JP3017556B2 - Modified epoxy resin and 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 a modified glycidylamine-based epoxy resin, an epoxy resin composition having improved toughness by adding the same, and a cured product thereof.

[0002]

2. Description of the Related Art Epoxy resins have been particularly actively modified, and the range of application thereof has been expanded. Epoxy resins have excellent electrical properties, adhesive properties, thermal properties, and the like, but are generally brittle and have a problem that cracks easily occur due to stress strain during curing or use, heat or mechanical impact. To solve this problem, use a curing agent having a long-chain aliphatic group or rubber-like properties, add a compound having an elastomeric property, add a plasticizer such as an asphalt substance, glycols, etc., glass fiber, aramid fiber, carbon The toughness of the epoxy compound is enhanced by the addition of fibers such as fibers and the introduction of a molecular group exhibiting rubber elasticity of the epoxy compound itself (Koichi Ochi, Polymer 38 (3), 200 (1989)).

[0003]

However, glycidylamine-based epoxy resins having excellent heat resistance, adhesiveness and chemical resistance are widely used mainly as fiber-reinforced epoxy resins, but are hard and brittle. There's a problem.
Attempts have been made to solve this problem by adding the rubber-like substance described above, but it is not possible to exert a sufficient effect because sufficient compatibility cannot be obtained, and the excellent properties of epoxy resins Impaired properties such as heat resistance and adhesiveness,
There are problems such as a very high cost. The present invention has been made in view of these problems, and it is an object of the present invention to provide a glycidylamine-based epoxy resin composition that provides improved toughness without reducing the heat resistance characteristics of the glycidylamine-based epoxy resin. .

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a glycidylamine-based epoxy resin, a curing agent and a phenolic hydroxyl group-containing aramid represented by the general formula (I). -It has been found that, by compounding a polybutadiene-acrylonitrile block copolymer as a main component, the toughness of the epoxy resin can be improved without reducing the properties of the epoxy resin and its cured product, and the present invention has been completed.

Embedded image (Where x is an integer of 3 to 7, y is an integer of 1 to 4, y /
(X + y) = 0.1 to 0.3, z = integer of 5 to 15, m
= An integer of 1 to 400, n = an integer of 1 to 400, n / (m
+ N) = 0.01 to 0.50, 1 = 1 to 50, A
r ¹ and Ar ³ represent a divalent aromatic group, and Ar ² represents a divalent aromatic group containing a phenolic hydroxyl group.

[0005] The modified epoxy resin of the present invention can be obtained by reacting a glycidylamine-based epoxy resin with a block copolymer (I) in an amide-based solvent. N, N-dimethylacetamide, N-
Methyl-2-pyrrolidone and the like are used. The amount of the epoxy resin used is 1 to 2 with respect to the block copolymer (I).
It is 0 equivalent, preferably 5 to 15 equivalent. The reaction temperature is 50 ° C. or higher, preferably 70 ° C. or higher.

In the epoxy resin composition of the present invention,
The phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (I) is preferably used in an amount of 0.1 to 15% by weight based on the epoxy resin.

In the present invention, the reason why the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile copolymer represented by the general formula (I) promotes the toughness of the glycidylamine epoxy resin is not clear, but these phenolic hydroxyl group-containing aramids are not known. -By reacting the hydroxyl group of the polybutadiene-acrylonitrile copolymer with the epoxy resin, compatibility with the epoxy resin is promoted, and an epoxy resin composition in which the aramid component is uniformly molecularly dispersed in the epoxy resin is obtained. Further, by heating and curing the epoxy resin composition, the polybutadiene-acrylonitrile component causes microphase separation, and the aramid component is fixed in a state of molecular dispersion in the epoxy component. By this mechanism, aramid chains with high rigidity and high glass transition point are molecularly dispersed in the epoxy resin, and not only the heat resistance and toughness of the epoxy resin are improved, but also the uniformly dispersed polybutadiene-acrylonitrile component has a stress moderating action. Therefore, it is estimated that the toughening is efficiently performed without lowering the heat resistance of the cured epoxy resin. The phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer has a toughening modifying effect,
This is achieved with a small amount of these copolymers. As a result, the heat resistance can be improved without impairing the excellent properties of the epoxy resin composition and the cured product thereof.

[0008] The block copolymer (I) used in the present invention can be synthesized by the following method. A dicarboxylic acid having a phenolic hydroxyl group-containing divalent aromatic group Ar ² in the general formula (I) and a divalent aromatic group A in the general formula (I)
general formula (I) in excess with respect to the dicarboxylic acid having r ¹
And a diamine having a divalent aromatic group Ar ³ in the organic solvent represented by N-methyl-2-pyrrolidone in the presence of, for example, a phosphite and a pyridine derivative. Heat and stir under an active atmosphere. As a result, the resulting phenolic hydroxyl group-containing polyaramid oligomer solution in which both ends were aminoaryl groups was added to a polybutadiene-containing carboxyl group at both ends.
An acrylonitrile copolymer is added and polycondensed to obtain a block copolymer (I).

As the Ar ² -containing dicarboxylic acid having a phenolic hydroxyl group, 4-hydroxyisophthalic acid, 5
-Hydroxyisophthalic acid, 2-hydroxyphthalic acid,
2-hydroxyterephthalic acid, Ar ¹ -containing dicarboxylic acids having no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,3′-methylene dibenzoic acid, 4'-
Methylene dibenzoic acid, 4,4'-oxydibenzoic acid,
4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'-
Carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like, but are not limited thereto. is not.
These aromatic dicarboxylic acids can be used alone or in combination.

As the above-mentioned Ar ³ -containing aromatic diamine, for example, m-phenylenediamine, p-phenylenediamine, 3,3′-oxydianiline, 3,4′-oxydianiline, 4,4′-oxydianiline Aniline, 3,3 '
-Diaminobenzophenone, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone,
Bis (4-aminophenyl) sulfide, 1,4-naphthalenediamine, 2,6-naphthalenediamine, 4,
4'-bis (4-phenoxy) diphenyl sulfone,
4,4'-bis (3-phenoxy) diphenylsulfone, 2,2 '-(4-aminophenyl) propane, bis (4-aminophenyl) methane, o-tolidine, o-dianiridine and the like can be mentioned. However, the present invention is not limited to this. These aromatic diamines can be used as a mixture.

A polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends is commercially available from Goodrich as Hycar CTBN, and these can be used.

Glycidylamine epoxy resinAs
Is tetraglycidyldiaminobenzidine,
Sidyldiaminodiphenylmethane, tetraglycidyldi
Amino diphenyl ether, tetraglycidyl diamino
Diphenyl sulfone, tetraglycidyl diamino dife
Nyl sulfone, tetraglycidyldiaminodiphenyl-
2,2'-propane, 1,4-bis (paradiglycidyl
Aminophenoxy) benzene, 2,2-bis (paradig)
Risidylaminophenoxyphenyl) propane, bis
(Paradiglycidylaminophenoxyphenyl) sulfo
Triglycidyl-paraaminophenol, triglyceride
Sidyl-metaaminophenol, tetraglycidylbis
Aminomethylcyclohexane, diglycidylamine naph
Tolls or their methylated or brominated productsThere
Can be. In the present invention, these epoxy resins are simply used.
It can be used alone or as a mixture.

As the curing agent used in the present invention, for example, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene, p-
Aromatic amine compounds such as phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-benzenediamine, 1,3- (p-aminophenyl) propane, and m-xylenediamine;
Aliphatic amines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polymethylenediamine and polyetherdiamine -Based compounds, polyaminoamide-based compounds, aliphatic acid anhydrides such as dodecyl succinic anhydride, polyadipic anhydride, and polyazeleic anhydride; alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride Phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, aromatic anhydrides such as ethylene glycol bis trimellitate, glycerol tristrimellitate, dicyandiamide, organic acid dihydrazide Basic active hydrogen compounds and the like,
Examples include, but are not limited to, imidazole compounds, Lewis acids and Breasted acid salts, polymercaptan compounds, phenolic resins, urea resins, melamine resins, isocyanates and blocked isocyanate compounds.

The epoxy resin composition of the present invention may contain a curing accelerator, a reaction diluent for epoxy resin, a dye, an oxidation stabilizer, a coupling agent, other resins, and the like, if necessary. Examples of the curing accelerator include phosphorus-based compounds such as triphenylphosphine and tertiary amine compounds such as triethanolamine, tetraethylamine, 1,8-diaza-bicyclo [5,4,0] -7-undecene (DBU), N, N −
Dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole,
Boron-based compounds such as N-methylpiperazine and the like, for example, 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate and the like are used.

The epoxy resin composition of the present invention preferably comprises a glycidylamine-based epoxy resin of the formula (I)
0.1 to 15% by weight of a copolymer and a curing agent of 2 to 80%
% By weight, preferably 5 to 60% by weight, and mixed. The epoxy resin composition of the present invention includes a composition comprising a modified epoxy resin, a glycidylamine-based epoxy resin, and a curing agent in a state before heat curing and a cured product after heat curing. In this case, the composition after heat curing can be supplied as various formed bodies. This heat curing is generally performed at 250 ° C. or lower for several hours, but in the present invention, this condition is not affected.

[0016]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (phenolic hydroxyl group contained in aramid portion is 2 mol%): 19.60 g (118 mmol) of isophthalic acid, 3,4'-oxydi 26.4 g (132 mmol) of aniline, 0.41 g (2.3 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, 12.1 g of calcium chloride, 240 ml of N-methyl-2-pyrrolidone and 54 ml of pyridine were added to 11-4. After placing it in a round-bottomed flask and stirring and dissolving, 74 g of triphenyl phosphite was added.
The reaction was carried out for a period of time to produce a phenolic hydroxyl group-containing aramid oligomer. A polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends (Hy
car CTBN, manufactured by BF Goodrich. A solution prepared by dissolving 48 g of acrylonitrile component contained in polybutadiene acrylonitrile part at 17 mol% and having a molecular weight of about 3600) in 240 ml of pyridine was added, and the mixture was further reacted for 4 hours.
The reaction solution is cooled to room temperature, and the reaction solution is poured into methanol 201, and an aramid-polybutadiene-acrylonitrile block containing about 2 mol% of a phenolic hydroxyl group containing 50 wt% of a polybutadiene-acrylonitrile copolymer part used in the present invention. The copolymer was precipitated. The precipitated polymer was further purified by washing with methanol and refluxing methanol. The intrinsic viscosity of this polymer is 0.85 dl
/ G (dimethylacetamide, 30 ° C). Was measured infrared spectrum by diffusion reflection method polymer powder, the amide carbonyl group to 1674cm ^-1, 285
The absorption based on C-H bonds of the butadiene part in 6-2975cm ^-1, revealed absorption based on nitrile group in 2245 cm ^-1.

Synthesis Example 2 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (phenolic hydroxyl group contained in aramid portion is 14 mol%): Synthesis Example 1
19.60 g (118 mmol) of isophthalic acid of 3,
26.4 g (132 mmol) of 4'-oxydianine,
0.41 g (2.3 mmol) of 5-hydroxyisophthalic acid
1) and polybutadiene having carboxyl groups at both terminals
48 g of the acrylonitrile copolymer was charged with 19.93 g (120 mmol) of isophthalic acid, 30.63 g (153 mmol) of 3,4'-oxydianiline and 3.64 (20 mmol) of 5-hydroxyisophthalic acid and carboxyl at both ends. Polymerization by the same procedure except that the polybutadiene-acrylonitrile copolymer having a group was changed to 55.5 g (Hycar CTBN, manufactured by BF Goodrich Co., Ltd .; acrylonitrile contained in the polybutadiene acrylonitrile portion was 17 mol% and the molecular weight was about 3600). After the same post-treatment, an aramid-polybutadiene-acrylonitrile block copolymer containing about 14 mol% of phenolic hydroxyl groups used in the present invention was precipitated. The intrinsic viscosity of this polymer is 0.82 dl / g (dimethylacetamide, 3
0 ° C). It was measured infrared spectrum by diffusion reflection method polymer powder, based amide carbonyl group 1675 cm ^-1, the absorption based on C-H bonds of the butadiene part in 2854-2971Cm ^-1, the nitrile group to 2243cm ^-1 absorption Admitted.

Example 1 After dissolving 24 g of a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer containing 2 mol% of phenolic hydroxyl groups obtained in Synthesis Example 1 in 200 g of dimethylformamide, tetraglycidylamino Phenylmethane epoxy resin (Araldide MY-720, epoxy equivalent: 115-135, CIBA
3.6 g) and 0.08 g of triphenylphosphine as a reaction accelerator were added, and the mixture was reacted at 90 ° C. for 2 hours. This was added to water to precipitate the resin, washing with warm water was repeated, and further tetrahydrofuran was added to azeotropically evaporate these solvents under reduced pressure, followed by vacuum drying, and the epoxy resin reacted with the aramid part. A resin composition was obtained. A solution of 1 mg of this product dissolved in about 30 ml of pyridine was added to a phenolic hydroxyl group color indicator (anhydrous iron chloride (II
I) 1 g was dissolved in 100 ml of chloroform, 8 ml of pyridine was further added, and the precipitate was filtered to prepare a red solution. A few drops of the solution were added and stirred, but no discoloration was observed. It was confirmed that all phenolic hydroxyl groups in the resin reacted with the glycidyl groups and were not contained.

Comparative Example 1 Tetraglycidylaminophenylmethane epoxy resin (Araldide MY-720, epoxy equivalent: 115)
To 135, manufactured by CIBA-GEIGY), 1.0 g of triethanolamine as a curing accelerator, and 4,4 as a curing agent.
30 g of 4'-diaminodiphenylsulfone was added, stirred and mixed uniformly, and then dried in vacuum to obtain a comparative epoxy resin sample.

Example 2 3.5 g of the product obtained in Example 1 and the epoxy resin 6.
5 g, 30 g of 4,4'-diaminodiphenyl sulfone as a curing agent, 1 g of tetraethylamine as a curing accelerator
Was melted and added, followed by stirring and uniform mixing to obtain an epoxy resin composition of the present invention.

Example 3 5.8 g of the product obtained in Example 1 and the epoxy resin 9
4.2 g, 30 g of 4,4'-diaminodiphenylsulfone as a curing agent, and 1 g of triethanolamine as a curing accelerator were melted, added, stirred, and uniformly mixed to obtain an epoxy resin composition of the present invention. .

Example 4 The phenolic hydroxyl group obtained in Synthesis Example 2 contained about 14 mol%
24 g of the contained aramid-polybutadiene acrylonitrile block copolymer, 9.1 g of epoxy resin, and 0.64 g of triphenylphosphine as a reaction accelerator were dissolved in 200 g of dimethylformamide, and the same operation as in Example 1 was carried out. A reaction product of a polybutadiene acrylonitrile block copolymer and an epoxy resin was obtained. To a solution obtained by dissolving 1 mg of this product in about 30 ml of pyridine, dissolve 1 g of a phenolic hydroxyl group color indicator liquid (100 g of anhydrous iron (III) chloride in 100 ml of chloroform), add 8 ml of pyridine, and filter the precipitate. Was added and stirred, but no discoloration was observed, and it was confirmed that this resin did not contain any phenolic hydroxyl groups reacted with glycidyl groups. .

Example 5 4.1 g of the product obtained in Example 4, 95.9 g of the epoxy resin, 30 g of 4,4'-diaminodiphenylsulfone as a curing agent, and 1 g of tetraethylamine as a curing accelerator The mixture was melted, added, stirred and uniformly mixed to obtain an epoxy resin composition of the present invention.

Example 6 6.9 g of the product obtained in Example 4 and the epoxy resin 9
3.1 g, curing agent 4,4'-diaminodiphenylsulfone 30 g curing accelerator tetraethylamine 1
g was melted and added, followed by stirring and uniform mixing to obtain an epoxy resin composition of the present invention.

After the epoxy resin compositions of Comparative Example 1 and Examples 2, 3, 5, and 6 were molded, they were heated at 80 ° C. for 3 hours and at 120 ° C. for 6 hours to prepare test pieces. Using this test piece, impact toughness was measured by the following method, and the obtained results are summarized in Table 1. Measurement of impact strength: Dynestst Feinm
echanic Ralf Kogel) using DIN-53453.
It went according to. The test piece was 15 × 10 × 2 (mm).

[0026]

[Table 1] a) Addition amount of block copolymer to epoxy resin b) In block copolymer, indicates mol% of hydroxyl group contained in aramid portion.

[0027]

The epoxy resin composition of the present invention exhibits, without impairing the heat resistance of the glycidyl amine-based epoxy resin cured product can be produced a molded body with improved toughness.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-222444 (JP, A) JP-A-2-133422 (JP, A) JP-A-2-135217 (JP, A) JP-A-1- 188521 (JP, A) JP-A-1-174519 (JP, A) JP-A-63-230725 (JP, A) JP-A-63-37116 (JP, A) JP-A-62-273224 (JP, A) JP-A-4-31718 (JP, A) JP-A-4-314722 (JP, A) JP-A-4-31716 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/14 C08G 59/50-59/62 C08L 63/00-63/10 C08L 53/00 C08L 87/00

Claims (3)

(57) [Claims] 1. A modified epoxy resin obtained by reacting a glycidylamine-based epoxy resin with a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (I). Embedded image (Where x is an integer of 3 to 7, y is an integer of 1 to 4, y /
(X + y) = 0.1 to 0.3, z = integer of 5 to 15, m
= An integer of 1 to 400, n = an integer of 1 to 400, n / (m
+ N) = 0.01 to 0.50, 1 = 1 to 50, A
r ¹ and Ar ³ represent a divalent aromatic group, and Ar ² represents a divalent aromatic group containing a phenolic hydroxyl group. 2. An epoxy resin composition comprising the modified epoxy resin according to claim 1, a glycidylamine-based epoxy resin, and a curing agent. 3. The phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (I) is contained in an amount of 0.1 to 15% by weight based on a glycidylamine epoxy resin. The epoxy resin composition according to claim 2, wherein