JPH03207746A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject epoxy resin composition having excellent heat resistance, flexibility, crack resistance and hydrophobic property by adding a specific copolymer to an epoxy resin with using polyallylphenol as a curing agent. CONSTITUTION:(A) 100 pts.wt. epoxy resin, preferably an epoxy resin of bisphenol-A type or cresol-novolak type, etc., is mixed with (B) 30-120 pts.wt. polyallylphenol having plural pieces of the unit expressed by formula I as a curing agent, e.g., a compound expressed by formula II or formula III and (C) 5-80 pts.wt. copolymer selected from an ethylene/alpha-olefin copolymer, a copolymer of polystyrene/polybutadiene/polystyrene having blocked terminals and an ethylene/propylene-based terpolymer, and further an inorganic filler, a curing accelerator, a coupling agent, a mold release material or a coloring material, etc., as necessary, to afford the aimed composition.

Description

[Detailed description of the invention] 〔overview〕 Regarding epoxy resin compositions.

The purpose of the present invention is to provide an epoxy resin composition with excellent heat resistance, flexibility, crack resistance, and hydrophobicity.

For 100 parts by weight of epoxy resin, 30 to 120 parts by weight of polyallylphenol having a plurality of structural units represented by the following formula (1) in the molecule, ethylene/α-olefin copolymer, polystyrene/polybutadiene Copolymers 5 to 8 selected from the group consisting of /polystyrene end block copolymer, ethylene/propylene ternary copolymer
The epoxy resin composition is configured to contain 0 parts by weight.

[Industrial application field]

The present invention relates to an epoxy resin composition, and more specifically, relates to an epoxy resin composition that is particularly excellent in heat resistance, flexibility, crank resistance, and hydrophobicity.The epoxy resin composition of the present invention has the above-mentioned advantages. Because of its properties, it can be advantageously used in various fields, particularly in the fields of multilayer lamination resins, conductive base electronic device protective films, adhesives, VI materials, sealing materials, and molding materials.

[Conventional technology]

BACKGROUND ART In recent years, electronics, electrical and electrical equipment, transportation equipment, etc. have become smaller, lighter, and more sophisticated, and along with this, materials with excellent heat resistance are desired.

Polyimide resin is generally known as a heat-resistant resin, but since it is a dehydration condensation type, voids are likely to occur in the cured product due to condensation water generated during the reaction, and the reliability of the cured product is reduced. On the other hand, polyimide itself is difficult to mold because it is insoluble and infusible.

Bismer imide resin is known as a polyimide with improved moldability, but it requires temperatures of 200°C or higher for molding, resulting in poor workability.

Bismaleimide resin has poor hydrophobicity, which significantly reduces the reliability of the cured product.

[Problem to be solved by the invention]

An object of the present invention is to eliminate the drawbacks of the conventional techniques as described above, in other words, the present invention can be advantageously used in various fields. An object of the present invention is to provide an epoxy resin composition having excellent heat resistance, flexibility, crack resistance, and hydrophobicity.

[Means to solve the problem]

According to the present invention, epoxy resin 100
Based on the weight part, 30 to 120 parts by weight of polyallylphenol having a plurality of structural units represented by the following formula (1) in the molecule, ethylene/α-olefin copolymer, polystyrene/polybutadiene/polystyrene terminal This is achieved by using an epoxy resin composition containing 5 to 80 parts by weight of a copolymer selected from the group consisting of block copolymers and ethylene/propylene ternary copolymers.

As the above-mentioned polyallylphenol, polyallylphenol represented by the following formula (2) can be used.

Further, as the above-mentioned polyallylphenol, polyallylphenol represented by the following formula (3) can be used.

The epoxy resin used as the base resin in the composition of the present invention is arbitrary. According to the findings of the inventors, examples of epoxy resins that can be advantageously used include bisphenol A epoxy resin, Talezol novolac epoxy resin, and phenol novolak epoxy resin 3 Tetramethylbiphenyl epoxy resin Examples include epoxy resins having two or more epoxy groups in the molecule, such as glycidyl ether type epoxy IM resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and halogenated epoxy resins. These epoxy resins may be used alone or in a mixture of two or more.

The polyallylphenol used as a curing agent in the composition of the present invention is as described above (1)<2)(3).
The expression expressed by the formula can be applied.

Polyarylphenol is a dark brown viscous substance with a temperature of 8
It exhibits a viscosity of about 25 to 35 P (poise) at 0°C, and the amount of filler such as inorganic filler can be increased.

Further, polyallylphenol having an equivalent weight (molecular weight per OH group) of about 135 to 160 can be preferably used.

The curing reaction between epoxy resin and polyallylphenol ((R), φ-0H) used as a curing agent is as follows (
proceed. R is an allyl group, and φ is a benzene ring.
(Catalyst) (R), φ-0-CH, -C
HR' ---→0-CH, -CHR' H ---→ Curing By using polyallylphenol as a curing agent, the heat resistance and hydrophobicity of the cured resin product can be improved. This effect is due to the allyl group of polyallylphenol. The blending amount of polyallylphenol is 10% of the epoxy resin.
The amount of polyallylphenol is preferably about 30 to 120 parts by weight relative to 0 parts by weight. If the amount of polyallylphenol is less than 30 parts by weight, the curing reaction will not proceed sufficiently, and if it exceeds 120 parts by weight, the heat resistance of the cured product will deteriorate. to degrade.

It has been found that the copolymer added to the epoxy resin as the base resin in the present invention is particularly effective in simultaneously improving crack resistance and flexibility. Note that the term "copolymer" hereinafter refers to these copolymers.

In the epoxy resin composition of the present invention, the copolymer can have a variety of structures and is, in fact, commercially available in a variety of forms. -For example, ethylene/α-
The olefin copolymer is Tafmer P P-0280 (manufactured by Mitsui Petrochemical), and the polystyrene/polybutadiene/polystyrene terminal block copolymer is Kraton G-
The ethylene/propylene ternary copolymer is available as JSI157P (manufactured by Japan Synthetic Rubber Co., Ltd.).These copolymers are generally rubbery copolymers.

The above-mentioned copolymers can be used in various amounts in the epoxy resin composition depending on the desired effect of addition. Although this amount can usually vary widely, - for boat fishing, it is preferably about 5 to 80 parts by weight per 100 parts by weight of epoxy resin, as detailed in the Examples section below. On the other hand, if it is less than 5 parts by weight, the effect of addition will not be apparent, and if it exceeds 80 parts by weight, the properties of the epoxy resin as heat-resistant InAl1 will deteriorate.

The composition of the present invention may contain the following components (1) as necessary.
) to (5) etc. can be added.

(1) Powdered inorganic fillers such as fused silica, crystalline silica, alumina, and calcium carbonate, and the amount of inorganic fillers added is preferably in the range of 30 to 85 wt% of the entire composition. The amount of added base material is 30w
This is because if it is less than t%, the effect of addition will be small, and if it is more than 85wt%, there is a possibility that workability will be lowered due to a decrease in flowability.

(2) A curing accelerator for accelerating the curing reaction between the epoxy resin and polyallylphenol. The amount of the curing accelerator added is preferably about 0.2 to 10 parts by weight per 100 parts by weight of the epoxy resin. Examples include imidazole series such as 2-methylimidazole, phosphine series such as triphenylphosphine, and DB such as phenol salts of DBU.
U (diazabicycloundecene) type etc. are used.

(3) When adding an inorganic filler, there is no coupling agent used to improve compatibility with the resin. For example, a silane coupling agent such as 3-aminopropyltriethoxysilane 3
Alternatively, a titanium-based coupling agent such as tetraoctyl bis(phosphite) titanate may be used. The amount of the coupling agent added depends on the type, amount, specific surface area, and minimum coverage area of the inorganic filler used, but in the present invention, it is 0.1 to 15 parts by weight per 100 parts by weight of the inorganic filler. Parts by weight are preferred.

(4) Carnauba wax, stearic acid and its metal salts, montan wax, etc. may be added as release agents, brominated epoxy resins, antimony dioxide, etc. may be added as flame retardants, and carbon black, etc. may be added as pigments.

(5) For the colored side, pigments such as titanium dioxide and carbon black are used.

The epoxy resin composition of the present invention can be prepared by heating the components listed above at a temperature of about 60 to 80°C using a means such as a roll, kneader, or extruder. Moreover, in the resin composition of the present invention,
After-curing after molding is preferably carried out in order to complete the curing reaction of the uncured epoxy resin in the cured product. After-curing after molding is carried out at a temperature similar to that during molding. Heat treatment may be performed for a predetermined period of time in a constant temperature bath.

[For production]

In the epoxy resin composition according to the present invention, the polyallylphenol used as a curing agent effectively acts on the epoxy resin used as the base resin to improve the heat resistance and hydrophobicity of the cured product, and furthermore, the copolymer As a result of acting effectively as a crack resistance improving material, improvements in heat resistance, flexibility and crack resistance can be realized.

〔Example〕

Next, the present invention will be described in detail with reference to Examples and Comparative Examples.

(Example I) Examples 1-9. Comparative examples 1 to 4 In this example, the following primary raw materials were used.

・Epoxy resin cresol novolasic type epoxy resin Japan Northeast EOC
N-1025 - Polyallylphenol Polyallylphenol/copolymer additive represented by formula (3) above. Ethylene/α-olefin copolymer from Mitsui Petrochemicals, available as Tafmer P P-0280.

The compositions shown in the Examples and Comparative Examples were prepared by mixing these raw materials in the amount ratios listed in Table 1 below in a pressurized double-arm kneader.
The desired composition was prepared by kneading at a temperature of 0 to 80°C.

In addition, the test pieces were prepared as follows.

First, the composition obtained by mixing wire was made into powder with 8 mesh passes, this powder was transferred to a press mold, and 200
The material was compression molded at 80 kg/d for 20 minutes at 200° C. and after-cured for 8 hours at 200° C.

Characteristics of the composition thus obtained were evaluated as follows.

・Glass transition temperature Measured using a thermomechanical analyzer (Shinku Riko) ・Bending strength According to JIS K6911.

・Crank sample after molding and cooling (lQx5X
30ms) section was evaluated using a microscope.

・Water absorption rate according to JIS K6911;
Boiling absorption rate.

The results of Examples and Comparative Examples in Example 1 are shown in Table 1, especially Examples 1 to 5 and Comparative Example 1.
From 2, adding the ethylene-α olefin copolymer improves the toughness and flexibility of the cured product, and the amount added is preferably 5 to 80 parts by weight, and the addition effect will not appear if the amount added is less than 5 parts by weight. , it can be seen that when the amount exceeds 80 parts by weight, the properties as a heat-resistant resin deteriorate.

From Examples 6 to 9 and Comparative Example 3.4, by using polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained, and the amount added is preferably 30 to 120 parts by weight. It can be seen that if the amount is less than 30 parts by weight, the curing reaction does not proceed sufficiently and a resin composition with hydrophobic and heat resistant properties cannot be obtained, and if it exceeds 120 parts by weight, the heat resistance of the cured product deteriorates.

(Example ■) Examples 10 to 18. Comparative Examples 5 to 8 The method of Example 1 (Examples 1 to 9, Comparative Examples 1 to 4) described above was repeated. However, in this example, among the raw materials, a polystyrene/polybutadiene/polystyrene end block copolymer available from Shell Chemical, available as Kraton G-1652, was used as a copolymer additive. The properties of the resulting composition were evaluated in the same manner as in Example 2 above, and the results shown in Table 2 were obtained.

From Examples 10 to 14 and Comparative Example 5.6, polystyrene/
By adding the polybutadiene/polystyrene terminal block copolymer, the toughness and flexibility of the cured product are improved, and the addition amount is preferably 5 to 80 parts by weight, and if the addition amount is less than 5 parts by weight, the addition effect will not appear. It can be seen that when the amount exceeds 80 parts by weight, the properties as a heat-resistant resin deteriorate. Example 1
5 to 18 and Comparative Example 7.8, by using polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained, and the amount added is preferably 30 to 120 parts by weight; If it is less than 1 part by weight, the curing reaction will not proceed sufficiently and a cured product with hydrophobic and heat resistant properties will not be obtained.
It can be seen that when the amount exceeds 12-0 parts by weight, the heat resistance of the cured product deteriorates.

(Example ■) Examples 19 to 27. Comparative Examples 9-12 The method of Example 1 (Examples 1-9, Comparative Examples 1-4) described above was repeated. However, in this example, among the raw materials, an ethylene/propylene ternary copolymer manufactured by Nippon Synthetic Rubber, available as JSR57P, was used as a copolymer additive. The properties of the resulting composition were evaluated in the same manner as in Example I above, and the results shown in Table 3 were obtained.

From Examples 19 to 23 and Comparative Examples 9 and 10, the addition of the ethylene/propylene ternary copolymer improved the toughness and flexibility of the cured product.

It can be seen that the amount added is preferably 5 to 80 parts by weight; if the amount added is less than 5 parts by weight, no effect of the addition is exhibited, and if it exceeds 80 parts by weight, the properties as a heat-resistant resin deteriorate. Example 24~
27 and Comparative Example 11.12, by using polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained, and the amount added is preferably 30 to 120 parts by weight, and the amount added is 30 parts by weight. It can be seen that if the amount is less than 120 parts by weight, the curing reaction will not proceed sufficiently and a cured product with excellent hydrophobicity and heat resistance properties cannot be obtained, and if it exceeds 120 parts by weight, the heat resistance of the cured product will deteriorate.

(Example ■) Examples 28 to 32. Comparative Example 13 In this example, the epoxy resin composition of Example 2 in Table 1 was filled by adding 20 to 90 wt% of silica powder (RD-8 manufactured by Tatsumori Corporation) as an inorganic filler to the entire composition. The effect of adding materials was evaluated.

By kneading the raw materials for the compositions shown in the Examples and Comparative Examples in the quantitative ratios listed in Table 4 in a pressurized double-arm kneader at a temperature of 80°C, the desired composition was prepared. did. The amount of silica powder, which is an inorganic filler, added was expressed in wt% with respect to the entire epoxy resin composition. Preparation of test piece is as per Example 1
I did the same thing. The composition obtained by mixing was made into an 8-mole bath powder, this powder was transferred to a press mold, compression molded at 200°C and 80kg/d for 20 minutes, and then after-cured at 200°C for 8 hours. A test piece with a size of 1010 x 5 x 30 was prepared. When the properties of the obtained composition were evaluated, the results shown in Table 4 were obtained. The melt viscosity was measured using a flow tester manufactured by Shimabara Seisakusho. A mixture of epoxy resin, polyallylphenol, ethylene/α-olefin, and silica powder at a predetermined mixing ratio was prepared using a pressurized double-arm kneader at a temperature of 80°C. The viscosity was measured at a temperature of 170'C.

From the results described, the bending strength is improved from 7 kg/@s'' in Example 2 to 9 to 18 kg/s by adding silica powder.The amount of silica powder added is as shown in Examples 28 to 31. Example 32 in which the amount of silica powder added is 20 wt%, which is preferably about 30 to 85 wt% of the total composition, has a bending strength of 9 kg/sn'' and the effect of addition is small, and the amount of silica powder added is 90 wt%. In Comparative Example 13, the melt viscosity at 170° C. was as high as 1000 P (voids), and workability was lowered due to lower flowability.

(Example ■) The procedure of Example I described above was repeated. However, in this example, among the raw materials, the above (2) as polyallylphenol was used.
Polyallylphenol represented by the formula was used. The properties of the obtained composition were evaluated in the same manner as in Example I described above, and the same results as in Example I were obtained.

〔Effect of the invention〕

According to the present invention, polyallylphenol is used as a curing agent and a specific copolymer is added to an epoxy resin as a base resin.

A resin composition having excellent heat resistance, flexibility, crack resistance, and hydrophobicity can be obtained.

Claims (3)

[Claims] (1) For 100 parts by weight of epoxy resin, the following formula (1)
30 to 120 parts by weight of polyallylphenol having a plurality of structural units represented by in the molecule, and ethylene/α-
Olefin copolymer, polystyrene/polybutadiene/
An epoxy resin composition comprising 5 to 80 parts by weight of a copolymer selected from the group consisting of a polystyrene end block copolymer and an ethylene/propylene ternary copolymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (2) The epoxy resin composition according to claim 1, wherein the polyallylphenol is represented by the following formula (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (3) The epoxy resin composition according to claim 1, wherein the polyallylphenol is represented by the following formula (3).