JPH0715043B2 - Epoxy resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition having improved toughness by adding a modified epoxy resin.

[0002]

2. Description of the Related Art The modification of epoxy resins has been particularly actively carried out, and its application range has been expanded. Epoxy resins are excellent in electrical properties, adhesiveness, thermal properties, etc., but are generally brittle, and there is a problem that cracks easily occur due to stress strain during curing or use, heat or mechanical impact. For this problem, use of hardeners with long-chain aliphatic groups or rubbery properties, addition of compounds with elastomeric properties, addition of asphalt substances, plasticizers such as glycols, glass fiber, aramid fiber, carbon Toughness has been achieved by adding fibers such as fibers and introducing molecular groups showing rubber elasticity into the epoxy compound itself (Koichi Ochi, Polymer 38 (3), 200 (1989)). ).

[0003]

However, these substances are not sufficiently compatible with the epoxy resin and sufficient compounding properties cannot be obtained, and the epoxy resin has excellent heat resistance and adhesive properties. However, there is a problem that the cost is very high and the cost is very high. Therefore, the compound effect cannot be sufficiently exerted, and the cost cannot be used. The present invention has been made in view of these problems, and it is an object of the present invention to provide an epoxy resin composition that provides improved toughness without reducing the heat resistance and other characteristics of the epoxy resin.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors to solve the above-mentioned problems, the general formula (I)
A bisphenol type epoxy resin represented by the formula, a curing agent, a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends, and a bisphenol type epoxy resin represented by the general formula (I) and a phenolic hydroxyl group-containing aramid represented by the general formula (II). It has been found that the toughness of the epoxy resin can be improved without reducing the properties of the epoxy resin and its cured product by containing the modified epoxy resin obtained by reacting with a polybutadiene-acrylonitrile block copolymer. The present invention has been completed.

The present invention is directed to a bisphenol type epoxy resin represented by the general formula (I), a curing agent, a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends, a bisphenol type epoxy resin represented by the general formula (I), and the following general compounds. An epoxy resin composition comprising a modified epoxy resin obtained by reacting with a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the formula (II).

[Chemical 4] (Wherein, R _{-C (CH 3) 2 -,} - CH (CH 3)
-, - CH ₂ -, or -SO ₂ -, R ¹ is -H, -CH
₃ or -Br, and n represents an integer of 0 to 70)

[Chemical 5] (In the formula, x = an integer of 3 to 7, y = 1 to an integer of 4, x /
(X + y) = 0.1 to 0.3, z = 5 to 20 integer, m = 0
~ 400 integer, n = 1-400 integer, n / (m +
n) = 0.01 to 0.50, l = 1 to an integer of 50, A is

[Chemical 6] Indicates)

The modified epoxy resin of the present invention can be obtained by reacting the epoxy resin (I) with the block copolymer (II) in a solvent. As the solvent, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like, ether solvents such as 1,4-dioxane and tetrahydrofuran are used. The amount of the epoxy resin (I) used is based on the phenolic hydroxyl group of the block copolymer (II).
It is 1 equivalent or more. The reaction temperature is 50 ° C or higher, preferably 70 ° C or higher.

In the epoxy resin composition of the present invention,
By adding 5 to 50% by weight of the polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends to the total epoxy resin in the epoxy resin composition of the present invention, the toughness is further enhanced.

In the epoxy resin composition of the present invention,
By containing a bisphenol type epoxy resin (I), a polybutadiene-acrylonitrile copolymer having a carboxyl group at both ends, a curing agent and a modified epoxy resin, the effect of further improving the toughness is shown.
The amount of the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (II) used for preparing the modified epoxy resin is the same as the total bisphenol type epoxy resin (I) in the epoxy resin composition of the present invention. On the other hand, 0.1 to 15% by weight is preferable.

In the present invention, the reason why the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (II) promotes toughness of the epoxy resin represented by the general formula (I) is not clear, but By reacting the hydroxyl group of the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile copolymer with the epoxy resin, an addition product having high compatibility with the epoxy resin can be obtained. As a result, an epoxy resin composition in which the aramid component is uniformly molecularly dispersed in the epoxy resin is obtained.

Further, by heat-curing the epoxy resin composition, the polybutadiene-acrylonitrile component causes microphase separation, and the aramid component is fixed in a state of being molecularly dispersed in the epoxy component. By this mechanism, the aramid chain having high rigidity and high glass transition point is uniformly molecularly dispersed in the epoxy resin, and not only the heat resistance and toughness of the epoxy resin composition are improved, but also the uniformly dispersed polybutadiene-acrylonitrile. Since the components also have a stress relaxation effect, it is presumed that toughening can be performed with high efficiency without lowering the heat resistance of the cured epoxy resin. The toughening modification effect of this phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer is achieved with a small amount of these copolymers added. As a result, the excellent properties of the epoxy resin composition and its cured product are not impaired.

The block copolymer (I used in the present invention
I) can be synthesized by the following method. An excess amount of oxydianiline is added to an aromatic dicarboxylic acid having a phenolic hydroxyl group and an aromatic dicarboxylic acid having no phenolic hydroxyl group, and these are added to, for example, N- in the presence of a phosphite ester and a pyridine derivative. In an organic solvent represented by methyl-2-pyrrolidone, the mixture is heated and stirred under an inert atmosphere such as nitrogen. As a result, a polybutadiene-acrylonitrile copolymer having a carboxyl group at both ends was added to the resulting polyaramid oligomer solution containing phenolic hydroxyl groups having aminoaryl groups at both ends, and the block copolymer was obtained by polycondensation. (II) is obtained. Aromatic dicarboxylic acids having a phenolic hydroxyl group include 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid, 2-hydroxyterephthalic acid, and aromatic compounds having no phenolic hydroxyl group. Examples of the dicarboxylic acid include phthalic acid, isophthalic acid and terephthalic acid, and examples of the aromatic diamine include 3,3′-oxydianiline and 3,3′-oxydianiline.
4'-oxydianiline, 4,4'-oxydianiline and the like are used.

BF Goodr is a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends.
It is commercially available from ich as Hycar CTBN, and these can be used. The degree of polymerization n in the bisphenol type epoxy resin (I) of the present invention is not particularly limited, but an average degree of polymerization of about 0 to 0.3 is good in handleability and easily obtained as a commercial product, and It is also preferable from the viewpoint of cost. Examples of the bisphenol type epoxy resin in this case include bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type and brominated products thereof. In the present invention, these epoxy resins can be used alone or as a mixture.

Examples of the curing agent used in the present invention include guanidine derivatives represented by dicyandiamide, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene and p-phenylene. Aromatic amine compounds such as diamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-benzenediamine, 1,3-di (p-aminophenyl) propane and m-xylenediamine,
Aliphatic amines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, menthenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polymethylenediamine, polyetherdiamine Compounds, polyaminoamide compounds, dodecyl succinic anhydride, polyadipic anhydride,
Aliphatic acid anhydrides such as polyazelaic acid anhydride, hexahydrophthalic anhydride, substitutional acid anhydrides such as methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol Aromatic acid anhydrides such as bis trimellitate and glycerol tris trimellitate, novolac resins such as phenol, cresol, alkylphenol, catechol, bisphenol A and bisphenol F, and halides of these phenolic resins, amino resins and urea resins , Melamine resins, dihydrazine compounds,
Polymercaptan compounds, high-melting active hydrogen compounds such as organic acid dihydrazine, tertiary amine salts represented by amine imide, imidazole salts, boron trifluoride, monomethylamine, piperidine, trifluoromethanesulfonic acid salts, etc. There is a Lewis acid or a Breasted acid salt, and a blocked isocyanate, but the present invention is not limited thereto, but a guanidine derivative is preferably used. Generally, the amount of these curing agents added to the epoxy resin is preferably in the range of 10 to 200% by weight.

Guanidine derivatives include guanidine sulfate, guanidine hydrochloride, guanidine nitrate, guanidine carbonate, methylguanidine hydrochloride, 1,1-dimethylguanidine hydrochloride and 1- (2,2-diethoxyethyl) guanidine sulfate. Salt, aminoguanidine carbonate, aminoguanidine nitrate, 1,3-diaminoguanidine hydrochloride, guanidine ethyl sulfate, dicyandiamide, 1- (o-
Trilyl) biguanide, dicyandimidine, guanidine acetic acid, guanidine thiocyanate, methylguanidine, guanidine thiourea, formylguanidine, acetylguanidine, chloroacetylguanidine, trichloroacetylguanidine, 1,2-N-diacetylguanidine,
1,3-N-diporopionylguanidine, hyprylguanidine, benzenes, luphonylguanidine, 1,3-diphenylguanidine, 1,3-diolototolylguanidine, 1-phenylguanidine, p-chlorophenylguanidine, guanyltoluene , Guanylurea, guanylhydrazine, 2-guanidinobenzeneimidazole, γ-
Examples thereof include guanidinobutyric acid and β-guanidinopropionic acid, but the present invention is not limited thereto.

Further, in the present invention, the reaction of the aramid-polybutadiene-acrylonitrile block copolymer (II) containing a phenolic hydroxyl group with the bisphenol type epoxy resin (I) and the bisphenol type epoxy resin (I), and carboxyl groups at both ends It is also possible to use a reaction accelerator for the reaction with the polybutadiene-acrylonitrile copolymer having a curing agent. As a reaction accelerator,
Phosphorus compounds such as triphenylphosphine, etc. Tertiary amine compounds such as triethylamine, tetraethanolamine, 1,8-diaza-bicyclo [5,4,0]
-7-undecene, N, N-dimethylbenzylamine,
1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N-methylpiperazine, etc.
A boron compound such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate is used.

Although the epoxy resin composition of the present invention can be formed by the above method, other additives may be added to the composition, if necessary. Other additives include natural waxes, synthetic waxes, metal salts of long-chain aliphatic acids, acid amides, esters, release agents such as paraffins, silicone rubber, nitrile rubber, butadiene rubber, polysiloxane. Etc.Stress relaxation agents, chlorinated paraffin, bromotoluene, hexabromobenzene, flame retardants such as antimony trioxide, silane coupling agents, titanate coupling agents, coupling agents such as aluminum coupling agents, fused silica , Crystalline silica, glass flakes, glass beads, glass balloons, talc,
Alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, lead, iron powder, iron oxide, metal powder such as iron sand, graphite, Inorganic fillers such as carbon, conductive particles, dyes, colorants such as pigments, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropy imparting agents, diluents, defoamers, and other resins are blended. You can also

The epoxy resin composition of the present invention includes the epoxy resin composition before heat curing and after heat curing. Production of the cured product of the epoxy resin composition of the present invention is generally
It is carried out at 250 ° C. or lower for several hours, but there is no limitation in the present invention. Further, the epoxy resin composition in the present invention also includes a molded product obtained by heat curing.

[0018]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 [Preparation of modified epoxy resin] Isophthalic acid 19.93
g (120 mmol), 3,4'-oxydianiline 3
0.63 g (153 mmol), 5-hydroxyisophthalic acid 3.64 g (20 mmol), lithium chloride 3.
9 g of calcium chloride, 12.1 g of calcium chloride, 240 ml of N-methyl-2-pyrrolidone, and 54 ml of pyridine were placed in a 1-liter 4-neck round bottom flask and dissolved by stirring, and then 74 g of triphenyl phosphite was added, The reaction was carried out at 90 ° C. for 4 hours to generate a phenolic hydroxyl group-containing aramid oligomer body.

In addition, polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends (Hycar CTBN
BF Goodrich polybutadiene acrylonitrile component contained in the acrylonitrile component is 17 mol%, a molecular weight of about 3600) 48g was added to a solution of pyridine dissolved in 240ml, and the mixture was further reacted for 4 hours, then cooled to room temperature,
This reaction solution was added to 20 liters of methanol, and an aramid-polybutadiene-acrylonitrile block copolymer containing about 14 mol% of a phenolic hydroxyl group whose content of the polybutadiene-acrylonitrile copolymer part used in the present invention was 50% by weight. The coalescence was precipitated. The precipitated polymer was further washed with methanol and refluxed with methanol for purification. The intrinsic viscosity of this polymer is 0.85 dl / g
(Dimethylacetamide, 30 ° C.). Measurement of the infrared absorption spectrum of polymer powder by diffusion reflection method, nitrile absorption based on the amide carbonyl group 1674Cm ^-1, the absorption based on C-H bonds of the butadiene part in 2856-2975Cm ^-1, the 2245 cm ^-1 Absorption based on groups was observed.

10 g of an aramid-polybutadiene-acrylonitrile block copolymer containing about 14 mol% of phenolic hydroxyl group obtained in the above step, an epoxy resin (Epicote 828, Yuka Shell Co., Ltd. average molecular weight:
380 epoxy equivalent: 190 ± 5) 90 g and 0.64 g of triphenylphosphine as a reaction accelerator were dissolved in 200 g of dimethylformamide and reacted at 90 ° C. for 2 hours. This was dried under vacuum to obtain an epoxy resin-modified product containing a reaction product of an aramid-polybutadiene-acrylonitrile block copolymer and an epoxy resin. To a solution prepared by dissolving 1 mg of this product in about 30 ml of pyridine, a color indicator of phenolic hydroxyl group (1 g of anhydrous iron (III) chloride was dissolved in 100 ml of chloroform, and 8 ml of pyridine was added, and the precipitate was filtered. Was obtained by adjusting the red solution) and stirred, but no discoloration was observed, and all the phenolic hydroxyl groups reacted with the glycidyl group and the resin contained unreacted phenol residues. Confirmed that not.

Synthesis Example 2 [Preparation of epoxy resin mixture of bisphenol type epoxy resin and polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends] Epoxy resin (Epicote 828, Yuka Shell Co., Ltd. average molecular weight: 38
0 epoxy equivalent: 190 ± 5) Polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends in 50 g (Hycar CTBN BF Goodrich Polybutadiene-
The acrylonitrile component contained in the acrylonitrile part is 27 mol% and the molecular weight is about 3400) 50 g is added,
The mixture was mixed at 130 ° C. for about 2 hours to prepare an epoxy resin composition containing 50% by weight of this polybutadiene-acrylonitrile copolymer in the epoxy resin.

Comparative Example 1 20 g of the epoxy resin mixture obtained in Synthesis Example 2, 80 g of epoxy resin (Epicoat 828, Yuka Shell Co., Ltd., average molecular weight: 380, epoxy equivalent: 190 ± 5), and curing agent 1- 60 g of 15.1 g of (o-tolyl) biguanide
After mixing and stirring at 80 ° C, 2 hours at 80 ° C, 6 ° C at 180 ° C
It was heat-cured for a time to obtain a comparative epoxy resin composition containing 10% by weight of a polybutadiene-acrylonitrile copolymer.

Example 1 Reaction formation of 20 g of the epoxy resin mixture obtained in Synthesis Example 2, 70 g of the epoxy resin used in Synthesis Example 1, the aramid-polybutadiene-acrylonitrile block copolymer obtained in Synthesis Example 1 and an epoxy resin. 10 g of the modified epoxy resin containing the compound and 14.9 g of the curing agent 1- (o-tolyl) biguanide were mixed at 60 ° C. and stirred, and then at 2 ° C. at 80 ° C.
By heating for 6 hours at 180 ° C., an epoxy resin composition of the present invention containing 10% by weight of polybutadiene-acrylonitrile copolymer and 1% by weight of aramid-polybutadiene-acrylonitrile block copolymer was obtained.

Example 2 In Example 1, 50 to 50 g of the epoxy resin was added.
10 g to 30 g of an epoxy resin modified product containing the reaction product of the aramid-polybutadiene acrylonitrile block copolymer obtained in Synthesis Example 3 and an epoxy resin.
In the same manner as above, except that the curing agent was changed from 14.9 g to 14.6 g, the polybutadiene-acrylonitrile copolymer contained 10% by weight and the aramid-polybutadiene-acrylonitrile block copolymer contained 3% by weight. An epoxy resin composition of the present invention was obtained.

Comparative Example 2 40 g of the epoxy resin mixture obtained in Synthesis Example 2, 60 g of the epoxy resin, and 13.4 g of the curing agent were mixed and stirred at 60 ° C., and then at 80 ° C. for 2 hours and at 180 ° C. for 6 hours. It was heat-cured for a time to obtain a comparative epoxy resin composition containing 20% by weight of a polybutadiene-acrylonitrile copolymer.

Example 3 In Comparative Example 2, 60 g to 50 g of the epoxy resin was added.
In the same manner as above, except that 12.9 g of the curing agent, 12.9 g, and 10 g of the modified epoxy resin obtained in Synthesis Example 1 were added to g, 20% by weight of polybutadiene-acrylonitrile copolymer and aramid- An epoxy resin composition of the present invention containing 1% by weight of a polybutadiene-acrylonitrile block copolymer was obtained.

Example 4 In Example 3, 50 g to 30 g of the epoxy resin was added.
10 g of the modified epoxy resin obtained in Synthesis Example 1
To 30 g, and from 13.3 g to 12.
Except for replacing with 9 g, polybutadiene-
20% by weight of acrylonitrile copolymer and aramid-
An epoxy resin composition of the present invention containing 3% by weight of a polybutadiene-acrylonitrile block copolymer was obtained.

Comparative Example 3 60 g of the epoxy resin mixture obtained in Synthesis Example 2, 40 g of the epoxy resin, and 11.7 g of the curing agent were mixed and stirred at 60 ° C., and then at 80 ° C. for 2 hours and at 180 ° C. for 6 hours. It was heat-cured for a period of time to obtain a comparative epoxy resin composition containing 30% by weight of a polybutadiene-acrylonitrile copolymer.

Example 5 In Comparative Example 3, 40 g to 30 g of the epoxy resin was added.
In the same manner as above, except that 11.6 g of the curing agent, 11.6 g, and 10 g of the modified epoxy resin obtained in Synthesis Example 1 were added to g, 30% by weight of polybutadiene-acrylonitrile copolymer and aramid- An epoxy resin composition of the present invention containing 1% by weight of a polybutadiene-acrylonitrile block copolymer was obtained.

Example 6 In Example 5, 30 g to 10 g of the epoxy resin was added.
10 g of the modified epoxy resin obtained in Synthesis Example 1
To 30 g, and from 11.6 g to 11.
Except for using 2 g, polybutadiene-
30% by weight of acrylonitrile copolymer and aramid-
An epoxy resin composition of the present invention containing 3% by weight of a polybutadiene-acrylonitrile block copolymer was obtained.

As described above, using the epoxy resin compositions of Comparative Examples 1 to 3 and Examples 1 to 6, pre-curing at 80 ° C. for 2 hours and then curing at 180 ° C. for 6 hours to form a cured product. Then, a test piece of 15 × 2 × 10 mm was prepared. The fracture toughness of this sample piece was measured by the following method, and the obtained results are shown in Table 1. Fracture toughness measurement: Instron type tensile tester (AGS-10
0A (manufactured by Shimadzu Corporation) according to ASTM E399-81,
The crosshead speed was 0.5 mm / min.

[0032]

TABLE 1 ──────────────────────────────── block copolymer of Example copolymer ^{a) b)} Fracture toughness Content (KgJ / m ² ) (wt%) (wt%) ────────────────────────────── Comparative Example 1 10-6.6 Example 1 1 10 1 9.3 Example 2 10 3 10.4 Comparative Example 2 20-7.6 Example 3 3 20 1 10.2 Example 4 4 20 3 10. 8 Comparative Example 3 30-8.2 Example 5 30 1 11.4 Example 6 30 3 12.3 ────────────────────────── ──────── a) Polybutadiene having carboxyl groups at both ends
Acrylonitrile copolymer b) Aramid-polybutadiene-acrylonitrile block copolymer shown in Synthesis Example 1

[0033]

The epoxy resin composition of the present invention can be used to produce an epoxy resin molded product having improved toughness.

Continuation of the front page (56) Reference JP 61-192719 (JP, A) JP 63-312315 (JP, A) JP 63-312316 (JP, A) JP 51-125466 (JP , A)

Claims (3)

[Claims] 1. A bisphenol type epoxy resin represented by the general formula (I), a curing agent, a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends, a bisphenol type epoxy resin represented by the general formula (I) and the following general formula (I): An epoxy resin composition characterized by containing a modified epoxy resin obtained by reacting the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer shown in II). [Chemical 1] (Wherein, R _{-C (CH 3) 2 -,} - CH (CH 3)
-, - CH ₂ -, or -SO ₂ -, R ¹ is -H, -CH
₃ or -Br, and n is an integer of 0 to 70) (In the formula, x = an integer of 3 to 7, y = 1 to an integer of 4, x /
(X + y) = 0.1 to 0.3, z = 5 to 20 integer, m = 0
~ 400 integer, n = 1-400 integer, n / (m +
n) = 0.01 to 0.50, l = 1 to an integer of 50, A is Indicates) 2. The epoxy resin composition according to claim 1, wherein the polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends is 5 to 50% by weight based on the bisphenol type epoxy resin represented by the general formula (I). ,
The epoxy resin according to claim 1, wherein the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (II) according to claim 1 is contained in an amount of 0.1 to 15% by weight. Composition. 3. The epoxy resin composition according to claim 1 or 2, wherein the curing agent is a guanidine derivative.