kN / m or more, particularly 1.2 kN / m or more.
Moreover, the base material is in the direction of being made thinner as the density is increased, and the warpage of the base material during heat treatment is required 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.
Furthermore, it is necessary to increase the number of layers by using a build-up material or the like for high density, and high reflow heat resistance is required. However, heat resistance with copper (T- 300) is desired that no blistering occurs for 30 minutes or more.

Further, as the density is increased, 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.
Furthermore, 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 2002-285015 A JP 2003-73543 A JP 2003-268136 A JP 2002-309085 A JP 2002-348469 A

  In view of the current situation, the object of the present invention is, in particular, copper foil adhesion, low thermal expansion, high glass transition temperature, low dielectric properties, solder heat resistance, heat resistance with copper, flame resistance, drilling workability It is an object of the present invention to provide a thermosetting resin composition that is also excellent, and a prepreg and laminate using the same.

As a result of earnest research to solve the above-mentioned problems, the present invention has resulted in excellent heat resistance, drilling workability, etc. obtained from a thermosetting resin composition containing a bismaleimide derivative having a specific structure. The inventors have found that the object can be achieved and have completed the present invention. The present invention has been completed based on such findings.
That is, the present invention provides the following bismaleimide derivatives and production methods thereof, as well as thermosetting resin compositions, prepregs, and laminates.

1. A bismaleimide derivative represented by the following general formula (I).

(In the formula, Ar ₁ is a residue represented by general formula (I-1), (I-2), (I-3) or (I-4), and Ar ₂ is represented by general formula (I-5) ) Or (I-6), R ₁ represents a hydroxyl group, carboxy group or sulfonic acid group which is an acidic substituent, R ₂ represents a hydrogen atom, an aliphatic hydrocarbon having 1 to 5 carbon atoms A group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5, and n is 0 or a positive number.)

（式中、Ｒ₃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）

(Wherein R ₃ 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、Ｒ₄及びＲ₅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 ₄ and R ₅ 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.)

（式中、ｒは１〜１０の整数である。）

(In the formula, r 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。）

（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。）

(Wherein, the aliphatic hydrocarbon group R ₆ and R ₇ are 1 to 5 carbon atoms each independently represents a methoxy group or a halogen atom, s, t are each independently an integer from 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.)

2. The 1-bismaleimide derivative represented by the following formula (II):

3. Compound (a) having at least two primary amino groups in one molecule represented by general formula (III), Compound having at least two aldehyde groups in one molecule represented by general formula (IV) By subjecting the amine compound (c) having an acidic substituent represented by (b) and the general formula (V) to a dehydration condensation reaction in an organic solvent, a primary amino group is formed at the terminal represented by the general formula (VI). The compound (A) having the formula (VII) and the maleimide compound (d) having at least two N-substituted maleimide groups in one molecule represented by the general formula (VII) and the organic solvent The bismaleimide derivative (B) represented by the general formula (I) is produced by a Michael addition reaction in the process, wherein the bismaleimide derivative according to 1 or 2 is produced.

（式中、Ａr₂は一般式（Ｉ）と同様である。）

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

（式中、Ｒ₁及びＲ₂、ｘ及びｙは一般式（Ｉ）と同様である。）

(In the formula, R ₁ and R ₂ , x and y are the same as those in the general formula (I).)

（式中、Ａr₂、及びＲ₁、Ｒ₂、及びｘ、ｙ、及びｎは一般式（Ｉ）と同様である。）

(In the formula, Ar ₂ , R ₁ , R ₂ , x, y, and n are the same as in general formula (I).)

（式中、Ａr₁は一般式（Ｉ）と同様である。）

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

4). A thermosetting resin composition comprising the bismaleimide derivative 1 or 2 above.
5. The thermosetting resin composition according to claim 4, comprising the bismaleimide derivative 1 or 2 and an epoxy resin.
6). A prepreg obtained by impregnating and coating a fiber sheet-like reinforcing base material with the thermosetting resin composition of 4 or 5 above and forming a B-stage.
7). A laminate obtained by laminate molding using the prepreg described in 6 above.

  The thermosetting resin composition containing the bismaleimide derivative of the present invention particularly has copper foil adhesion, low thermal expansion, and high glass transition temperature, and also has low dielectric properties, solder heat resistance, heat resistance with copper, difficulty. Excellent in flammability and drillability, and is low in toxicity and excellent in safety and working environment. Therefore, the laminated board obtained by carrying out lamination molding using the prepreg which consists of this thermosetting resin composition can be used conveniently for an electronic component etc. as a multilayer printed wiring board.

3 is an FT-IR measurement chart of a compound (A-1) having a primary amino group at the terminal obtained in Production Example 1. 2 is an FT-IR measurement chart of a bismaleimide derivative (B-1) obtained in Production Example 1.

First, the bismaleimide derivative of the present invention will be described. The bismaleimide derivative of the present invention is a compound represented by the following general formula (I).

(In the formula, Ar ₁ is a residue represented by general formula (I-1), (I-2), (I-3) or (I-4), and Ar ₂ is represented by general formula (I-5) ) Or (I-6), R ₁ represents a hydroxyl group, carboxy group or sulfonic acid group which is an acidic substituent, R ₂ represents a hydrogen atom, an aliphatic hydrocarbon having 1 to 5 carbon atoms A group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5, and n is 0 or a positive number.)

（式中、Ｒ₃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）

(Wherein R ₃ 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、Ｒ₄及びＲ₅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 ₄ and R ₅ 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.)

（式中、ｒは１〜１０の整数である。）

(In the formula, r 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。）

（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。）

(Wherein, the aliphatic hydrocarbon group R ₆ and R ₇ are 1 to 5 carbon atoms each independently represents a methoxy group or a halogen atom, s, t are each independently an integer from 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.)

As the bismaleimide derivative of the present invention, a bismaleimide derivative represented by the following formula (II) can be exemplified.

  Next, the manufacturing method of the bismaleimide derivative of this invention is demonstrated. The bismaleimide derivative (B) of the present invention includes a compound (a) having at least two primary amino groups in one molecule represented by the general formula (III), and one molecule represented by the general formula (IV) A compound (b) having at least two aldehyde groups therein and an amine compound (c) having an acidic substituent represented by the general formula (V) are subjected to a dehydration condensation reaction in an organic solvent to thereby give a general formula (VI The compound (A) having a primary amino group at the terminal represented by the formula (A), and then the compound (A) and at least two N-substituted maleimides in one molecule represented by the general formula (VII) The maleimide compound (d) having a group can be produced by a Michael addition reaction in an organic solvent.

（式中、Ａr₂は一般式（Ｉ）と同様である。）

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

（式中、Ｒ₁及びＲ₂、ｘ及びｙは一般式（Ｉ）と同様である。）

(In the formula, R ₁ and R ₂ , x and y are the same as those in the general formula (I).)

（式中、Ａr₂、及びＲ₁、Ｒ₂、及びｘ、ｙ、及びｎは一般式（Ｉ）と同様である。）

(In the formula, Ar ₂ , R ₁ , R ₂ , x, y, and n are the same as in general formula (I).)

（式中、Ａr₁は一般式（Ｉ）と同様である。）

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

  Examples of the compound (a) having at least two primary amino groups in one molecule represented by the above general formula (III) include 4,4′-diaminodiphenylmethane, 4,4′-diamino-3, 3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4 , 4′-diaminodiphenyl ketone, benzidine, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, -Bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino) Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- ( And aromatic amines such as 3-aminophenoxy) phenyl) sulfone and 9,9-bis (4-aminophenyl) fluorene.

  As the compound (a) having at least two primary amino groups in one molecule, among these, 4,4′-diaminodiphenylmethane, which has a high reaction rate at the time of synthesis and can achieve higher heat resistance, '-Diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4- Aminophenoxy) phenyl) sulfone and the like are more preferable and 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4′-diamino-3,3′-diethyl-diphenylmethane is particularly preferred.

  Examples of the compound (b) having at least two aldehyde groups in one molecule represented by the general formula (IV) 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.

Examples of the amine compound (c) having an acidic substituent represented by the general formula (V) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, and m-aminobenzoic acid. O-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like.
Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable in terms of solubility and synthesis yield, and have high heat resistance, low thermal expansion, and high glass. P-aminophenol and p-aminobenzoic acid are particularly preferred because they have a transition temperature (Tg) and are inexpensive.

In this reaction, a compound (a) having at least two primary amino groups in one molecule, a compound (b) having at least two aldehyde groups in one molecule, and an amine compound (c) having an acidic substituent Is used as follows: The number of primary amino groups in compound (a) [namely, the mass of compound (a) used / the amount of primary amino group equivalents in compound (a)] and the number of primary amino groups in compound (c) [ie compound (c) Used mass / primary amino group equivalent of compound (c)] exceeds the number of aldehyde groups of compound (b) [that is, used mass of compound (b) / aldehyde group equivalent of compound (b)] It is desirable to do. Moreover, it is desirable to use it so that the number of primary amino groups of compound (a) may exceed the number of primary amino groups of compound (c).
If the total number of primary amino groups in compound (a) and the number of primary amino groups in compound (c) is less than or equal to the number of aldehyde groups in compound (b), gelation or insolubilization may occur during synthesis, or bismaleimide obtained therefrom The heat resistance of the derivative may decrease. Moreover, the heat resistance of the bismaleimide derivative obtained from this may fall that the number of primary amino groups of a compound (a) is below the number of primary amino groups of a compound (c).

The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, γ-butyrolactone, etc. These ester solvents can be used, and one kind or a mixture of two or more kinds can be used. 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 a residual solvent at the time of producing a prepreg, are more preferable.
Moreover, since this 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, per 100 parts by mass of the total of compound (a), compound (b), and compound (c). 40 to 500 parts by mass is particularly preferable. 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 reaction takes a long time and the production cost increases.

  In this reaction, a reaction catalyst can be optionally used as necessary. Examples of reaction catalysts include, but are not limited to, acidic catalysts such as p-toluenesulfonic acid, amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus systems such as triphenylphosphine. A catalyst etc. are mentioned, 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-mentioned synthesis raw material, organic solvent, and if necessary, a reaction catalyst is charged into a synthesis kettle, and if necessary, stirred for 0.1 to 10 hours while being heated and kept warm, and subjected to a dehydration condensation reaction. A compound (A) having a primary amino group at the terminal is produced.
The reaction temperature is preferably 25 to 200 ° C. When the reaction temperature is less than 25 ° C, the reaction rate is slow, and when the reaction temperature exceeds 200 ° C, gelation is likely to occur.
It is desirable to use dimethylformamide, dimethylacetamide, etc., which have excellent solubility, and an aromatic solvent such as toluene, xylene, etc. to remove the by-product water by azeotropy, and the reaction temperature is azeotropic. A certain range of 120 ° C. to 200 ° C. is particularly preferable.

The obtained compound (A) having a primary amino group at the terminal represented by the general formula (VI) can be confirmed by taking a small amount of sample and performing GPC measurement and IR measurement. The peaks of compound (a), compound (b), and compound (c), which are synthetic raw materials, disappear by GPC measurement, and the aldehyde group of compound (b), which has an aldehyde group, which is a synthetic raw material, by IR measurement due to 1700 cm ^-1, and 2750 cm ^-1, a peak of 2800 cm ^-1 disappeared, by a peak of 1620 cm ^-1 due to Schiff base (-N = CH-) to verify that the appearance, good It can be confirmed that the synthesis reaction proceeds and the desired compound (A) is produced.

  The bismaleimide derivative (B) of the present invention represented by the general formula (I) is prepared as described above, the compound (A) having a primary amino group at the terminal represented by the general formula (VI), and the above The maleimide compound (d) having at least two N-substituted maleimide groups in one molecule represented by the general formula (VII) is stirred for 0.1 to 10 hours in an organic solvent while heating and holding as necessary. Produced by Michael addition reaction.

Examples of the maleimide compound (d) having at least two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide represented by the following general formula (VII ′), Bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, Examples include m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, and the like.
Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-, which has a high reaction rate and can have higher heat resistance. Diphenylmethane bismaleimide and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferable, and 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane is preferable from the viewpoint of solubility in a solvent. Bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred because it is inexpensive.

（式中、ｒは１〜１０の整数である。）

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

  In this reaction, the amount of the maleimide compound (d) and the compound (A) having a primary amino group at the terminal is the number of maleimide groups in the compound (d) (that is, the amount of compound (d) used / compound (d). 2-10 times the number of primary amino groups of the compound (A) having a primary amino group at the terminal (that is, the amount of the compound (A) used / the primary amino group equivalent of the compound (A)). It is desirable that If it exceeds 10 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 times, gelation may occur or the heat resistance of the thermosetting resin may decrease. There is a case. The amount of the organic solvent used is preferably 25 to 2000 parts by mass per 100 parts by mass of the total of the compound (d) and the compound (A) having a primary amino group at the terminal (solid content). It is more preferable to set it as 1000 mass parts, and it is especially preferable to set it as 40-500 mass parts. If the blending amount of the organic solvent is less than 25 parts by mass, the solubility is insufficient, and if it is more than 2000 parts by mass, the reaction takes a long time and the production cost increases.

  The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, γ-butyrolactone, etc. These ester solvents can be used, and one kind or a mixture of two or more kinds can be used. 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 a residual solvent at the time of producing a prepreg, are more preferable. An organic solvent is also used in producing the compound (A) having a primary amino group at the terminal, and this organic solvent is used continuously in producing the bismaleimide derivative (B). This is particularly preferable from the viewpoint of manufacturing cost.

In this reaction, a reaction catalyst can be optionally used as necessary. The reaction catalyst is not particularly limited, and examples 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, or 2 or more types can be mixed and used.
As the reaction method, the maleimide compound (d), the compound having a primary amino group at the terminal (A), an organic solvent, and if necessary, a reaction catalyst is charged into a synthesis kettle, and if necessary, heated for 0.1 to 10 hours while maintaining the temperature. The bismaleimide derivative (B) is produced by stirring and Michael addition reaction.
The reaction temperature is preferably 25 ° C to 200 ° C, particularly preferably 100 ° C to 160 ° C. If the reaction temperature is less than 25 ° C, the reaction rate is slow, and if it exceeds 200 ° C, gelation tends to occur.
The obtained bismaleimide derivative (B) can be confirmed by taking out a small amount of sample and performing IR measurement of the sample purified by reprecipitation. The disappearance of the peak of the primary amino group of 3400 cm ⁻¹ due to the Michael addition reaction, the appearance of the Schiff base (—N═CH—) peak of 1620 cm ⁻¹ , and the bismaleimide derivative 1710 to 1720 cm ⁻¹ ketone peak. By confirming, it can be confirmed that the synthesis reaction proceeds well and the desired compound is produced.

  The thermosetting resin composition of the present invention is characterized in that it contains a bismaleimide derivative, and if necessary, together with a bismaleimide derivative, an epoxy resin, a curing accelerator, a flame retardant such as a metal hydrate, and inorganic filling An agent or the like may be contained, and various properties can be further improved by containing them. For example, by including an epoxy resin in the thermosetting resin composition of the present invention, it is possible to impart good moldability with less generation of voids, heat resistance, flame resistance, and copper foil adhesion. Etc. can be improved.

In the case of containing an epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable from the viewpoint of heat resistance. For example, bisphenol A, bisphenol F, biphenyl, Examples include novolak, polyfunctional phenol, naphthalene, alicyclic, and alcoholic glycidyl ethers, glycidylamine, and glycidyl ester epoxy resins. Can do.
Among these, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion Resin, phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable, and bisphenol F type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin from the viewpoint of flame retardancy and molding processability, A cresol novolac type epoxy resin is more preferable, and a biphenylaralkyl type epoxy resin represented by the following general formula (VIII) is particularly preferable from the viewpoint of good drilling workability and high flame retardancy. In the general formula (VIII), m is a positive number of 1 or more.

When an epoxy resin is contained, the amount used (in terms of solid content) is preferably 10 to 200 parts by mass and more preferably 20 to 200 parts by mass per 100 parts by mass of the bismaleimide derivative in terms of solid content. It is particularly preferably 20 to 100 parts by weight.
When the blending amount of the epoxy resin is less than 10 parts by mass, the copper foil adhesion and chemical resistance may be insufficient, and when it exceeds 200 parts by mass, the heat resistance, the low thermal expansion property, and the high elastic modulus are deteriorated. Sometimes.

  Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts. Among them, imidazoles and derivatives thereof are preferable from the viewpoint of high elastic modulus and flame retardancy, copper foil adhesion, and the like, and further, a compound in which an imidazole group represented by the following general formula (IX) is substituted with an epoxy resin, A compound substituted with an isocyanate resin represented by the following general formula (X) is more preferable because it is excellent in curing moldability at a relatively low temperature at 200 ° C. or lower and the aging stability of a varnish or prepreg, and the following general formula ( The compound represented by XI) or (XII) may be used in a small amount and is particularly preferable because it is commercially inexpensive.

（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、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 represent 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. , 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。）

(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 D represents an alkylene group or an aromatic hydrocarbon group. It is a residue of an isocyanate resin such as

  When a curing accelerator is contained, the amount used is preferably 0.1 to 10 parts by mass per 100 parts by mass of the sum of the bismaleimide derivative of the present invention and the epoxy resin in terms of solid content. More preferably 5 parts by mass. If the amount of curing accelerator used is less than 0.1 parts by mass, heat resistance, flame retardancy, copper foil adhesion, etc. may be insufficient, and if it exceeds 10 parts by mass, heat resistance and stability over time will decrease. There are things to do.

The thermosetting resin composition of the present invention may contain a flame retardant for the purpose of improving flame retardancy. By containing an appropriate flame retardant, it is possible to impart high flame retardancy with little deterioration of various properties such as heat resistance, copper foil adhesiveness, high elastic modulus, and low thermal expansion coefficient.
Examples of flame retardants include metal hydrates such as aluminum hydroxide and magnesium hydroxide, phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate compounds, phosphazenes, and red phosphorus. Examples include inorganic flame retardant aids such as a flame retardant, antimony trioxide, and zinc molybdate. Halogen-containing flame retardants containing bromine or chlorine as flame retardants 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 highly adaptable and can be used preferably.
Furthermore, among these metal hydrates, a compound in which boehmite type aluminum hydroxide (AlOOH) and gibbsite type aluminum hydroxide [Al (OH) 3] are adjusted to a thermal decomposition temperature of 300 ° C. or higher by heat treatment, thermal decomposition Metal hydrates such as magnesium hydroxide having a temperature of 300 ° C. or higher have excellent heat resistance and are therefore more preferably used.
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 used especially suitably.

  When the flame retardant is contained, when the flame retardant is a metal hydrate, the amount used is 10 to 300 parts by mass per 100 parts by mass of the total of the bismaleimide derivative of the present invention and the epoxy resin in terms of solid content. It is preferable to use 10 to 250 parts by mass, and 50 to 200 parts by mass is particularly preferable. 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 is a phosphorus flame retardant, the phosphorus atom content is 0.1 to 10.0 parts by mass per 100 parts by mass of the total of the bismaleimide derivative of the present invention and the epoxy resin 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, It is especially preferable to mix | blend so that it may become 1.0-8.0 mass part. If the amount is less than 0.1 parts by mass, the flame retardancy may be insufficient. If the amount exceeds 10.0 parts by mass, chemical resistance such as plating solution resistance, heat resistance, and copper foil adhesion may be deteriorated. .

  When using an inorganic flame retardant auxiliary such as antimony trioxide, zinc molybdate as a flame retardant auxiliary, the amount used is per 100 parts by mass of the total of the bismaleimide derivative of the present invention and epoxy resin in terms of solid content, It is preferable to set it as 0.1-20 mass parts, and it is more preferable to set it as 0.1-10 mass parts. If it 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 an appropriate inorganic filler for the purpose of improving low thermal expansion property, high elastic modulus property, heat resistance, and flame retardancy.
Examples of inorganic fillers include silica, alumina, mica, talc, short glass fiber or fine powder and hollow glass, calcium carbonate, quartz powder, etc. Among these, 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.

  When the inorganic filler is included, the amount used is preferably 10 to 300 parts by mass per 100 parts by mass of the total of the bismaleimide derivative of the present invention and the epoxy resin in terms of solid content, and 20 to 200 parts by mass. It is more preferable to set it to 30 to 200 parts by mass. If the content of the inorganic filler exceeds 300 parts by weight, chemical resistance such as plating solution resistance and moldability may be deteriorated.

In the thermosetting resin composition of the present invention, a known thermoplastic resin, elastomer, organic filler and the like can be used in combination as long as the object of the present invention is not adversely affected.
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 organic fillers 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. For example, ultraviolet absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, thioxanthones, fluorescent whitening agents such as stilbene derivatives, Examples include urea compounds such as urea silane and adhesion improvers such as silane coupling agents.

The prepreg of the present invention is obtained by impregnating and applying the thermosetting resin composition of the present invention to a fiber 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 fiber sheet-like reinforcing base material and semi-curing (B-stage) by heating or the like.
As the prepreg fiber sheet reinforcing substrate, known materials used for various laminates for electrical insulating materials can be used. 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 fiber sheet-shaped reinforcing substrate 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 Those subjected to are suitable from the viewpoints 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 above-described 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 2 to 100 kg / cm ^2, can be molded in the range of the heating time from 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) Linear thermal expansion coefficient A 5-mm square evaluation board | substrate which removed the copper foil by immersing a copper clad laminated board in a copper etching liquid was produced, and the evaluation board | substrate of the evaluation board | substrate was used using the TMA test apparatus (the Du Pont company make, TMA2940). The linear thermal expansion coefficient of 30 to 100 ° C. in the thickness direction (Z direction) was measured.

(3) 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.

(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 2 atm, 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) 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). (If there is a blister when the temperature rises, mark it as “blister”.)

(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) 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 tangent were measured.

(8) 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.

Production Example 1: Production of Compound (A-1) and Bismaleimide Derivative (B-1) Solution Having Primary Amino Group at Terminal
In a 3 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser, a terephthalaldehyde: 134.0 g, p-aminophenol: 109.0 g, N, N-dimethyl Acetamide: 1157.0 g and toluene: 115.7 g were added, and kept at 80 ° C. for 1 hour with stirring. Next, 198.0 g of diaminodiphenylmethane was added, the temperature was raised and reflux dehydration reaction was performed at about 130 to 145 ° C., the temperature was raised to 160 ° C. and concentrated at normal pressure, and then cooled to 120 ° C. A solution of the compound (A-1) having a secondary 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 whose elution time appears around 13.7 minutes, and around 12.8 minutes The peaks derived from p-aminophenol and diaminodiphenylmethane appearing in 1 disappeared.
Further, a small amount of the reaction solution was taken out, dropped into a mixed solvent of methanol and benzene (mixing weight ratio 1: 1) and reprecipitated to take out the purified solid content, and FT-IR measurement was performed. The measurement results are shown in FIG.
From the measurement result, the vicinity of 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 confirmed, 1620 cm due to Schiff base (-N = CH-) A strong peak in the vicinity of ^-1 was confirmed, confirming that the compound of the following chemical formula (XIII) was produced.

Next, 716.0 g of bis (4-maleimidophenyl) methane: 716.0 g is added to the above reaction solution, kept at 120 ° C. for 6 hours with stirring, and then cooled to obtain a solution of the bismaleimide derivative (B-1). Obtained. A small amount of this reaction solution was taken out and dropped into a mixed solvent of methanol and benzene (mixing weight 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.
From the measurement result, the disappearance of the peak of the primary amino groups of 3400 cm ^-1 by Michael addition reaction, the peak of 1620 cm ^-1 of the Schiff base (-N = CH-), and ketones 1710～1720Cm ^-1 bismaleimide derivative It was confirmed that the bismaleimide derivative of the following chemical formula (II) was produced by confirming the appearance of the peak.
In Production Example 1, the total number of primary amino groups of diaminodiphenylmethane and p-aminophenol is 3.0, and the number of aldehyde groups of terephthalaldehyde is 2.0. The number of maleimide groups in bis (4-maleimidophenyl) methane is 4.0 times the number of primary amino groups in compound (A-1).

Production Example 2: [Production of Compound (A-2) and Bismaleimide Derivative (B-2) Solution Having Primary Amino Group at Terminal]
In a reaction vessel with 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, 134.0 g of terephthalaldehyde, 137.0 g of p-aminobenzoic acid, and N. N-dimethylacetamide: 1637.0 g and toluene: 363.8 g were blended and kept warm at 80 ° C. for 1 hour with stirring.
To this was added 4,4′-diamino-3,3′-dimethyl-diphenylmethane: 226.0 g, and the mixture was heated to reflux dehydration reaction at about 130 to 145 ° C. Subsequently, after heating up to 160 degreeC and concentrating at normal pressure, it cooled to 120 degreeC and the solution of the compound (A-2) which has a primary amino group at the terminal was obtained.
Next, 1140.0 g of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane: 1140.0 g was added to the solution, and the mixture was kept at 120 ° C. for 6 hours with stirring, then cooled to bismaleimide derivative ( A solution of B-2) was obtained.
In Production Example 2, the total number of primary amino groups of 4,4′-diamino-3,3′-dimethyl-diphenylmethane and p-aminobenzoic acid is 3.0, and the number of aldehyde groups of terephthalaldehyde is 2.0. It is. The number of maleimide groups in 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane is 4.0 times the number of primary amino groups in compound (A-2).

Production Example 3: Production of Compound (A-3) and Bismaleimide Derivative (B-3) Solution Having Primary Amino Group at Terminal
In a reaction vessel with a volume of 5 liters that can be heated and cooled, equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser, isophthalaldehyde: 268.0 g, m-aminophenol: 109.0 g, and N, N -Dimethylacetamide: 1769.0 g and toluene: 393.1 g were blended and kept warm at 80 ° C for 1 hour with stirring.
To this, 4,8.0'-diamino-3,3'-diethyl-diphenylmethane: 508.0 g was added, and the mixture was heated to reflux dehydration reaction at about 130 to 145 ° C. Subsequently, after heating up to 160 degreeC and concentrating at normal pressure, it cooled to 120 degreeC and the solution of the compound (A-3) which has a primary amino group at the terminal was obtained.
Next, 884.0 g of 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide: 884.0 g was added to the solution, and the mixture was kept at 120 ° C. for 6 hours with stirring, and then cooled to bismaleimide. A solution of the derivative (B-3) was obtained.
In Production Example 3, the total number of primary amino groups of 4,4′-diamino-3,3′-diethyl-diphenylmethane and m-aminophenol is 5.0, and the number of aldehyde groups of terephthalaldehyde is 4.0. is there. The number of maleimide groups in 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide is 4.0 times the number of primary amino groups in compound (A-3).

Production Example 4: [Production of Compound (A-4) and Bismaleimide Derivative (B-4) Solution Having Primary Amino Group at Terminal]
In a reaction vessel with a volume of 3 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 134.0 g of terephthalaldehyde, 109.0 g of p-aminophenol, and N, N -Dimethylacetamide: 1189.0 g and toluene: 264.2 g were blended and kept at 80 ° C. for 1 hour with stirring.
To this was added 410.0 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane: the temperature was raised and a reflux dehydration reaction was carried out at about 130-145 ° C. Subsequently, after heating up to 160 degreeC and concentrating at normal pressure, it cooled to 120 degreeC and the solution of the compound (A-4) which has a primary amino group at the terminal was obtained.
Next, 536.0 g of m-phenylene bismaleimide was added, and the mixture was kept at 120 ° C. for 6 hours with stirring, and then cooled to obtain a solution of a bismaleimide derivative (B-4).
In Production Example 4, the total number of primary amino groups of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and p-aminophenol is 3.0, and the number of aldehyde groups of terephthalaldehyde is 2. 0. The number of maleimide groups in m-phenylene bismaleimide is 4.0 times the number of primary amino groups in compound (A-4).

Production Example 5: [Production of Compound (A-5) and Bismaleimide Derivative (B-5) Solution Having Primary Amino Group at Terminal]
In a reaction vessel with a volume of 3 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 134.0 g of terephthalaldehyde, 109.0 g of p-aminophenol, and N, N -Dimethylacetamide: 882.0g and toluene: 196.0g were mix | blended and it heat-retained at 80 degreeC for 1 hour, stirring.
To this was added 3,3′-dihydroxybenzidine: 216.0 g, and the temperature was raised to perform a reflux dehydration reaction at about 130 to 145 ° C. Subsequently, after heating up to 160 degreeC and concentrating at normal pressure, it cooled to 120 degreeC and the solution of the compound (A-5) which has a primary amino group at the terminal was obtained.
Next, 423.0 g of 4-methyl-1,3-phenylenebismaleimide was added, and the mixture was kept at 120 ° C. for 6 hours while stirring, and then cooled to obtain a solution of a bismaleimide derivative (B-5). .
In Production Example 5, the total number of primary amino groups of 3,3′-dihydroxybenzidine and p-aminophenol is 3.0, and the number of aldehyde groups of terephthalaldehyde is 2.0. The number of maleimide groups in 4-methyl-1,3-phenylenebismaleimide is 3.0 times the number of primary amino groups in compound (A-5).

Production Example 6 [Production of Compound (A-6) and Bismaleimide Derivative (B-6) Solution Having Primary Amino Group at Terminal]
In a reaction vessel with a volume of 3 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 134.0 g of terephthalaldehyde, 109.0 g of p-aminophenol, and N, N -Dimethylacetamide: 1215.0g and toluene: 270.0g were mix | blended, and it heat-retained at 80 degreeC for 1 hour, stirring.
Bis [4- (4-aminophenoxy) phenyl] sulfone: 432.0 g was added thereto, the temperature was raised, and a reflux dehydration reaction was performed at about 130 to 145 ° C. Subsequently, after heating up to 160 degreeC and concentrating at normal pressure, it cooled to 120 degreeC and the solution of the compound (A-6) which has a primary amino group at the terminal was obtained.
Next, 540.0 g of bis (4-maleimidophenyl) ether was added, and the mixture was kept at 120 ° C. for 6 hours with stirring, and then cooled to obtain a solution of a bismaleimide derivative (B-6).
In Production Example 6, the total number of primary amino groups of bis [4- (4-aminophenoxy) phenyl] sulfone and p-aminophenol is 3.0, and the number of aldehyde groups of terephthalaldehyde is 2.0. The number of maleimide groups in bis (4-maleimidophenyl) ether is 3.0 times the number of primary amino groups in compound (A-6).

Production Example 7: [Production of Compound (A-7) and Bismaleimide Derivative (B-7) Solution Having Primary Amino Group at Terminal]
In a reaction vessel with a volume of 3 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 134.0 g of terephthalaldehyde, 109.0 g of p-aminophenol, and N, N -Dimethylacetamide: 987.0g and toluene: 219.3g were mix | blended, and it heat-retained at 80 degreeC for 1 hour, stirring.
To this was added 368.0 g of 4,4′-bis (4-aminophenoxy) biphenyl, and the mixture was heated to reflux dehydration reaction at about 130 to 145 ° C. Subsequently, after heating up to 160 degreeC and concentrating at normal pressure, it cooled to 120 degreeC and the solution of the compound (A-7) which has a primary amino group at the terminal was obtained.
Next, 376.0 g of bis (4-maleimidophenyl) sulfone was added, and the mixture was kept at 120 ° C. for 6 hours with stirring, and then cooled to obtain a solution of a bismaleimide derivative (B-7).
In Production Example 7, the total number of primary amino groups of 4,4′-bis (4-aminophenoxy) biphenyl and p-aminophenol is 3.0, and the number of aldehyde groups of terephthalaldehyde is 2.0. The number of maleimide groups in bis (4-maleimidophenyl) sulfone is 2.0 times the number of primary amino groups in compound (A-7).

Production Example 8: [Production of Compound (A-8) and Bismaleimide Derivative (B-8) Solution Having Primary Amino Group at Terminal]
In a reaction vessel with a volume of 3 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, terephthalaldehyde: 67.0 g, p-aminobenzoic acid: 68.5 g, and N, N-dimethylacetamide: 1143.5 g and toluene: 254.1 g were blended and kept warm at 80 ° C. for 1 hour with stirring.
11,4 g of 4,4′-diamino-3,3′-dimethyl-diphenylmethane: 113.0 g was added thereto, and the mixture was heated to reflux dehydration reaction at about 130 to 145 ° C. Subsequently, after heating up to 160 degreeC and concentrating at normal pressure, it cooled to 120 degreeC and the solution of the compound (A-8) which has a primary amino group at the terminal was obtained.
Next, 895.0 g of bis (4-maleimidophenyl) methane was added, and the mixture was kept at 120 ° C. for 6 hours with stirring, and then cooled to obtain a solution of a bismaleimide derivative (B-8).
In Production Example 8, the total number of primary amino groups of 4,4′-diamino-3,3′-dimethyl-diphenylmethane and p-aminobenzoic acid is 1.5, and the number of aldehyde groups of terephthalaldehyde is 1.0. It is. The number of maleimide groups in bis (4-maleimidophenyl) methane is 10.0 times the number of primary amino groups in compound (A-8).

Examples 1-18, Comparative Examples 1-6
Solutions of bismaleimide derivatives obtained in Production Examples 1 to 8 (Tables 1 to 3) or bismaleimide derivatives listed in Table 4, or epoxy resins, curing accelerators, inorganic fillers, flame retardants And was mixed at a blending ratio (parts by mass) shown in Tables 1 to 4 using 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 applied to an E glass cloth having a thickness of 0.2 mm and dried by heating at 160 ° C. for 10 minutes to produce a prepreg having a resin content of 55% by mass.
Further, four of these prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 25 kg / cm ² and a temperature of 230 ° C. for 120 minutes to produce a copper clad laminate.
Using the copper-clad laminate thus obtained, copper foil adhesion (copper foil peel strength), heat resistance [glass transition temperature (Tg), solder heat resistance and heat resistance with copper], flame retardancy, Dielectric characteristics [relative permittivity (1 GHz) and dielectric loss tangent (1 GHz)] and drill workability were measured and evaluated by the above methods. The results are shown in Tables 1 to 4.

The epoxy resins, curing accelerators, inorganic fillers, flame retardants and bismaleimide derivatives (used in comparative examples) in Tables 1 to 4 are as follows.
(1) Bismaleimide derivative / bis (4-maleimidophenyl) methane (manufactured by Keiai Kasei Co., Ltd.)
・ 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane (Wakayama Seika Co., Ltd.)
(2) Epoxy resin / NC-3000-H: biphenylaralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name NC-3000H, epoxy equivalent 290)
N-770: phenol aralkyl epoxy resin (Mitsui Chemicals, trade name E-XL-3L, epoxy equivalent 235)
YX-4000: biphenyl type epoxy resin (manufactured by Japan Epoxy Resin, trade name YX-4000, epoxy equivalent 190)

(3) Curing accelerator P-200 (Epoxy mask imidazole manufactured by Japan Epoxy Resin Co., Ltd .: trade name)
G-8809L (Daiichi Kogyo Seiyaku Co., Ltd. isocyanate mask imidazole: trade name)

(4) Inorganic filler / fused silica (manufactured by Admatechs: trade name SO-25R)
(5) Flame retardant / 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.)
TPP: Triphenyl phosphate (manufactured by Kanto Chemical Co., Inc., phosphorus content: 9.6 to 9.7% by mass)

As is apparent from Tables 1 to 3, in the examples of the present invention, copper foil adhesion, low thermal expansion, high glass transition temperature, solder heat resistance, heat resistance with copper, flame resistance, low dielectric constant Pre-pregs and laminates excellent in properties and drillability are obtained.
On the other hand, as is clear from Table 4, in Comparative Examples 1 to 6 not containing the bismaleimide derivative of the present invention, copper foil adhesion, low thermal expansion, high glass transition temperature, solder heat resistance, with copper The heat resistance, flame retardancy, low dielectric properties, and drill workability are inferior to those of the examples.

  By using the bismaleimide derivative of the present invention, it has particularly remarkable copper foil adhesion, low thermal expansion, high glass transition temperature, low dielectric properties, solder heat resistance, heat resistance with copper, flame resistance, drill A thermosetting resin composition having excellent processability can be obtained, and a prepreg and a laminate can be provided, and it is advantageously used as an electronic device as a multilayer printed wiring board.

Claims (7)

A bismaleimide derivative represented by the following general formula (I).

(In the formula, Ar ₁ is a residue represented by general formula (I-1), (I-2), (I-3) or (I-4), and Ar ₂ is represented by general formula (I-5) ) Or (I-6), R ₁ represents a hydroxyl group, carboxy group or sulfonic acid group which is an acidic substituent, R ₂ represents a hydrogen atom, an aliphatic hydrocarbon having 1 to 5 carbon atoms A group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5, and n is 0 or a positive number.)

(Wherein R ₃ 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 ₄ and R ₅ 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, r is an integer of 1 to 10.)

(Wherein, the aliphatic hydrocarbon group R ₆ and R ₇ are 1 to 5 carbon atoms each independently represents a methoxy group or a halogen atom, s, t are each independently an integer from 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 bismaleimide derivative according to claim 1, which is represented by the following formula (II).

Compound (a) having at least two primary amino groups in one molecule represented by general formula (III), Compound having at least two aldehyde groups in one molecule represented by general formula (IV) By subjecting the amine compound (c) having an acidic substituent represented by (b) and the general formula (V) to a dehydration condensation reaction in an organic solvent, a primary amino group is formed at the terminal represented by the general formula (VI). The compound (A) having the formula (VII) and the maleimide compound (d) having at least two N-substituted maleimide groups in one molecule represented by the general formula (VII) and the organic solvent The bismaleimide derivative production method according to claim 1 or 2, wherein the bismaleimide derivative (B) represented by the general formula (I) is produced by Michael addition reaction therein.

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

(In the formula, R ₁ and R ₂ , x and y are the same as those in the general formula (I).)

(In the formula, Ar ₂ , R ₁ , R ₂ , x, y, and n are the same as in general formula (I).)

(In the formula, Ar ₁ is the same as in the general formula (I).)   A thermosetting resin composition comprising the bismaleimide derivative according to claim 1.   The thermosetting resin composition of Claim 4 containing the bismaleimide derivative and epoxy resin of Claim 1 or 2.   A prepreg obtained by impregnating and coating a fiber sheet-like reinforcing base material with the thermosetting resin composition according to claim 4 or 5 to form a B-stage.   A laminate obtained by laminate molding using the prepreg according to claim 6.

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