JPH09124897A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin composition which is excellent in heat resistance, moisture resistance, dielectric characteristics, thermal expansion, flame retardancy and moldability, and useful as an electric and electronic material such as sealing material and laminates by mixing a mixture or condensate of a phenol, an aldehyde and a compound having a triazine ring with an imide bearing ethylenically unsaturated groups. SOLUTION: (A) A mixture or a condensation product of a phenol, an aldehyde and a triazine ring-containing compound (free from aldehyde and substantially bearing no methylol group), is mixed with (B) an imide having at least two of ethylenically unsaturated groups. The compound bearing the triazine ring is preferably represented by formula I and/or formula II (R1 -R3 are each independently amino, alkyl, phenyl; R4 -R6 are each independently H, an alkyl, phenyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition suitable for electric / electronic materials such as encapsulating materials and laminated plates, or for molding materials.

[0002]

2. Description of the Related Art Phenolic resins are mainly used for molding materials, laminates and industrial resins (adhesives or binders) by taking advantage of various excellent physical properties. However, since known phenolic resin contains a large amount of components such as volatile components derived from condensed water and curing agent during molding (= curing), it is difficult to obtain a thick molded body such as a sealing material. However, it is difficult to use it alone for electric and electronic materials because of its poor moisture resistance. Further, the phenol resin is fragile and has a drawback that it has poor workability such as drilling workability and machinability.

On the other hand, epoxy resin is widely used for electric and electronic materials, but it is required to meet high demand levels such as heat resistance, moisture resistance, flame retardancy, low dielectric constant and low thermal expansion due to technological innovation. It is not possible to respond enough.

[0004]

The present invention has excellent heat resistance, moisture resistance, dielectric properties, thermal expansion properties, flame retardancy, and moldability, and is used for electrical and electronic materials such as encapsulants and laminates. Alternatively, it is intended to provide a thermosetting resin composition suitable for molding materials and the like.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above circumstances, the present inventors have found that a mixture or cocondensate having a specific composition such as a phenol and a compound having a specific triazine ring is It was found that the above problems can be solved when used together with an imide compound having an unsaturated group, and the present invention has been completed.

That is, the present invention comprises a mixture or condensate of a phenol, a compound having a triazine ring and an aldehyde, wherein the mixture or condensate does not contain unreacted aldehydes and substantially contains a methylol group. And a imide compound having at least two ethylenically unsaturated groups in the molecule, and a thermosetting resin composition.

INDUSTRIAL APPLICABILITY The present invention can provide a cured product having excellent heat resistance, moisture resistance, dielectric properties, thermal expansion properties, flame retardancy, and moldability, and is used for electrical and electronic materials such as encapsulants and laminates. ,
Alternatively, the invention provides a thermosetting resin composition suitable for molding materials and the like.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Resin composition (A) in the present invention
The above-mentioned phenols for obtaining is not particularly limited, and examples thereof include phenol, or alkylphenols such as cresol, xylenol, ethylphenol, butylphenol, nonylphenol, octylphenol, bisphenol A, bisphenol F, bisphenol S, resorcin, Examples thereof include polyphenols such as catechol, halogenated phenols, phenylphenols and aminophenols. The use of these phenols is not limited to one kind alone, and two or more kinds can be used in combination.

Further, the compound containing a triazine ring for obtaining the resin composition (A) of the present invention is not particularly limited, but is represented by the following general formula (I) and / or general formula (II). It is preferably a compound represented.

[0010]

Embedded image

(In the formula, R ₁ , R ₂ and R ₃ are amino group, alkyl group, phenyl group, hydroxyl group, hydroxylalkyl group, ether group, ester group, acid group, unsaturated group, cyano group and halogen. Represents one of the atoms)

[0012]

Embedded image

(Wherein R ₄ , R ₅ and R ₆ are hydrogen atom, alkyl group, phenyl group, hydroxyl group, hydroxylalkyl group, ester group, acid group, unsaturated group, cyano group,
Representing any of halogen atoms) In the general formula (I), it is preferable that at least two of R ₁ , R ₂ and R ₃ are amino groups.

As the compound represented by the general formula (I)
Is specifically melamine or acetoguanamine,
Guanamine derivatives such as benzoguanamine, cyanuric
Acid or methyl cyanurate, ethyl cyanurate
Cyanide such as acetyl cyanurate, cyanuric chloride
And the like. Among these, R₁,
R_Two, R _ThreeAny two or three of the above are amino groups
Melamine, acetoguanamine, benzoguanamine, etc.
Are more preferred.

Further, in the general formula (II), it is preferable that at least one of R ₄ , R ₅ and R ₆ is a hydrogen atom.
Specific examples of the compound represented by the general formula (II) include isocyanuric acid, methyl isocyanurate, ethyl isocyanurate, allyl isocyanurate, 2-hydroxyethyl isocyanurate, 2-carboxylethyl isocyanurate, and chlorinated isocyanurate. And isocyanuric acid derivatives such as acids. Among these, R
Isocyanuric acid in which all of ₄ , R ₅ and R ₆ are hydrogen atoms is most preferred. Cyanuric acid, which is a compound represented by the general formula (I), which is a tautomer, is also a preferable compound.

These compounds are not limited to one kind in use, and two or more kinds can be used in combination. Aldehydes for obtaining the phenolic composition of the present invention are not particularly limited, but formaldehyde is preferred from the viewpoint of easy handling. The formaldehyde is not particularly limited, but typical sources include formalin, paraformaldehyde and the like.

The phenol resin composition of the present invention is characterized by containing no unreacted aldehydes and substantially containing no methylol group. By containing no unreacted aldehydes and substantially not containing a methylol group, it is possible to suppress the generation of volatile components during molding and obtain a uniform cured product.

The unreacted monofunctional phenolic monomer contained in the phenolic resin composition of the present invention is preferably 3% by weight or less. By setting the amount of the unreacted monofunctional phenol monomer to 3% by weight or less, there is an effect that heat resistance and moisture resistance of the obtained cured product are improved.

The unreacted monofunctional phenolic monomer as used herein means a phenolic monomer containing only one phenolic hydroxyl group capable of reacting with an epoxy group in one molecule.

A typical method for obtaining the phenol resin composition of the present invention will be described below. First, the above-mentioned phenols, aldehydes and compounds having a triazine ring are reacted under a basic or acidic catalyst. At this time, the pH of the system is not particularly limited, but since many compounds containing a triazine ring are easily dissolved in a basic solution, it is preferable to react under a basic catalyst,
Further, it is preferable to use amines as the basic catalyst. Also, the reaction order of each raw material is not particularly limited, and even if a compound having a triazine ring is first reacted with a phenol or an aldehyde, then a compound having a triazine ring is reacted with an aldehyde and then the phenol is reacted. The raw materials may be added, or all the raw materials may be added at the same time and reacted. At this time, the molar ratio of the aldehydes to the phenols is not particularly limited, but is 0.2 to 1.5.
And preferably 0.4 to 0.8. The weight ratio of the compound having a triazine ring to the phenols is 1
0 to 98:90 to 2, preferably 30 to 80:70 to 2
0. If the weight ratio of phenols is 10% or less, it becomes difficult to form a resin, and if it is 80% or more, a sufficient crosslinking density cannot be obtained, which is not preferable.

Although the catalyst is not particularly limited, examples of the basic catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and barium hydroxide, and these. Oxides, ammonia, primary to tertiary amines, hexamethylenetetramine, sodium carbonate and the like, and examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and sulfonic acid, organic acids such as oxalic acid and acetic acid, Examples thereof include Lewis acids and divalent metal salts such as zinc acetate.

When the phenol resin composition of the present invention is used as a resin for electric and electronic materials, it is not preferable that an inorganic substance such as a metal remains as a catalyst residue. Therefore, an amine is used as a basic catalyst. It is preferable to use an organic acid as the acidic catalyst.

From the viewpoint of reaction control, the reaction may be carried out in the presence of various solvents. Next, if necessary, impurities such as salts are removed by neutralization and washing with water. However, when amines are used as the catalyst, it is desirable not to carry out.

After completion of the reaction, unreacted aldehydes, phenols, solvents and the like are removed by ordinary methods such as atmospheric distillation and vacuum distillation. At this time, a heat treatment at 120 ° C. or more is required to obtain a resin composition substantially free of unreacted aldehydes and methylol groups, which is a feature of the curing agent resin composition of the present invention. It is difficult to substantially eliminate the methylol group by heat treatment at 120 ° C. or lower. If the temperature is 120 ° C. or higher, the methylol group can be eliminated by taking a sufficient time, but it is preferable to perform a heat treatment at a higher temperature, preferably 150 ° C. or higher for efficient elimination. At this time, at a high temperature, it is preferable to carry out distillation together with heating, according to a conventional method for obtaining a novolak resin. At this time, as described above, the content of the unreacted monofunctional phenol monomer is preferably set to 3% by weight or less.

The thus-obtained phenolic resin composition is characterized by containing no unreacted aldehydes and containing substantially no methylol group. The imide compound (B) having an ethylenically unsaturated group of the present invention
Means at least 2 ethylenically unsaturated groups in the molecule.
It refers to an imide compound having more than one, where the ethylenically unsaturated group refers to, for example, vinyl group, allyl group, isopropenyl group, acryloyl group, methacryloyl group, alicyclic unsaturated group, etc. It refers to a compound having an imide ring in the structure. Although such compounds are not particularly limited, the following compounds are preferred.

Those having at least two maleimide structures in the molecule, for example, bismaleimide such as 4,4'-diphenylmethane-bismaleimide, 1,4-phenyl-bismaleimide, or the general formula (III). Compound

[0027]

Embedded image

(R represents an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 1 to 5 phenylene groups in the main chain), specifically diphenylmethane-4,4-
Bisallyl nadimide, hexamethylene-4,4-
Alkenyl-substituted nadic imide monomers such as bisallyl nadimide and their polymers, nadic imide monomers such as bis nadimide and phenyl nadimide and their polymers, maleimide monomers such as bismaleimide and phenyl maleimide and their polymers, etc. Is mentioned. Among these, the following general formula (IV)
Diphenylmethane-4,4-bisallyl nadimide represented by

[0029]

Embedded image

And hexamethylene-4,4-bisallylnadic imide represented by the following general formula (V)

[0031]

Embedded image

Is most preferable because it exhibits extremely high heat resistance and flame retardancy. Alternatively, a compound having two nadiimide groups represented by general formula (VI)

[0033]

Embedded image

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, or 5 to 5 carbon atoms.
8 represents a cycloalkyl group, an aromatic hydrocarbon group, or a benzyl group, and X is a divalent linking group having 2 to 2 carbon atoms.
20 alkylene group, a cycloalkylene group of 5 to 8 carbon atoms, an aromatic hydrocarbon _{group, -C 6 H 4 -Y-C} 6 H 4 - [Y is _{CH 2, C (CH 3)} 2, CO, O , S, SO ₂ ].

Examples of the compound having two nadiimide groups represented by the general formula (V1) include N, N'-ethylene-bis (bicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide), N, N'-hexamethylene-bis (bicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide), N, N'-hexamethylene-bis (methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p or m-phenylene-bis (Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p or m-phenylene-bis (methylbicyclo [2.2.1]]
Hept-5-ene-2,3-dicarboximide), N,
N'-p or m-xylylene-bis (bicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide), bis {4- (bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane,
Bis {4- (isopropylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl}
Examples include methane.

The mixing ratio of the phenol resin composition of the present invention and the imide compound having an ethylenically unsaturated group is not particularly limited, but the phenol resin composition (A) and the ethylenically unsaturated group are mixed. The weight ratio with the imide compound (B) is preferably A: B = 90 to 20:10 to 80, and the compound having an active amino group equivalent of the phenol resin composition and an ethylenically unsaturated group is preferably added. It is more preferable that the unsaturated group equivalent is mixed with 1: 0.8 to 1.6. This is because a compounding that does not leave unreacted amino groups or unsaturated groups in the resin is necessary to obtain good physical properties.

The thermosetting resin composition of the present invention can be diluted with a solvent if necessary. The solvent is not particularly limited, and various solvents can be used as necessary.
Examples thereof include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone, methylene chloride, methanol, ethanol, butanol, and the like. Can be appropriately used as a mixed solvent of two or more kinds. Considering the solubility of the imide compound, it is preferable to use N, N-dimethylformamide or N-methylpyrrolidone.

Various additives, flame retardants, fillers and the like can be appropriately added to the thermosetting resin composition of the present invention, if necessary. The thermosetting resin composition of the present invention,
It can be used for not only electric and electronic materials and molding materials but also casting materials, housings, flooring materials, adhesives, paints, and the like.

[0039]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Hereinafter,% means “% by weight” and “part” means “part by weight”.

[Synthesis Example 1] (Synthesis Example of Phenol Resin Composition) 94 parts of phenol, 19 parts of melamine, 43 parts of 41.5% formalin, and 0.19 part of triethylamine were added, and the temperature was raised to 100 ° C. After reacting at 100 ° C for 5 hours, the temperature was raised to 180 ° C over 2 hours while removing water under normal pressure, and then unreacted phenol was removed under reduced pressure to remove phenol having a softening point of 127 ° C. A resin composition was obtained.

Hereinafter, this composition is abbreviated as "N1". The weight ratio of the phenols to the compound having a triazine ring, the amount of unreacted formaldehyde, the presence or absence of methylol groups, and the amount of unreacted phenol monomer in the obtained composition were determined as follows. <Weight ratio of phenol to triazine ring-containing compound (melamine)> 180 ° C, the phenol content in the effluent removed outside the reaction system under reduced pressure was calculated by gas chromatography, and subtracted from the number of charged phenol parts to obtain the composition. It was defined as the amount of phenol present. Melamine was included in the composition as it was charged. The ratio between the two was defined as the abundance ratio. Column: 30% Celite 545 carnauba wax 2mx
3 mmΦ column temperature: 170 ° C. inlet temperature: 230 ° C. detector: FID carrier gas: N ₂ gas 1.0 kg / cm 2 measuring method: internal standard method <amount of unreacted formaldehyde> about 5 g of composition finely pulverized in 50 g of distilled water Was added and the mixture was kept at room temperature for 24 hours.
Set to pH meter, add N / 10 hydrochloric acid aqueous solution to obtain pH =
It was adjusted to 4.0. 7% adjusted to pH = 4.0
50 ml of an aqueous hydroxylamine solution was added, sealed with an aluminum foil or the like, and left for 30 minutes. Then set it on the pH meter,
Titrate with 1N sodium hydroxide solution until neutralized to pH = 4.0. The amount of free formaldehyde was determined by the following formula.

[0042] <Presence or absence of methylol group> The methylol group present in the resin composition was measured using C13-NMR. Device: JSX GSX270 Proton: 270MHz Measuring solvent: Deuterated methanol or deuterated acetone Reference substance: Tetramethylsilane Measuring condition Pulse condition: 45 ° x 4000times Pulse interval: 2 seconds Appeared in 60-70ppm of the obtained chart , A peak that can be clearly distinguished from noise was used for the determination. A case where a peak was observed was evaluated as “present”, and a case where no peak was observed was evaluated as “absent”. <Amount of Unreacted Phenol Monomer> The content of phenol monomer in the composition was measured under the same measurement conditions as in the gas chromatography described above. The amounts of the components thus obtained are summarized in Table 1.

[Synthesis example 2] (Synthesis example of phenol resin composition) 41.5 parts of phenol 94 parts and benzoguanamine 66 parts
% Formalin 49 parts and triethylamine 0.7 parts were added and reacted at 100 ° C. for 3 hours. The temperature was raised to 120 ° C. while removing water under normal pressure, and the reaction was carried out for 3 hours while maintaining the temperature. 18 while removing water under normal pressure
The temperature was raised to 0 ° C over 2 hours, and then unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 135 ° C. The weight ratio of phenol and benzoguanamine, the amount of unreacted formaldehyde, the presence or absence of methylol groups, and the amount of unreacted phenol monomer were determined, and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N2". [Synthesis Example 3] (Synthesis Example of Phenol Resin Composition) 58 parts of 41.5% formalin and 0.47 part of triethylamine were added to 94 parts of phenol, and the mixture was reacted at 80 ° C. for 3 hours. Next 9 parts of melamine and 3 parts of benzoguanamine
8 parts was added and the reaction was further continued for 2 hours. The following reaction was performed in the same manner as in Synthesis Example 2 to obtain a phenol resin composition having a softening point of 138 ° C. The weight ratio of phenol to melamine and benzoguanamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, and the amount of unreacted phenol monomer were determined in the same manner as in Synthesis Example 1, and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N3". Phenol novolac resin [TD-2131 manufactured by Dainippon Ink and Chemicals, Inc.] is abbreviated as "PN". The amount of unreacted formaldehyde, the presence or absence of a methylol group, and the amount of unreacted phenol monomer were determined according to the method described above, and the results are shown in Table 1.

[0046]

[Table 1] Examples 1 to 4 The compounds N1 to N3 were melted at 200 ° C., the imide compound containing an ethylenically unsaturated group was added thereto according to the ratio shown in Table 2, and the mixture was melt-mixed.
It was poured into a thick glass mold and heat-cured at 180 ° C. for 2 hours and then at 200 ° C. for 2 hours to obtain a cast plate. When each physical property test was conducted, the results shown in Table 2 were obtained.

Comparative Example 1 Epoxy resin (Epiclon 850 [Dainippon Ink and Chemicals
Co., Ltd.] 100 parts of epoxy equivalent 190) was mixed with 55 parts of PN as a curing agent. At this time, an accelerator (2E4MZ) was added to PN in advance and the temperature was maintained at 170 ° C. to melt it. Similarly, add the heated epoxy resin, stir well, and pour it into a glass mold with a thickness of 3 mm.
It was heat-cured at 0 ° C. for 2 hours to obtain a cast plate. When each physical property test was conducted, the results shown in Table 2 were obtained.

Comparative Example 2 10 parts of hexamethylenetetramine was mixed with 100 parts of PN and pulverized, and gradually hardened by repeating pressurization and depressurization,
Molding was performed at 170 ° C. for 2 hours. The obtained molded body was post-cured at 170 ° C. for 4 hours. When each physical property test was conducted, the results shown in Table 2 were obtained.

[0049]

[Table 2]

[0050]

INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention can give a cured product excellent in heat resistance, moisture resistance, dielectric properties, thermal expansion properties, flame retardancy, and moldability.

Claims (11)

[Claims] 1. A mixture or condensate of a phenol, a compound having a triazine ring and an aldehyde, wherein the mixture or the condensate does not contain unreacted aldehydes and does not substantially contain a methylol group. A thermosetting resin composition comprising the resin composition (A) and the imide compound (B) having at least two ethylenically unsaturated groups in the molecule. 2. The composition according to claim 1, wherein the compound having a triazine ring is a compound represented by the general formula (I) and / or a compound represented by the general formula (II). Embedded image (Wherein, R ₁ , R ₂ and R ₃ represent an amino group, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group,
Ether group, ester group, acid group, unsaturated group, cyano group,
Represents any of halogen atoms) (Wherein, R ₄ , R ₅ , and R ₆ represent a hydrogen atom, an alkyl group, a phenyl group, a hydroxyl group, a hydroxylalkyl group,
Represents any of ester group, acid group, unsaturated group, cyano group and halogen atom) 3. In the general formula (I), any _{two of} R ₁ , R ₂ and R ₃ are amino groups.
A composition as described. 4. The composition according to claim ₂ , wherein R ₁ , R ₂ and R _{3 in the} general formula (I) are amino groups. 5. The composition according to any one of claims 1 to 4, wherein R ₄ , R ₅ and R _{6 in the} general formula (II) are hydrogen. 6. The composition according to claim 1, wherein the unreacted monofunctional phenolic monomer contained in the mixture or the condensate is 3% by weight or less. 7. The composition according to claim 1, wherein the imide compound (B) is a compound having at least two maleimide structures in the molecule. 8. The imide compound (B) is a compound represented by the general formula (III).
A composition according to any one of the preceding claims. Embedded image (R represents an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 5 phenylene groups in the main chain.) 9. The imide compound (B) is diphenylmethane-4,4′-bisallylnadic imide represented by the general formula (IV), according to any one of claims 1 to 6. Composition. Embedded image 10. The imide compound (B) is hexamethylene-4,4-bisallylnadic imide represented by the general formula (V), according to any one of claims 1 to 6. Composition. Embedded image 11. The composition according to any one of claims 1 to 6, wherein the imide compound (B) is a compound having two nadiimide groups represented by the general formula (VI). [Chemical 6] [Wherein, R represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
Represents an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aromatic hydrocarbon group, or a benzyl group, and X is a divalent linking group, and an alkylene group having 2 to 20 carbon atoms. A cycloalkylene group having 5 to 8 carbon atoms, an aromatic hydrocarbon group, —C ₆ H ₄ —Y—C ₆ H ₄ — [Y is CH ₂ , C
(CH ₃ ) ₂ , CO, O, S, SO ₂ ]