JP3525152B2 - Epoxy resin curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin curable composition. More specifically, the present invention relates to a new composition for a cured epoxy resin having a high crosslinking density, low water absorption and low hygroscopicity, and excellent dielectric properties.

[0002]

2. Description of the Related Art Conventionally, epoxy resin cured products have been widely used for various structural materials and functional materials because of their excellent hardness, strength and heat resistance. In recent years, cured epoxy resin products are
It is also indispensable for electronic equipment and electronic parts.

However, a cured epoxy resin is usually produced by the reaction of various epoxy compounds with a phenolic compound, and a hydroxyl group remains in the side chain with respect to the main chain of the polymer forming the cured resin. It is not always satisfactory in terms of water absorption and hygroscopicity, and there is room for improvement in terms of dielectric properties. Therefore, the present invention solves the problems of the prior art as described above, without having a hydroxyl group in the side chain, the crosslink density of the cured resin is high, water absorption, low hygroscopicity, good dielectric properties, It is intended to provide a new epoxy resin curing composition.

[0004]

The present invention is to solve the above-mentioned problems by providing the following formula (I) in an epoxy resin in the presence or absence of a catalyst.

[0005]

[Chemical 3]

(In the formula, A represents an aromatic ring, R ¹ represents an aliphatic or aromatic carbon group, m is a positive number, and n is 0.
Or a positive number and when n is 0, m is a positive number of 2 or more) and an acid chloride represented by the following formula (II)

[0007]

[Chemical 4]

(Wherein B represents an aromatic ring, R ² represents a hydroxy group or a mercapto group, R ³ represents an aliphatic or aromatic hydrocarbon group, and p is a positive number, r
Is 0 or a positive number, and when r is 0, p is a positive number of 2 or more), an ester compound obtained by reaction with at least one of a phenol resin and polyvinylphenol. The present invention provides a curable epoxy resin composition, characterized in that

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized in that 1) an epoxy resin as described above, 2) a catalyst (if necessary), and 3) an ester compound are blended. The ester compound was formed by the reaction of an acid chloride of formula (I) as described above with at least one phenol (or mercaptan) of a compound of formula (II), a phenolic resin and polyvinylphenol. It is also characterized by being an ester.

With respect to the epoxy resin, those having various structures known so far are used in the present invention. For example, more specifically, diglycidyl ether type epoxy resin of bisphenol A, phenol resin type epoxy resin, aliphatic ether type epoxy resin, alicyclic ether type epoxy resin, ester type epoxy resin, polyfunctionality Glycidylamine type epoxy resin, epoxy resin composed of heterocyclic polyfunctional glycidyl compound,
Alternatively, modified products thereof and the like can be mentioned.

Needless to say, the cured product is obtained as a curing reaction between the epoxy monomer compound forming the epoxy resin and the above ester compound. Further, as a typical catalyst, the catalysts represented by the formulas (R) ₃ N, (R) ₃ P, [(R) ₄ N] ⁺ X ⁻
Or [(R) ₄ P] ⁺ X ⁻ (wherein R represents an aliphatic, aromatic or alicyclic hydrocarbon group, and X represents a halogen atom or another acid residue) Examples thereof include nitrogen-containing compounds, organic phosphorus compounds, crown ethers, and complexes of crown ethers with inorganic or organic compounds.

Of course, in the present invention, the catalyst is
Various types may be used as long as they accelerate the curing reaction, and in some cases, no catalyst may be added. Various types of ester compounds may be used. For example, more specifically, acetoxybenzoic acid, propionyloxybenzoic acid, butyryloxybenzoic acid, isobutyryloxybenzoic acid, pivaloyloxybenzoic acid, benzoyloxybenzoic acid, terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, And acid chloride of at least one carboxylic acid of pyromellitic acid and hydroquinone, resorcin, bisphenol A, bisphenol S, phloroglucin, hydroxybenzoic acid x4w, dehydroxybenzoic acid x4w, polyvinylphenol, and cresol novolac And an ester with at least one phenol.

These esters are basically characterized as the reaction products of the reaction of carboxylic acid chlorides with polyfunctional phenols or the reaction of polyfunctional carboxylic acid chlorides with phenols. Of course, in the compound represented by the above formula, the aromatic ring may include a monocyclic ring, a polycyclic ring, and an aromatic alicyclic ring. It may have any organic group.

The blending ratio of the epoxy resin, the catalyst and the ester compound will vary depending on the use of the cured product and the required properties, but in general, it is generally based on the epoxy group of the epoxy monomer compound forming the epoxy resin. , An ester compound in an equimolar amount as a standard is 0.1 to 1.2.
It may be about a molar ratio. Of course this is not limiting.

When a catalyst is used, it may be, for example, about 0.01 to 0.05 in molar ratio with respect to the epoxy group. If necessary, a bulking material, various fillers, a coloring material and the like may be added to the cured product. In the present invention, the ester compound is characterized as an active ester, and the epoxy resin cured by the ester compound forms a crosslinked structure having no hydroxyl group in the side chain, and thus has low water absorption. , Excellent dielectric properties.

Therefore, in the present invention, a novel polyfunctional active ester compound having an internal ester bond is similarly synthesized as a polyfunctional active ester compound by utilizing the insertion reaction of an internal ester group into an epoxy group, The epoxy resin is cured by using them as a curing agent. As a result, physical properties such as an increase in the cross-linking density of the cured resin and an increase in Tg are improved.

Examples will be shown below to describe the embodiments of the present invention in more detail.

[0018]

EXAMPLES Example 1 <Synthesis of tetrafunctional active ester: 1,4-bis (4-acetoxybenzoyl) benzene (BABH)> Hydroquinone (5.0 g, 45 mmol) and triethylamine (TEA) (10.0 g, 100 mmol) was dissolved in 200 ml of tetrahydrofuran, and 4-acetoxybenzoic acid chloride (20.0 g, 100 mmo) was cooled with ice.
1) was slowly added dropwise. After heating at 50 ° C. for 2 hours with stirring, the mixture was allowed to cool to room temperature and poured into a large amount of water to obtain a precipitate. This was washed well with water, dried and then recrystallized from benzene to obtain white scale-like crystals. The structure was confirmed by IR, ¹ H-NMR and elemental analysis.

[0019]

[Table 1]

Example 2 <Synthesis of 1,3-bis (4-acetoxybenzoyl) benzene (BABR)>

[0021]

[Chemical 5]

Resorcinol (5.0 g, 45 mmo
l) and triethylamine (TEA) (10.0 g, 10
0 mmol) was dissolved in 120 ml of tetrahydrofuran, and 4-acetoxybenzoic acid chloride (2
0.0 g, 100 mmol) was slowly added dropwise. After heating to 50 ° C. for 1 hour with stirring, the mixture was allowed to cool to room temperature and poured into a large amount of water to obtain a precipitate. This was washed well with water and dried, then benzene / petroleum ether (1:
Recrystallization from 1) gave white powdery crystals. The structure was confirmed by IR, ¹ H-NMR and elemental analysis.

[0023]

[Table 2]

Example 3 <Synthesis of hexafunctional active ester: 1,3,5-tri (4-acetoxybenzoyl) benzene (TABB)>

[0025]

[Chemical 6]

Trihydroxybenzene (THB) (0.
58 g, 4.5 mmol) and triethylamine (TE
A) (14.4 mmol) was dissolved in tetrahydrofuran, and 4-acetoxybenzoic acid chloride (3.0 g, 15.1 mmol) was slowly added dropwise while cooling with ice. After heating at 60 ° C. for 15 hours with stirring, the mixture was allowed to cool to room temperature and poured into a large amount of water to obtain a precipitate. This was washed well with water, dried and then recrystallized from methanol to give white needle crystals. The structure is confirmed by IR, ¹ H
-NMR and elemental analysis were performed.

[0027]

[Table 3]

Example 4 <Polyfunctional active ester: resorcinol bisacetoxyphenylcarbonylisophthalate (BAPIR)> Resorcinol (1.10 g, 10.0 mmol) and triethylamine (TEA) (2.20 g, 20.0 mmo)
l) was dissolved in 80.0 ml of tetrahydrofuran, and isophthalic dichloride (1.015 g, 5.
(0 mmol) dissolved in 20.0 ml of THF was slowly added dropwise. After completion of dropping, the mixture was stirred for 4 hours as it was, cooled again with ice, and then mixed with 20.0 ml of THF.
3.97 g of acetoxybenzoic acid chloride (20.0 m
(mol) was slowly added dropwise, and after completion of the addition, the solution was poured into an aqueous sodium carbonate solution to obtain a white precipitate. The precipitate was suction filtered, washed well with water and methanol, and dried under reduced pressure to give white needle crystals having the structure of the following formula. The structure was confirmed by IR, ¹ H-NMR and elemental analysis.

[0029]

[Chemical 7]

Example 1)

[0031]

[Table 4]

Example 2) The yield was 53.7% in the same manner. Tm: 179.8 ° C. Example 3) Similarly, the yield is 53.4%. Tm: 183.3 ° C. Example 5 <Hexafunctional active ester: 1,3,5-tri (4-methoxycarbonyl) phenyleneoxycarbonyl) benzene (TMB)> 1) Synthesis of trimesic acid chloride (TMC) Trimesic acid (TMA) (3 g, Thionyl chloride (30 ml) and 3 drops of DMF were added to 14.3 mmol), and the temperature was adjusted to 80 ° C.
After refluxing for 2 hours, excess thionyl chloride was distilled off under reduced pressure.

Yield 87.9% 2) 1,3,5-tri (4-methoxycarbonyl) phenyleneoxycarbonyl) benzene (TMPB)

[0034]

[Chemical 8]

Methyl 4-hydroxybenzoate (2.33)
g, 15.3 mmol) and triethylamine (TEA)
(14.8 mmol, 1.49 g) was dissolved in 100.0 ml of tetrahydrofuran, and a solution of the above trimesic acid chloride (1.2 g, 4.5 mmol) in a small amount of tetrahydrofuran was slowly added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 2 hours, further refluxed for 3 to 4 hours, and then poured into a large amount of water containing anhydrous sodium carbonate to obtain a precipitate. The precipitate was filtered, dried and recrystallized from benzene to give white needle crystals. The structure was confirmed by IR, ¹ H-NMR and elemental analysis.

Yield 73.2% Example 6 <Curing reaction: curing with 4-bis (4-acetoxybenzoyl) benzene (BABH)> Bisphenol A diglycidyl ether (DGEBA) and BABH were mixed in an equimolar ratio, Stir well at a temperature of 130-150 ° C and when uniform, triphenylphosphine (TPP)
2.5 mol% was added to the epoxy group. The solution was immediately poured into a Teflon mold, and heat-cured on a hot press at 150 ° C. for 5 hours and then at 170 ° C. for 2 hours.

Tg: 102 ° C. Example 7 <Curing by 1,3-bis (4-acetoxybenzoyl) benzene (BABR)> DGEBA and BABR were mixed in an equimolar ratio, and the mixture was well stirred at a temperature of 130-150 ° C. When it became uniform, 2.5 mol% of TPP was added to the epoxy group. The solution was immediately poured into a Teflon mold and heat-cured on a hot press at 140 ° C. for 5 hours.

Tg: 104 ° C. Example 8 <Curing by 1,3,5-tri (4-acetoxybenzoyl) benzene (TABB)> DGEBA and TABB were mixed in an equimolar ratio, and well mixed, and when uniform, 4.0 mol% of TPP was added to the epoxy group.
The solution was immediately poured into a mold made of silicon, degassed under reduced pressure, and then hot-pressed at 160 ° C. for 4 hours, and further 18 times.
It was heat-cured at 0 ° C. for 2 hours.

Tg: 130 ° C. The formation reaction of the cured product can be shown as follows. After curing, no hydroxyl group remains and the number of side chain ester groups is extremely small.

[0040]

[Chemical 9]

Example 9 <Curing with resorcinol bisacetoxyphenylcarbonylisophthalate (BAPIR)> Example 1) DGEBA and BAPIR were mixed in an equimolar ratio and well mixed. When uniform, TPP was mixed with epoxy group 3 0.5 mol% was added. Immediately pour the solution into a mold made of silicon, degas under reduced pressure, and then press on a hot press for 16 minutes.
It was heat-cured at 0 ° C. for 1 hour.

Tg: 144 ° C. Example 2) The compounding ratio of DGEBA and BAPIR is 1: 1 (equimolar ratio).
And stir well, and when it becomes uniform, add 3.5 mol% of TPP to the epoxy group and pour it into the mold.
After deaeration under reduced pressure, it was heat-cured on a hot press at 170 ° C. for 1 hour.

Tg: 142 ° C.

[0044]

As described above in detail, according to the present invention, since the cured product forms a crosslinked structure having no hydroxyl group, it has low water absorption and excellent dielectric properties. In the present invention, a novel polyfunctional active ester compound having an internal ester bond is similarly synthesized as a polyfunctional active ester compound by utilizing the insertion reaction of an internal ester group into an epoxy group and used as a curing agent. It is used to cure the epoxy resin. As a result, physical properties such as an increase in the cross-linking density of the cured resin and an increase in Tg are improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-53327 (JP, A) JP 55-9639 (JP, A) JP 54-155298 (JP, A) JP 54- 142244 (JP, A) JP 8-143642 (JP, A) JP 7-82348 (JP, A) JP 7-53675 (JP, A) JP 7-292067 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/00-59/72

Claims (5)

(57) [Claims] 1. An epoxy resin in the presence or absence of a catalyst, represented by the following formula (I): (A in the formula represents an aromatic ring, R ¹ represents an aliphatic or aromatic hydrocarbon group, m is a positive number, n is 0 or a positive number, and when n is 0, Is an acid chloride represented by the following formula (II): (B in the formula represents an aromatic ring, R ² represents a hydroxy group or a mercapto group, R ³ represents an aliphatic or aromatic hydrocarbon group, p is a positive number, and r is 0. Alternatively, when r is 0 and p is a positive number of 2 or more), a compound represented by the formula, an ester compound obtained by a reaction with at least one of a phenol resin and polyvinylphenol is blended. An epoxy resin curable composition, characterized in that 2. The catalyst is of the formula (R) ₃ N, (R) ₃ P,
[(R) ₄ N] ⁺ X ⁻ or [(R) ₄ P] ⁺ X ⁻ (In the formula, R represents an aliphatic, aromatic or alicyclic hydrocarbon group, and X is a halogen atom or another. The composition of claim 1 which is at least one compound represented by 3. The composition according to claim 1, wherein the catalyst is a crown ether, or a complex of a crown ether and an inorganic or organic compound. 4. A diglycidyl ether type epoxy resin whose epoxy resin is bisphenol A, a phenol resin type epoxy resin, an aliphatic ether type epoxy resin, an alicyclic ether type epoxy resin, an ester type epoxy resin,
The composition according to any one of claims 1 to 3, which is a polyfunctional glycidylamine type epoxy resin, an epoxy resin comprising a heterocyclic polyfunctional glycidyl compound, or at least one of these modified products. 5. The ester compound is acetoxybenzoic acid, propionyloxybenzoic acid, butyryloxybenzoic acid, isobutyryloxybenzoic acid, pivaloyloxybenzoic acid, benzoyloxybenzoic acid, terephthalic acid,
Acid chloride of at least one carboxylic acid of isophthalic acid, phthalic acid, trimellitic acid, and pyromellitic acid, and hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phloroglucin, polyvinylphenol, and cresol novolac A composition according to any one of claims 1 to 4 which is an ester with at least one of the polyfunctional phenols.