JPH11269272A - Epoxy resin composition and cured article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide-acrylonitrile-butadiene block copolymer with a high affinity for an epoxy resin by using a specific diamine in a specified ratio for forming the polyamide blocks of the copolymer. SOLUTION: This block copolymer, represented by the formula, is prepd. by polycondensing (A) an aminoaryl-terminated polyamide formed by polycondensing an arom. dicarboxylic acid component and an arom. diamine component and (B) a carboxy-terminated acrylonitrile-butadiene copolymer. In the formula, Ar<1> and Ar<2> are each a divalent arom. group; and x, y, z, n, and m are each an integer indicating a degree of polymn. and x is 3-7, y is 1-4, z is 5-15, n is 1-50, and m is 1-20. The arom. diamine component contains at least 30 mol.% 2,2-bis(4-(4-aminophenoxy)phenyl)propane. The block copolymer has a wt. average mol.wt. of 20,000-1,000,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel block copolymer, an epoxy resin composition containing the same, and a cured product thereof.

[0002]

2. Description of the Related Art Aromatic polyamide resin is not only excellent in heat resistance but also excellent in film forming property.
Widely used in various industrial fields. However,
Aromatic polyamide resins have problems in solubility in organic solvents, and it has been difficult to make full use of their excellent heat resistance. As a solution to this problem, the present inventors have proposed polyamide-acrylonitrile-butadiene block copolymers (Japanese Patent Publication No. 6-89150, Japanese Patent Publication No. 7-5729, Japanese Patent Application No. 8-249193). It is also known that the epoxy resin can be toughened by compounding the block copolymer with an epoxy resin (Japanese Patent Application Laid-Open No. 5-86166). However, the conventionally proposed polyamide-acrylonitrile-butadiene block copolymer has good solvent solubility, but has sufficient affinity with the epoxy resin, such as requiring a solvent when complexed with the epoxy resin. Instead, there was a problem in the application in the epoxy resin field. On the other hand, the modification of epoxy resins has been actively conducted, and the biggest drawbacks are the use of long-chain aliphatic groups or hardeners with rubber-like properties, the addition of compounds with elastomeric properties, Toughening is performed by adding agents and inorganic fibers. However, these substances are not sufficiently compatible with the epoxy resin, and sufficient composite properties have not been obtained.
Further, when combined, there is a fatal problem that the excellent heat resistance of the epoxy resin is impaired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems in the prior art. Accordingly, an object of the present invention is to provide a novel block copolymer having a high affinity for an epoxy resin, and an epoxy resin composition in which the block copolymer has improved the impact resistance of an epoxy resin and a cured product thereof. To provide.

[0004]

The present inventors have conducted various studies to solve the problems in the prior art, and as a result, when producing a polyamide-acrylonitrile-butadiene block copolymer, the present inventors have specified the formation of the amide. It has been found that the above problem can be solved by using a diamine. Further, they have found that the toughening of the epoxy resin can be achieved by compounding the block copolymer with an epoxy resin, and completed the present invention. The present invention is a polyamide having an aminoaryl group at both terminals formed by polycondensation of an aromatic dicarboxylic acid and an aromatic diamine,
Acrylonitrile having carboxyl groups at both ends
A block copolymer comprising a polycondensate with a butadiene copolymer and represented by the following general formula (1), wherein the aromatic diamine has at least 2,2'-bis (4- (4-aminophenoxy) Phenyl) propane is contained in an amount of 30 mol% or more, and has a weight average molecular weight of 20,000 to 1,000,000.
(Polystyrene equivalent)
It is an acrylonitrile-butadiene block copolymer.

Embedded image (Wherein, Ar ¹ and Ar ² represent a divalent aromatic group, and X and
Y, Z, n and m are each an average degree of polymerization,
X = 3-7, Y = 1-4, Z = 5-15, n = 1-5
0, m = an integer of 1 to 20)

The aromatic dicarboxylic acid used for the polyamide constituting the present invention includes, for example, isophthalic acid,
Terephthalic acid, 4,4'-biphenyldicarboxylic acid,
3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyl dibenzoic acid, 4,
4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, phenylmalonic acid, benzylmalonic acid, phenylsuccinic acid, phenylglutaric acid, homophthalic acid, 1,
3-phenylene diacetate, 1,4-phenylene diacetate, 4
-Carboxyphenylacetic acid, 5-bromo-N- (carbomethyl) anthranilic acid, 3,3'-bis (4-carboxyphenyl) propane, bis (4-carboxyphenyl) methane, 3,3'-bis (4-carboxy) Phenyl) hexapropane, 3,5-dicarboxybenzenesulfonic acid, 3,4-dicarboxybenzenesulfonic acid,
5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,5-dihydroxy-1,4-benzenediacetic acid, 4-hydroxy-2,5-dicarboxy Pyridine, 2-hydroxyterephthalic acid and the like can be mentioned. Phthalic acid and its derivatives are preferred. These may be used in combination. In the present invention, a block copolymer of the general formula (1) can be produced by adding a dicarboxylic acid having a phenolic hydroxyl group to these dicarboxylic acids.

Examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4'-diaminodiphenyl ether,
3,3-methyl-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,
4'-diaminodiphenylthioether, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6
-Naphthalenediamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,
3'-dihydroxy-4,4'-diaminobiphenyl,
3,3'-diaminobiphenyl, m-xylenediamine, p-xylenediamine, 1,3-bis (methaminophenyl) -1,1,3,3-tetramethyldisiloxane, 4,4'-diaminodiphenyl Sulfoxide,
4,4'-diaminodiphenyl sulfone, 4,4'-bis (3-aminophenoxydiphenyl sulfone, 3,
3'-bis (4-aminophenoxydiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,3-
Bis (4-aminophenoxy) benzene, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4 '
-Diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenoxy) benzophenone, 4,4'-bis (3-aminophenoxy) benzophenone, 4,4'-bis (3-amino Phenylmercapto) benzophenone, 2,2'-bis (3
-Aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-hydroxy-3-aminophenyl) hexafluoropropane,
2,2'-bis (4- (4-aminophenyl) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-4-aminophenoxy) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-5-aminophenoxy) hexafluoropropane,
2,2'-bis (4- (3-trifluoromethyl-5-
Aminophenoxy) hexafluoropropane, 2,2 '
-Bis (4- (4-trifluoromethyl-5-aminophenoxy) hexafluoropropane, 2,2'-bis (4- (2-nonafluorobutyl-5-aminophenoxy) hexafluoropropane, 2,2 ' -Screw (4-
(4-nonafluorobutyl-5-aminophenoxy) hexafluoropropane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,5 -Diaminopyridine, bis (4-amino-3
-Methylphenyl) methane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, bis (4 -Amino-3-ethyl-
5-methylphenyl) methane, bis (4-amino-3,
5-diethylphenyl) methane, bis (4-amino-3)
-Propylphenyl) methane, bis (4-amino-3,
5-dipropylphenyl) methane, bis (4-amino-
3-Isopropylphenyl) methane, bis (4-amino-
3,5-diisopropylphenyl) methane, bis (4-
Amino-3-isopropylpropyl) methane, bis (4-
Amino-3,5-diisopropylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane and the like. These may be used in combination.

In the acrylonitrile-butadiene copolymer having carboxyl groups at both ends, the stereochemical structure of the double bond may be either a cis structure or a trans structure. The average degree of polymerization Z is 5 to 15 in consideration of the tensile strength and the tensile modulus of the normally produced block copolymer.
Is suitable. As such an acrylonitrile-butadiene copolymer, Hycar CTBN or the like manufactured by Goodrich is commercially available, and these can be used.

The polyamide of the present invention-acrylonitrile-
Butadiene copolymer is composed of aromatic dicarboxylic acid and 2,2 '
Reacting -bis (4- (4-aminophenoxy) phenyl) propane (hereinafter referred to as compound A) to obtain a polyamide, and reacting the polyamide with a butadiene-acrylonitrile copolymer having carboxyl groups at both ends. Manufactured from The step of reacting the aromatic dicarboxylic acid with the compound A to obtain a polyamide can be easily performed by a known polycondensation reaction. The step of reacting the polyamide with a butadiene-acrylonitrile copolymer having carboxyl groups at both ends can also be easily performed by a known polycondensation reaction. Specifically, an excess amount of an aromatic diamine is added to an aromatic dicarboxylic acid, and these are added to an organic solvent such as N-methyl-2-pyrrolidone and dimethylacetamide in the presence of, for example, a phosphite and a pyridine derivative. In an inert atmosphere, a solution of an aramid oligomer having an aminoaryl group at each end is formed by heat polymerization, and then an acrylonitrile-butadiene copolymer having a carboxyl group at each end is added to this aramid oligomer solution. Is added and polycondensed to obtain the polyamide-acrylonitrile-butadiene block copolymer of the present invention. At the time of this polycondensation reaction, lithium chloride, calcium chloride or the like may be added as a stabilizer, if necessary.

The intrinsic viscosity of the block copolymer of the present invention is 0.1 to 3.0 dl / g, especially 0.2 to 2.0 dl / g.
Is preferred. When the intrinsic viscosity value is lower than 0.1 dl / g, film formation is poor, and toughness when combined with an epoxy resin is not exhibited. On the other hand, if it is higher than 3.0 dl / g, the processability deteriorates, so that it becomes somewhat difficult to form a composite with an epoxy resin. The intrinsic viscosity value is a value measured at 30 ° C. of a dimethylacetamide solution having a sample concentration of 0.5 g / dl. An Ostwald viscometer No. 1 was used for the measurement. The weight average molecular weight of the block copolymer of the present invention is 20,000 to 10,000.
00 (in terms of styrene), preferably 50,000 to 500
000. The molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. Column: Shodex KD-806M, constant temperature bath (column)
Temperature: 40 ° C., detector: RI, eluent: 0.1% by weight L
a solution of iBr in NMP (N-methyl-2-pyrrolidone),
Flow rate: 0.5 ml / min, sample amount: 1 mg / 10 m
l.

The epoxy resin used in the present invention includes, for example, glycidyl ethers, glycidyl esters, glycidylamines, linear aliphatic epoxides, alicyclic epoxides, hydantoin epoxides and the like. Examples of the glycidyl ether include glycidyl ether of bisphenol, polyglycidyl ether of phenol novolak, glycidyl ether of alkylene glycol or polyalkylene glycol, and the like. Examples of the glycidyl ether of bisphenol include diphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrachlorobisphenol A, and tetrabromobisphenol A. The glycidyl ether of the polyglycidyl ether of phenol novolak is, for example, a polyglycidyl ether of a novolak resin such as phenol novolac, cresol novolac, and brominated phenol novolak is a glycidyl ether of alkylene glycol or polyalkylene glycol, for example, polyethylene glycol Of glycols such as polypropylene, polypropylene glycol and butanediol Ether and the like. Examples of glycidyl esters include glycidyl esters of hexahydrophthalic acid and dimer acid, and examples of glycidylamines include triglycidylaminodiphenylmethane, triglycidylaminophenol, and triglycidyl isocyanurate. Examples of the linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil. Examples of the alicyclic epoxides include 3,4-epoxy-
6-methylcyclohexylmethyl carboxylate,
3,4-epoxycyclohexylmethyl carboxylate, hydrogenated bisphenol epoxy, and the like. Examples of the hydantoin type epoxide include diglycidyl hydantoin, glycidylglycidoxyalkylhydantoin, and the like. These may be used in combination of two or more. In particular, divalent phenolol glycidyl ether type epoxy resins are preferred.

When the epoxy resin composition of the present invention and a curing agent are uniformly mixed and cured, a toughened epoxy resin cured product is obtained. The epoxy resin composition and the curing agent may be mixed in a solvent. Curing takes place at around room temperature with catalysts and enzymes,
Any of room temperature curing caused by moisture, heat curing, and light curing caused by an acid generated by irradiation with ultraviolet rays may be used.
As the curing agent used in the present invention, for example, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-benzenediamine,
Aromatic diamine curing agents such as 1,3- (p-aminophenyl) propane and m-xylenediamine, ethylenediaminediethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, mentendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) aliphatic amine-based curing agents such as methane, polymethylenediamine, polyetherdiamine, polyaminoamide-based curing agents, dodecyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, etc. Aliphatic acid anhydride hardeners, aromatic acid anhydrides such as ethylene glycol bistrimellitate, glycerol tristrimellitate, phenol compounds and phenol resins, urea resins, melamine resins, and dicyandiamide. Bleed acids, di-hydrazines, imidazoles, isocyanates, blocked isocyanates, polymercapto compounds, Lewis acids, and Bronsted acid salts. Further, a curing accelerator can be used if necessary. Examples of the curing accelerator include phosphorus compounds such as triphenylsulfone, tertiary amines such as triethylamine, triethanolamine, 1,8-diazabicyclo (5,4,0) -7-undecene, N, N
Boric acid compounds such as -dimethylbenzylamine, 2-ethyl-4-methylimidazole and the like, for example, 1,8-diazabicyclo (5,4,0) -7-undecenium tetraphenylborate and the like are used.

Other additives can be added to the epoxy resin composition of the present invention. Examples of additives include natural waxes, synthetic waxes, plasticizers such as metal salts of long-chain fatty acids, release agents such as acid amides, esters, and paraffins, stress relaxation agents such as nitrile rubber, chlorinated paraffins,
Flame retardants such as bromobenzene and antimony trioxide, silane-based coupling agents, titanate-based coupling agents, fused silica, glass flakes, glass beads, glass balloons, talc, alumina, calcium silicate, aluminum hydroxide, calcium carbonate, Metal powders such as barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, lead, iron powder, iron oxide, iron sand, etc., graphite, carbon, red iron oxide, graphite, etc. Colorants such as dyes and pigments, inorganic fillers or conductive particles, inorganic fibers such as carbon fiber, glass fiber, boron fiber, silicon carbide fiber, alumina fiber, silica-alumina fiber, aramid fiber, polyester fiber, cellulose Fiber, organic fiber such as carbon fiber, oxidation stabilizer, light stabilizer,
Examples include a moisture resistance improver, a thixotropic agent, a diluent, an antifoaming agent, a resin, a tackifier, an antistatic agent, a lubricant, and an ultraviolet absorber.

The epoxy resin composition of the present invention can be obtained by heating and mixing an epoxy resin and a block copolymer (1) as a powder. At this time, if necessary, N, N
An amide-based solvent such as -dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, a mixed solvent of tetrahydrofuran, cyclohexane, a solvent in which an epoxy resin is soluble, and the above solvent may be used. If necessary, an epoxy resin curing accelerator such as triayanylphosphine, N, N-dimethylbenzene, 2-
An epoxy resin curing accelerator such as ethyl-4-methylimidazole can also be used. By using the reaction accelerator, it is possible to shorten the heating and mixing time of the epoxy resin and the block copolymer (1) and to lower the heating temperature. The temperature at the time of mixing is generally equal to or higher than the melting point of the epoxy resin.
A temperature of 130 ° C. is preferred. The amount of the epoxy resin used is 1 to 50 times, preferably 2 to 25 times the weight of the block copolymer (1). The epoxy resin composition of the present invention,
It can be used in the form of a solid, powder, paste or the like, and the shape can be selected according to the purpose of use. Also, coils,
It can be used for casting, molding, potting, sealing, bonding, coating, etc. for insulation of capacitors, diodes, transistors, ICs, thermistors, resistors, liquid crystals and the like.

[0014]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 40 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and bis (4
-Amino-3-ethyl-5-methylphenyl) methane 5
Synthesis of a polyamide-acrylonitrile-butadiene block copolymer using 9.2 mol% and 50% by weight of an acrylonitrile-butadiene copolymer. 14.28 g (85.96 mmol) of isophthalic acid, 5
2.24 g of hydroxyisophthalic acid (12.28 mm
o1), 2,2'-bis (4- (4-aminophenoxy) phenyl) propane (BAPP manufactured by Wakayama Seika Kogyo)
8.78 g (45.77 mmol), bis (4-amino-3-ethyl-5-methylphenyl) methane 18.74
g (66.36 mmol), lithium chloride 2.6 g, calcium chloride 7.8 g, N, N-dimethylacetamide 330 g, pyridine 32 g, triphenyl phosphite 70
g was placed in a 2-liter three-neck round bottom flask and reacted at 95 ° C. for 2 hours with stirring to produce a polyamide having an aminoaryl group at the terminal. X = 5, y =
Acrylonitrile-butadiene copolymer having carboxyl groups at both ends of 1, z = 11 (Hycar CTBN1300 × 8
50 g (13.89 mmol) from N, N
-A solution dissolved in 195 g of dimethylacetamide was added, and the mixture was further reacted for 2 hours, and then cooled to room temperature. This reaction solution was charged into 5 liters of methanol, the content of the acrylonitrile-butadiene copolymer was about 50% by weight, and the content of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane in the aromatic diamine. Content is 40.8mo
1% of a polyamide-acrylonitrile-butadiene block was precipitated. The precipitate was further washed with methanol, purified, and dried to obtain a polyamide-acrylonitrile-butadiene block copolymer of the present invention in a yield of 98%. The weight average molecular weight of this block copolymer is 2350
00. The intrinsic viscosity is 0.5 g / dl of a polymer solution in N, N-dimethylacetamide at 30 ° C.
Was 0.67 dl / g. Further, the IR spectrum (KBr tablet method) was measured to confirm the structure. As a result, an absorption based on an amide carbonyl group was observed around 1650 cm ⁻¹ , an absorption based on a nitrile group was observed near 2240 cm ⁻¹ , and a compound was detected near 2900 cm ⁻¹ . A (2,2'-bis (4- (4-aminophenoxy) phenyl) propane)
The absorption based on the alkyl group derived from was recognized, and it was confirmed that the compound was the target compound.

Example 2 32.8 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and 3
Synthesis of a polyamide-acrylonitrile-butadiene block copolymer using 47.2% by mole of 4'-oxydianiline and 50% by weight of an acrylonitrile-butadiene copolymer. The amount of the raw material used in Example 1 was changed to isophthalic acid16.
96 g (102.13 mmol), 2-hydroxyisophthalic acid 2.66 g (14.59 mmol), 2,2 '
-Bis (4- (4-aminophenoxy) phenyl) propane was changed to 17.60 g (42.89 mmol) and triphenyl phosphite to 81 g, and bis (4-amino-3-ethyl-5-methylphenyl) methane was changed to A polyamide-acrylonitrile-butadiene block copolymer (containing an acrylonitrile-butadiene copolymer) of the present invention in the same manner as in Example 1 except that the amount was changed to 17.56 g (87.69 mmol) of 3,4′-oxydianiline. About 50
% By weight of 2,2'-bis (4- (4
-Aminophenoxy) phenyl) propane content of 3
2.8 mol%) in 97% yield. The weight average molecular weight of this block copolymer was 210,000. The intrinsic viscosity was 0.65 dl / g. Also, IR
Measured spectrum (KBr tablet method), was to confirm the structure, from absorption due to the amide carbonyl group near 1650 cm ^-1 is absorption based on nitrile group near 2240 cm ^-1 is the compound A in the vicinity of 2900 cm ^-1 Absorption based on the alkyl group was observed, confirming that the compound was the target compound.

Example 3 58.8 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and 1,1
3-bis (4-aminophenoxy) benzene 41.2m
% of the acrylonitrile-butadiene copolymer is 50% by weight.
Synthesis of butadiene block copolymer. The amount of the raw materials used in Example 1 was changed to isophthalic acid 2.1.
4 g (12.86 mmol), 14.05 g (77.16 mmol) of 5-hydroxyisophthalic acid, 2,2'-
Bis (4- (4-aminophenoxy) phenyl) propane was changed to 25.06 g (61.05 mmol) and triphenyl phosphite to 65 g, and bis (4-amino-3-ethyl-5-methylphenyl) methane was changed to 1 , 3-bis (4-
12.53 g of aminophenoxy) benzene (42.86)
mmol) in the same manner as in Example 1 except that the content of the polyamide-acrylonitrile-butadiene block copolymer (acrylonitrile-butadiene copolymer is about 50% by weight, 2,2% in the aromatic diamine). 2 '
-Bis (4- (4-aminophenoxy) phenyl) propane content was 58.8 mol%) in a yield of 95%. The weight average molecular weight of this block copolymer is 1800
00. The intrinsic viscosity was 0.60 dl / g. Also, the IR spectrum (KBr tablet method) was measured,
When checking structure, 1655 cm ^-1 vicinity based on the amide carbonyl group absorption, absorption based on the nitrile group near 2240 cm ^-1 is 2900 cm around ^-1 Compound A
The absorption based on the alkyl group derived from was recognized, and it was confirmed that the compound was the target compound.

EXAMPLE 4 72.7 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and bis (4-amino-3,5-diethylphenyl) methane 2
Synthesis of a polyamide-acrylonitrile-butadiene block copolymer in which acrylonitrile-butadiene copolymer is 50% by weight using 7.3 mol%. 11. The amount of the raw materials used in Example 1 was changed to isophthalic acid.
47 g (75.06 mmol), 5-hydroxyisophthalic acid 2.28 g (12.51 mmol), 2,2'-
Bis (4- (4-aminophenoxy) phenyl) propane was changed to 30.29 g (73.81 mmol) and triphenyl phosphite to 63 g, and bis (4-amino-3-ethyl-5-methylphenyl) methane was changed to bis (4-amino-3-ethyl-5-methylphenyl) methane. (4-amino-
8.58 g of 3,5-diethylphenyl) methane (27.
65 mmol), and the polyamide-acrylonitrile-butadiene block copolymer of the present invention (acrylonitrile-butadiene copolymer content was about 50% by weight, 2,2% in the aromatic diamine). 2'-Bis (4- (4-aminophenoxy) phenyl) propane content was 72.7 mol%, and the yield was 95%. The weight average molecular weight of this block copolymer was 180,000. The intrinsic viscosity is 0.61 dl
/ G. Also, by measuring its IR spectrum (KBr tablet method), was to confirm the structure, absorption based on the amide carbonyl group near 1655 cm ^-1 is absorption based on nitrile group near 2240 cm ^-1 The compound near 2900 cm ^-1 Absorption based on the alkyl group derived from A was observed, and it was confirmed that the compound was the target compound.

Example 5 A polyamide-acrylonitrile-butadiene block copolymer containing 100 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and 50% by weight of an acrylonitrile-butadiene copolymer in an aromatic diamine. Synthesis of polymer. 11. The amount of the raw materials used in Example 1 was changed to isophthalic acid.
01g (72.31 mmol), 1.88 g (10.33 mmol) 5-hydroxyisophthalic acid, 2,2'-
Bis (4- (4-aminophenoxy) phenyl) propane was changed to 39.62 g (96.54 mmol) and triphenyl phosphite to 60 g, and bis (4-amino-3-ethyl-5-methylphenyl) methane was used. A polyamide-acrylonitrile-butadiene block copolymer of the present invention (the content of the acrylonitrile-butadiene copolymer was about 50% by weight,
The content of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane in the aromatic diamine is 100 mo
1%) in a yield of 95%. The weight average molecular weight of this block copolymer was 195,000. The intrinsic viscosity was 0.62 dl / g. Further, the IR spectrum (KBr tablet method) was measured and the structure was confirmed.
The absorption based on the amide carbonyl group at around 55 cm ^-1
At around 2240 cm ^{−1, the} absorption based on the nitrile group was 29%.
An absorption based on an alkyl group derived from Compound A was observed at around 00 cm ^−1, confirming that the compound was the target compound.

Comparative Example 1 An aromatic diamine was prepared by adding 0 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and bis (4-
(Amino-3-ethyl-5-methylphenyl) methane 10
Synthesis of a polyamide-acrylonitrile-butadiene block copolymer with 50% by weight acrylonitrile-butadiene copolymer using 0 mmol%. The amount of the raw materials used in Example 1 was changed to isophthalic acid
99 g (96.24 mmol), 2.92 g (16.04 mol) of 5-hydroxyisophthalic acid, bis (4-amino-3-ethyl-5-methylphenyl) methane 35.
63 g (126.17 mol) and 78 g of triphenyl phosphite were used in the same manner as in Example 1 except that 2,2'-bis (4- (4-aminophenoxy) phenyl) propane was not used. A polyamide-acrylonitrile-butadiene block copolymer for comparison (having an acrylonitrile-butadiene copolymer content of about 50% by weight and 2,2'-bis (4- (4-aminophenoxy) phenyl) in an aromatic diamine; ) Propane content is 0mo
1%) in a yield of 95%. The weight average molecular weight of this block copolymer was 175,000. The intrinsic viscosity was 0.60 dl / g. Further, the IR spectrum (KBr tablet method) was measured and the structure was confirmed.
The absorption based on the amide carbonyl group at around 55 cm ^-1
An absorption based on a nitrile group was observed at around 2240 cm ^−1, confirming that the compound was the target compound.

Comparative Example 2 Aromatic diamine was prepared by adding 0 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and 3,4'-
Synthesis of a polyamide-acrylonitrile-butadiene block copolymer containing 50% by weight of an acrylonitrile-butadiene copolymer using 100 mmol% of oxydianiline. The amount of the raw material used in Example 1 was 20.
43 g (123.0 mmol), 3.73 g (20.5 mmol) of 5-hydroxyisophthalic acid and 98 g of triphenyl phosphite were changed to bis (4-amino-3-ethyl-5-methylphenyl) methane and 2,2 2'-bis (4
-(4-Aminophenoxy) phenyl) propane is converted to 3,
In the same manner as in Example 1 except that the content was changed to 4'-oxydianiline (31.52 g / mmol), a comparative polyamide-acrylonitrile-butadiene block copolymer (content of the acrylonitrile-butadiene copolymer was about 50%).
% By weight of 2,2'-bis (4- (4
-Aminophenoxy) phenylpropane content of 0 m
ol%) in a yield of 97%. The weight average molecular weight of this block copolymer was 165,000. The intrinsic viscosity was 0.57 dl / g. In addition, the IR spectrum (KBr tablet method) was measured and the structure was confirmed.
655cm based on the amide carbonyl group near ^-1 absorption, observed absorption based on nitrile group near 2240 cm ^-1, it was confirmed that the compound of interest.

Comparative Example 3 0 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and 100 mmol% of 1,3-bis (4-aminophenoxy) benzene were added to an aromatic diamine.
Acrylonitrile-butadiene copolymer using
Synthesis of a polyamide-acrylonitrile-butadiene block copolymer at 0% by weight. The amount of the raw material used in Example 1 was changed to isophthalic acid 2.5.
3 g (15.22 mmol), 5-hydroxyisophthalic acid 16.63 g (91.32 mol) and triphenyl phosphite 75 g were changed to bis (4-amino-3-ethyl-5-methylphenyl) methane and 2,2 2'-bis (4
-(4-Aminophenoxy) phenyl) propane is
3-bis (4-aminophenoxy) benzene 35.20
g (120.44 mmol) in the same manner as in Example 1, except that polyamide-acrylonitrile-
Butadiene block copolymer (content of acrylonitrile-butadiene copolymer is about 50% by weight, 2,2'-bis (4- (4-aminophenoxy)) in aromatic diamine
Phenylpropane content was 0 mol%) in a yield of 97%. The weight average molecular weight of this block copolymer is 1
65,000. The intrinsic viscosity is 0.58 dl /
g. Also, by measuring its IR spectrum (KBr tablet method), it was to confirm the structure, absorption based on the amide carbonyl group near 1655 cm ^-1 is observed absorption based on nitrile group near 2240 cm ^-1, with a compound of interest It was confirmed that there was.

COMPARATIVE EXAMPLE 4 Aromatic diamine was prepared by adding 0 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and bis (4-
Amino-3,5-diethylphenyl) methane 100 mm
% acrylonitrile-butadiene copolymer using 50% by weight of polyamide-acrylonitrile
Synthesis of butadiene block copolymer. The amount of the raw material used in Example 1 was changed to isophthalic acid 2.5.
3 g (15.22 mmol), 5-hydroxyisophthalic acid 16.63 g (91.32 mol) and triphenyl phosphite 75 g were changed to bis (4-amino-3-ethyl-5-methylphenyl) methane and 2,2 2'-bis (4
-(4-Aminophenoxy) phenyl) propane is
3-bis (4-aminophenoxy) benzene 35.20
g (120.44 mmol) in the same manner as in Example 1, except that polyamide-acrylonitrile-
Butadiene block copolymer (content of acrylonitrile-butadiene copolymer is about 50% by weight, 2,2'-bis (4- (4-aminophenoxy)) in aromatic diamine
Phenyl) propane was obtained with a yield of 97%. The weight average molecular weight of this block copolymer was 175,000. The intrinsic viscosity is 0.58 dl
/ G. Also, by measuring its IR spectrum (KBr tablet method), it was to confirm the structure, absorption based on the amide carbonyl group near 1655 cm ^-1 is observed absorption based on nitrile group near 2240 cm ^-1, with a compound of interest It was confirmed that there was.

COMPARATIVE EXAMPLE 5 18.7 mol% of 2,2'-bis (4- (4-aminophenoxy) phenyl) propane and bis (4-amino-3-ethyl-5-phenyl) methane 8 were added to an aromatic diamine.
Synthesis of a polyamide-acrylonitrile-butadiene block copolymer in which the acrylonitrile-butadiene copolymer is 50% by weight using 1.3 mmol%. The amount of the raw materials used in Example 1 was changed to isophthalic acid
34 g (92.33 mmol), 5-hydroxyisophthalic acid 2.40 g (13.19 mol), 2,2'-bis (4- (4-aminophenoxy) phenyl) propane 9.14 g (22.28 mol), bis ( 4-amino-
27.43 g of 3-ethyl-5-phenyl) methane (9
7.13 mol), a polyamide for comparison was prepared in the same manner as in Example 1 except that 74 g of triphenyl phosphite was used.
Acrylonitrile-butadiene block copolymer (content of acrylonitrile-butadiene copolymer is about 50% by weight, 2,2'-bis (4- (4- (4-
Aminophenoxy) phenyl) propane content is 1
8.7 mol%) in a 92% yield. The weight average molecular weight of this block copolymer was 170,000. The intrinsic viscosity was 0.58 dl / g. Also, IR
Spectrum was measured (KBr tablet method), was to confirm the structure, absorption based on the amide carbonyl group near 1655 cm ^-1 is absorption based on nitrile group near 2240 cm ^-1 is 2900 cm ^-1 near the formula (2) Absorption based on the alkyl group derived from the aromatic diamine was recognized, and it was confirmed that the compound was the target compound.

Example 6 Bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 190 ± 5) 90 g
Then, 10 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 1 and 0.2 g of dimethylbenzylamine as a reaction accelerator were added, and mixed at 120 ° C. After 1 hour, 10% by weight of a polyamide-acrylonitrile-butadiene block copolymer was added to the epoxy resin.
The resulting homogeneous and transparent epoxy resin composition was obtained.

Example 7 Bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 190 ± 5) 90 g
Then, 10 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 2 and 0.2 g of dimethylbenzylamine as a reaction accelerator were added thereto, followed by mixing at 120 ° C. After 1 hour, 10% by weight of a polyamide-acrylonitrile-butadiene block copolymer was added to the epoxy resin.
The resulting homogeneous and transparent epoxy resin composition was obtained.

Example 8 Bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 190 ± 5) 90 g
Then, 10 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 3 and 0.2 g of dimethylbenzylamine as a reaction accelerator were added, and mixed at 120 ° C. After 1 hour, 10% by weight of a polyamide-acrylonitrile-butadiene block copolymer was added to the epoxy resin.
The resulting homogeneous and transparent epoxy resin composition was obtained.

Example 9 Bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 190 ± 5) 90
g, 10 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 4 and 0.2 g of dimethylbenzylamine as a reaction accelerator were added and mixed at 120 ° C. After 1 hour, a uniform and transparent epoxy resin composition containing 10% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Example 10 The polyamide-acrylonitrile-butadiene block obtained in Example 2 was added to 95 g of bisphenol A type epoxy resin (Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 925 ± 50, softening point: 97 ° C.). 5 g of polymer
And 0.5 g of triphenylphosphine as a reaction accelerator were added and mixed at 130 ° C. After 1 hour, a uniform and transparent epoxy resin composition containing 5% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Example 11 An o-cresol novolak type epoxy resin (YDCN-701,
Toto Kasei Co., Ltd., epoxy equivalent 215 ± 15, softening point 65
C) 95 g, 5 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 3, and 0.5 g of 2-ethyl-4-methylimidazole as a reaction accelerator.
g was added and mixed at 130 ° C. After 1 hour, a uniform and transparent epoxy resin composition containing 5% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Example 12 Tetrabromobisphenol A type epoxy resin (YDB-36)
0, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 360 ± 10, softening point: 57 ° C.) 95 g, 5 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 4, and 2-ethyl-4- as a reaction accelerator. 0.5 g of methyl imidazole was added and mixed at 130 ° C. After 1 hour, a uniform and transparent epoxy resin composition containing 5% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Example 13 Bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 190 ± 5) 90
g, 10 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 5 and 0.2 g of dimethylbenzylamine as a reaction accelerator were added, and mixed at 120 ° C. After 30 minutes, a uniform and transparent epoxy resin composition containing 10% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Example 14 The polyamide-acrylonitrile-butadiene block obtained in Example 5 was added to 95 g of bisphenol A type epoxy resin (Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 925 ± 50, softening point: 97 ° C.). 5 g of polymer
And 0.5 g of triphenylphosphine as a reaction accelerator were added and mixed at 130 ° C. After 30 minutes, a uniform and transparent epoxy resin composition containing 5% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Example 15 o-Cresol novolak type epoxy resin (YDCN-701,
Toto Kasei Co., Ltd., epoxy equivalent 215 ± 15, softening point 65
C) 95 g, 5 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 5, and 0.5 g of 2-ethyl-4-methylimidazole as a reaction accelerator.
g was added and mixed at 130 ° C. After 30 minutes, a uniform and transparent epoxy resin composition containing 5% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Example 16 Tetrabromobisphenol A type epoxy resin (YDB-36)
0, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 360 ± 10, softening point: 57 ° C.) 95 g, 5 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Example 5, and 2-ethyl-4- as a reaction accelerator. 0.5 g of methyl imidazole was added and mixed at 130 ° C. After 30 minutes, a uniform and transparent epoxy resin composition containing 5% by weight of a polyamide-acrylonitrile-butadiene block copolymer in the epoxy resin was obtained.

Comparative Example 6 Bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., epoxy equivalent 190 ± 5) 90
g, 10 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Comparative Example 1 and 0.2 g of dimethylbenzylamine as a reaction accelerator were added, and mixed at 120 ° C. However, even after mixing for 3 hours, the polyamide-acrylonitrile-butadiene block copolymer was not uniformly dispersed in the epoxy resin, and an uneven epoxy resin composition in which a part of the block remained was obtained.

Comparative Example 7 The polyamide-acrylonitrile-butadiene block obtained in Comparative Example 2 was mixed with 95 g of bisphenol A type epoxy resin (Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 925 ± 50, softening point: 97 ° C.). 5 g of polymer
And 0.5 g of triphenylphosphine as a reaction accelerator were added and mixed at 130 ° C. However, even after mixing for 3 hours, the polyamide-acrylonitrile-butadiene block copolymer was not uniformly dispersed in the epoxy resin, and an uneven epoxy resin composition in which a part of the block remained was obtained.

Comparative Example 8 o-Cresol novolak type epoxy resin (YDCN-701,
Toto Kasei Co., Ltd., epoxy equivalent 215 ± 15, softening point 65
C) 95 g, 5 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Comparative Example 3 and 0.5 of 2-ethyl-4-methylimidazole 0.5 as a reaction accelerator.
g was added and mixed at 130 ° C. However, even after mixing for 3 hours, the polyamide-acrylonitrile-butadiene block copolymer was not uniformly dispersed in the epoxy resin, and an uneven epoxy resin composition in which a part of the block remained was obtained.

Comparative Example 9 Tetrabromobisphenol A type epoxy resin (YDB-36)
0, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 360 ± 10, softening point: 57 ° C), 95 g, 5 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Comparative Example 4, and 2-ethyl-4- as a reaction accelerator. 0.5 g of methyl imidazole was added and mixed at 130 ° C. However, even after mixing for 3 hours, the polyamide-acrylonitrile-butadiene block copolymer was not uniformly dispersed in the epoxy resin, and an uneven epoxy resin composition in which a part of the block remained was obtained.

Comparative Example 10 Bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 190 ± 5) 90
g, 10 g of the polyamide-acrylonitrile-butadiene block copolymer obtained in Comparative Example 5 and 0.2 g of dimethylbenzylamine as a reaction accelerator were added, and mixed at 120 ° C. However, even after mixing for 3 hours, the polyamide-acrylonitrile-butadiene block copolymer was not uniformly dispersed in the epoxy resin, and an uneven epoxy resin composition in which a part of the block remained was obtained.

Examples 17 to 27 To the epoxy resin compositions obtained in Examples 6 to 16 were added 4,4'-diaminodiphenylmethane as a curing agent to obtain 1
Stir and mix at 00 ° C until uniform. The amount of the curing agent used was adjusted so that the epoxy group of each epoxy resin and the active amino group of the curing agent were equivalent. Thereafter, the mixed epoxy resin composition is cast, and the mixture is further heated at 180 ° C. for 2 hours at 180 ° C.
For 6 hours to produce a cured product of the present invention. A test piece of 30 mm × 30 mm × 5 mm (thickness) was prepared from this casting, and the impact strength of the cured product was evaluated by the following method. Table 1 shows the results.

Comparative Examples 11 to 15 In Examples 17 to 27, the epoxy resin compositions of Comparative Examples 6 to 10 were used in place of the epoxy resin compositions of Examples 6 to 16; The impact strength of the cured product was evaluated in the same manner. Table 1 shows the results.

Comparative Examples 16 to 19 4,4'-Diaminodiphenylmethane was added as a curing agent to the epoxy resin, and the mixture was stirred and mixed at 100 ° C. until uniform. The amount of the curing agent used was adjusted so that the epoxy group of each epoxy resin and the active amino group of the curing agent were equivalent.
Thereafter, the mixed epoxy resin composition was cast and heated at 80 ° C. for 2 hours and further at 180 ° C. for 6 hours to prepare a cured product of the present invention. 30mm x 30mm x 5m from this casting
An m (thickness) test piece was prepared, and the impact strength of the cured product was evaluated by the following method. Table 1 shows the results. The compound A in the table means 2,2'-bis (4- (4-aminophenoxy) phenyl) propane.

Measurement of Impact Strength (50% Breaking Energy) of Cured Product An impact test of the cured product was performed using a DuPont type tester (II-200, manufactured by Toyo Seiki Seisaku-sho, Ltd.). From the results of the impact test, a 50% breaking energy (impact energy when 50% of the number of test pieces break) was determined based on Japanese Industrial Standards (JIS-K7211 method for testing a pyramid of hard plastic). Test pieces: 20, weight mass: 300g

[0044]

[Table 1]

It can be seen that the cured epoxy resin using the block copolymer of the present invention is tougher than the cured epoxy resin alone. This example is a cured product composed of a composition obtained by mixing and dispersing (compatibility) a copolymer and an epoxy resin in a solventless system, and is a block copolymer excellent in compatibility in a solventless system. .

[0046]

As described above, the polyamide-acrylonitrile-butadiene block copolymer of the present invention comprises a conventional polyamide-acrylonitrile-butadiene block copolymer.
The affinity for the epoxy resin is improved as compared with the acrylonitrile-butadiene copolymer. This facilitates the preparation of a thermosetting composition such as an epoxy resin,
The cured product has remarkably improved impact strength, and can be applied to thermosetting resins represented by engineering plastics, adhesives, and the like.

Claims (3)

[Claims] 1. Polycondensation of a polyamide having an aminoaryl group at both terminals formed by polycondensation of an aromatic dicarboxylic acid and an aromatic diamine with an acrylonitrile-butadiene copolymer having a carboxyl group at both terminals. A block copolymer represented by the following general formula (1), wherein the aromatic diamine has at least 2,2′-
Bis (4- (4-aminophenoxy) phenyl) propane contains at least 30 mol% and has a weight average molecular weight of 2000
A polyamide-acrylonitrile-butadiene block copolymer having a molecular weight of 0 to 1,000,000 (in terms of styrene). Embedded image (Wherein, Ar ¹ and Ar ² represent a divalent aromatic group, and X and
Y, Z, n and m are each an average degree of polymerization,
X = 3-7, Y = 1-4, Z = 5-15, n = 1-5
0, m = an integer of 1 to 20) 2. An epoxy resin composition comprising the polyamide-acrylonitrile-butadiene block copolymer according to claim 1 and an epoxy resin. 3. A cured epoxy resin comprising the polyamide-acrylonitrile-butadiene block copolymer according to claim 1 and an epoxy resin.