JP2001335674A - Epoxy resin composition and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition with a low viscosity and excellent dissolving/dispersing ability, the cured resin of which has high mechanical strength and good heat-cycling characteristic, and to provide a method of producing the same. SOLUTION: This epoxy resin composition comprises (A) an epoxy resin and (B)a rubber-reinforced thermoplastic resin wherein (B) is obtained by polymerizing a vinyl-based monomer (styrene or the like) in the presence of a rubbery polymer (polybutadiene latex or the like) wherein (B) comprises particles having a diameter of 50 to less than 180 nm and particles having 180 to less than 1,800 nm, and the content of the latter particles takes 80 wt.% or more (more than 90%) in the total particles, and the rate of grafted portion is 10 to 200% (preferably 50 to 55%).

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 low viscosity and excellent dissolution and dispersibility and a method for producing the same, and more particularly, to an epoxy resin composition having a high mechanical strength of a cured product thereof and excellent heat cycle properties. About things.

[0002]

2. Description of the Related Art It has been known that a cured product of an epoxy resin has excellent physical and chemical properties. For example, since they are excellent in heat resistance, corrosion resistance, electrical properties, and chemical resistance, they are used in a wide range of fields such as adhesives, paints, sealing materials, sealing materials, and laminates. However, a cured product of an epoxy resin has these excellent properties, but has a weak point of being brittle. There is a strong demand in the epoxy resin industry to compensate for this brittleness and obtain a product having excellent impact resistance and flexibility. To solve this problem, Japanese Patent Publication No. 55-33732.
As disclosed in Japanese Patent Application Publication No. 57-30133, a modified acrylonitrile-butadiene copolymer (modified NBR) into which various functional groups such as a carboxyl group which can be expected to react with an epoxy resin or a curing agent is introduced. It is used as a modifier for epoxy resins. In some applications, silicone oil modified with a functional group is also used. However, since the polymers used as these modifiers are all uncrosslinked polymers, depending on the type and curing conditions of the curing agent, the particle size of the polymer dispersed in the epoxy resin composition and the Since the distribution changes and the dispersion state of the polymer in the epoxy resin differs, there is a disadvantage that the characteristics of the cured product of the epoxy resin change.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and solves the above-mentioned problems.
Excellent dissolution and dispersibility, high mechanical strength of the cured product,
An object of the present invention is to provide an epoxy resin composition having excellent heat cycle properties and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on the relationship between the epoxy resin composition and the viscosity and dissolution and dispersibility, and the physical properties and heat cycle properties of the cured product. Reached. The epoxy resin composition of the first invention is an epoxy resin composition containing an epoxy resin (A) and a rubber-reinforced thermoplastic resin (B), wherein (B) has a particle diameter of 50 nm or more and less than 180 nm. Containing particles and particles having a particle diameter of 180 nm or more and less than 1800 nm, and a particle diameter of 50 nm or more and 1800 n.
group of vinyl-based compounds in the presence of a rubbery polymer having a distribution of particles having a particle size of less than 80% by weight (preferably at least 85% by weight, more preferably at least 90% by weight) of all particles. The polymer is obtained by polymerizing at least one monomer compound selected from the group consisting of: and a graft ratio of 10 to 200%.

[0005] The particle size distribution of the rubbery polymer is closely related to the heat cycle property and the composition viscosity. When the particle size distribution falls within the above range, the heat cycle property and the composition viscosity are improved. Further, the particle diameter is 50 nm or more and 1800
If the number of particles having a diameter of less than 80 nm is less than 80% by weight of the total particles, it is not preferable because the heat cycle property and the viscosity of the composition cannot be compatible.

The rubbery polymer particles have a particle diameter of 50 nm.
The weight ratio of the particles having a particle diameter of 180 nm or more to less than 180 nm and the particles having a particle diameter of 180 nm or more and less than 1800 nm is 1-90 / 99-10 (preferably 10-90 /
90-10, more preferably 15-85 / 85-15)
It can be. When the weight ratio falls within the range, the heat cycle property is improved. When the weight ratio is 91
In the case of ９９99 / 9〜1, heat cycleability is undesirably reduced.

The epoxy resin composition of the third invention is an epoxy resin composition containing an epoxy resin (A) and a rubber-reinforced thermoplastic resin (B), wherein the (B) has a particle diameter of 50 nm or more and 180 nm. At least one member selected from the group consisting of vinyl compounds in the presence of the first rubbery polymer (b1) containing particles of less than 80% by weight (preferably at least 85% by weight, more preferably at least 90% by weight) And a graft ratio of 10
The first rubber-reinforced thermoplastic resin (B1) which is up to 200%
And a second rubbery polymer (b) containing at least 80% by weight (preferably at least 85% by weight, more preferably at least 90% by weight) of particles having a particle diameter of 180 nm or more and less than 1800 nm.
A second rubber-reinforced thermoplastic resin (B2) obtained by polymerizing at least one monomer compound selected from the group of vinyl compounds in the presence of 2) and having a graft ratio of 10 to 200%; , Is characterized.

[0008] The particle size distribution of the first rubbery polymer and the second rubbery polymer is closely related to the heat cycle property and the viscosity of the composition. If the particle size distribution and the content are within the above ranges, In addition, the balance between the heat cycle property and the viscosity of the composition becomes good. When the particle size distribution and the content of the first rubbery polymer and the second rubbery polymer do not fall within the above ranges, the balance between the heat cycle property of the epoxy resin composition and the viscosity of the composition becomes unbalanced, which is preferable. Absent.

The weight ratio of the first rubbery polymer (b1) to the second rubbery polymer (b2) is 1-90 / 99-10, as shown in the fourth invention. . When the weight ratio falls within the range, the balance between the heat cycle property and the composition viscosity is improved. Also, when the weight ratio is 91 to 9
In the case of 9 / 9-1, the above balance cannot be obtained, which is not preferable.

[0010] The method for producing an epoxy resin composition of the fifth invention comprises the steps of:
Particles having a particle diameter of 180 nm or more and less than 1800 nm, and the content of the particles having a particle diameter of 50 nm or more and less than 1800 nm is 80% by weight or more (preferably 85% by weight or more, more preferably 90% by weight or more). A rubber-reinforced thermoplastic resin (B) having a graft ratio of 10 to 200% is produced by polymerizing at least one monomer compound selected from the group of vinyl compounds in the presence of a rubbery polymer having a distribution. The rubber-reinforced thermoplastic resin (B) and the epoxy resin (A) are blended.

The method for producing an epoxy resin composition according to the sixth aspect of the present invention comprises the steps of:
0% by weight or more (preferably 85% by weight or more, more preferably 90% by weight or more) of the first rubbery polymer (b
In the presence of 1), at least one monomer compound selected from the group of vinyl compounds is polymerized to have a graft ratio of 10
The first rubber-reinforced thermoplastic resin (B1) having a particle size of 180 nm or more and less than 1800 nm is contained in an amount of 80% by weight or more (preferably 85% by weight or more, more preferably 90% by weight or more). Rubber-reinforced thermoplastic resin having a graft ratio of 10 to 200% by polymerizing at least one monomer compound selected from the group of vinyl compounds in the presence of the second rubbery polymer (b2) (B
2) is manufactured, and thereafter, the first rubber-reinforced thermoplastic resin (B1), the second rubber-reinforced thermoplastic resin (B2), and the epoxy resin (A) are blended.

The particle diameters of the rubbery polymer according to the first and fifth aspects of the present invention and the first rubbery polymer and the second rubbery polymer according to the third and sixth aspects of the present invention are as follows. Is the outer diameter of the polymer particles themselves. The particle size of the rubbery polymer can be determined by the measuring method described in Examples.

The “graft ratio” in the first, third, fifth, and sixth inventions is the ratio of the monomer compound grafted to the rubbery polymer. The graft ratio can be 10 to 200%, preferably 1
It is in the range of 5 to 180%, more preferably in the range of 20 to 150%. When the graft ratio is less than 10%, the particles are aggregated, and the dispersion in the epoxy resin is poor.
If the ratio exceeds the above, the rubber efficiency is low and the bending strength is low, and both are not preferred. When the graft ratio is in the range of 10 to 200%, the dispersibility in the epoxy resin and the physical properties of the cured product are good. In addition, this graft ratio is determined by the measuring method shown in the examples.

The "rubber polymer" is not particularly limited as long as it is a polymer showing rubber. Examples thereof include polybutadiene, hydrogenated polybutadiene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene (non-conjugated diene) copolymer, ethylene-
Hydrogenated diene such as butene-1- (non-conjugated diene) copolymer, isobutylene-isoprene copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, SEBS, etc. (Block, random or homo) (co) polymers, polyurethane rubbers and silicone rubbers. Examples of the styrene-butadiene copolymer include a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, and a hydrogenated product of a styrene-butadiene block copolymer. Preferred rubbery polymers among these are polybutadiene and styrene-
Butadiene copolymer and butadiene-acrylonitrile copolymer. The rubbery polymer of the present invention can be used alone or in combination of two or more.

The "vinyl monomer compound" used in the polymerization in the presence of the rubbery polymer includes (1) styrene, t-butylstyrene, octylstyrene, α-methylstyrene, methyl-α-methylstyrene. , P-methylstyrene, ethylstyrene, α-ethylstyrene, vinyltoluene, vinylxylene, vinylpyridine, dimethylstyrene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene,
N, N-diethyl-p-aminomethylstyrene, divinylbenzene, monochlorostyrene, dichlorostyrene,
Aromatic vinyl monomers such as trichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, vinylnaphthalene and sodium styrenesulfonate; (2) vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; (3) methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, n-hexyl acrylate,
n-octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate,
Examples include (meth) acrylate monomers such as benzyl methacrylate and glycidyl methacrylate.
Among these, preferred monomer compounds are styrene and methyl methacrylate. These can be used alone or in combination of two or more.

In addition to the above monomer compounds, if necessary, polymerizable monomer compounds such as unsaturated acid anhydrides,
Unsaturated acids, unsaturated compounds containing an amino group, imide compounds of unsaturated dicarboxylic acids and the like can be used. As unsaturated acid anhydrides, maleic anhydride, itaconic anhydride,
And citraconic anhydride. As unsaturated acids,
Examples include acrylic acid and methacrylic acid. Examples of the amino group-containing unsaturated compound include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and the like. As an imide compound of an unsaturated dicarboxylic acid, maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide,
N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like can be mentioned. These can be used alone or in combination of two or more.

The above-mentioned "epoxy resin (A)" includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, cycloaliphatic type epoxy resin, and long chain aliphatic type resin. Examples thereof include an epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, an isocyanate type epoxy resin, a dimer acid modified epoxy resin, an NBR modified epoxy resin, and a urethane modified epoxy resin, which can be selected according to the purpose of use. When a cured product is obtained, a curing agent and a curing accelerator can be applied depending on the purpose of use.

The epoxy resin composition of the present invention may contain, if necessary, known stabilizers, plasticizers, flame retardants, flame retardant auxiliaries, antioxidants, softeners, various inorganic or organic fillers, reinforcing materials, and the like. An additive such as an agent, a cross-linking agent, an antistatic agent, a coloring agent, a coupling agent, a viscosity modifier, a weathering agent, a lubricant, and silicone oil can be blended.

The above rubber-reinforced thermoplastic resin (B1, B2)
The order of production of the components does not matter. Further, the types of the vinyl monomer compounds polymerized with the rubbery polymers (b1, b2) may be the same or different. Furthermore,
The order of blending the first rubber-reinforced thermoplastic resin (B1), the second rubber-reinforced thermoplastic resin (B2), and the epoxy resin (A) does not matter.

Examples of the above polymerization method include emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.
Solution polymerization is preferably used. In producing the rubber-reinforced thermoplastic resin (B), the rubbery polymer and the vinyl monomer compound are added in a lump in the presence of the total amount of the rubber polymer. The polymerization may be carried out in a divided or continuous manner. Further, the whole or a part of the rubbery polymer may be added during the polymerization for polymerization.

When producing by emulsion polymerization, a polymerization initiator,
Chain transfer agents (molecular weight regulators), emulsifiers, water and the like are used. Examples of the polymerization initiator include a combination of an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, or paramenthane hydroperoxide, and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation. Or persulfates such as potassium persulfate, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauroyl peroxide, t-
Peroxides such as butylperoxylaurate and t-butylperoxymonocarbonate are exemplified. The polymerization initiator can be added all at once or continuously. Further, the amount of the polymerization initiator used is usually 0.1 to 3.0% by weight, preferably 0.1 to 3.0% by weight based on the total amount of the vinyl monomer compound.
~ 1.5% by weight.

Examples of the chain transfer agent include n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan and the like. Hydrocarbons such as mercaptans, tetraethylthiuram sulfide, carbon tetrachloride, ethylene bromide, and pentaphenylethane;
Terpenes, or acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycol,
and α-methylstyrene dimer. These chain transfer agents can be used alone or in combination of two or more. Examples of the method of adding the chain transfer agent include batch addition, divisional addition, continuous addition, and a combination thereof. The amount of the chain transfer agent used is 0.05 to 2.0% by weight based on the total amount of the vinyl monomer compound.

As the emulsifier used in the case of emulsion polymerization, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used. Among them, examples of the anionic surfactant include sulfates of higher alcohols, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylate, phosphorus Acid salts and the like. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenyl ether type or the like of ordinary polyethylene glycol is used. Further, as the amphoteric surfactant, a carboxylate, a sulfate, a sulfonate,
Examples of the phosphate ester salt include those having an amine salt, a quaternary ammonium salt, or the like as a cation moiety. These emulsifiers can be used alone or in a combination of two or more. Examples of the method for adding the emulsifier include batch addition, divisional addition, continuous addition, and a combination thereof. Further, the amount of the emulsifier used is about 0.3 to 5.0% by weight based on the total amount of the vinyl monomer compound. In the emulsion polymerization, a preferable polymerization temperature is 10 to 95 ° C, more preferably 30 to 95 ° C.

When the rubber-reinforced thermoplastic resin (B) is produced by emulsion polymerization, usually, the powder obtained by coagulation with a coagulant is washed with water, dried and refined into a powder. Examples of the coagulant include acids such as sulfuric acid, acetic acid, and hydrochloric acid, and inorganic salts such as magnesium sulfate, aluminum sulfate, calcium chloride, magnesium chloride, and sodium chloride. It is preferably used. In addition, spray drying with a spray dryer may be performed without coagulation. Further, atomizer coagulation, which is a spray coagulation method, may be performed. Further, in the case of the production method of the sixth invention, a method of separately pulverizing the first rubber-reinforced thermoplastic resin (B1) and the second rubber-strong or thermoplastic resin (B2), There is a method of blending (B1) and the second rubber strong or thermoplastic resin (B2) in a latex state, and then pulverizing, and any method may be used.

When a cured product of the above epoxy resin composition is obtained, the curing agent may be diethylenetriamine, triethylenetetramine, isophoronediamine, ethylenediamine, m-phenylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, piperidine, N , N'-dimethylpiperazine, 1,
4-diazadicyclo (2,2,2) octane, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), dimethyl Benzylamine, dimethylcyclohexylamine, dimethylhexylamine, dimethylaminomethylphenol, dimethylamino p-cresol, tetraethylenepentamine, N-aminoethylpiperazine, trisdimethylaminomethylphenol, dicyandiamide, 4,
4'-diaminodiphenyl sulfone, 2-n-heptadecyl imidazole, melamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, boron trifluoride-monoethylamine and the like. These can be used alone or in combination of two or more.

The amount of the curing agent used depends on the purpose,
1 to 200 parts by weight per 100 parts by weight of the epoxy resin,
Preferably, it is used in the range of 1 to 180 parts by weight. In addition, a tertiary amine is generally used as a curing accelerator,
Others include 2-ethyl-4-methylimidazole, D
BU, quaternary phosphonium salts, amine imides, triphenylphosphine and the like. The curing accelerator is used in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the epoxy resin.

The method for curing the epoxy resin composition of the present invention includes the following methods and the like, which can be appropriately selected according to the application. The curing temperature is
The temperature ranges widely from room temperature to 200 ° C., and varies greatly depending on the type of curing agent used. A method in which a rubber-reinforced thermoplastic resin (B) is directly added to an epoxy resin (A), dissolved and dispersed, and then a curing agent, a curing accelerator, and other additives are added, followed by curing at a predetermined temperature. The rubber-reinforced thermoplastic resin (B) is mixed with an organic solvent [xylene,
After dissolving and dispersing in toluene, methyl ethyl ketone, butanol, ethyl acetate, butyl acetate, cellosolve (mono or diether of methyl, ethyl or butyl) etc., add to the epoxy resin (A), evaporate the solvent and cure. A method of adding a curing agent, a curing accelerator, and other additives, and heating and curing at a predetermined temperature. In the above method, the solvent is cured without removing the solvent.

The above-mentioned epoxy resin (A), rubber-reinforced thermoplastic resin (B), curing agent and other methods of mixing can be performed by a conventional processing machine such as a disper, a kneader, a planetary mixer, a paddle mixer, an intermixer, and a homomixer. , A Banbury mixer, various extruders and the like. The epoxy resin composition of the present invention can be molded by a molding method such as compression molding, lamination molding, transfer molding, cast molding, and press molding.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, parts and percentages are by weight unless otherwise specified. Various evaluation methods are as follows.

1. Evaluation method The evaluation method used in this example is as follows. (1) Measurement of particle size distribution of rubbery polymer The particle size distribution of the rubbery polymer was measured by a light scattering method. The measurement was performed by a laser particle size analysis system “LPA-3100” manufactured by Otsuka Electronics Co., Ltd., and the particle size distribution was measured by using the cumulant method at 70 times integration.

(2) Graft ratio A certain amount (W1) (about 1.0 g) of a rubber-reinforced thermoplastic resin is weighed and placed in a 100 ml Meyer flask. Add 20 ml of acetone to this, shake for 2 hours with a shaker,
Dissolve the free (co) polymer and centrifuge 2
The mixture was centrifuged at 3,000 rpm for 1 hour to separate insoluble matter and soluble matter, and the insoluble matter was removed at 120 ° C. for 2 hours using a vacuum dryer.
After drying for a time, the soluble (W2) and insoluble (W3) components after drying
Was measured, and the graft ratio was calculated from the following equation. Soluble fraction (%) = (W2 / W1) × 100 Insoluble fraction (%) = (W3 / W1) × 100 Insoluble content (%) = [insoluble fraction / (soluble fraction + insoluble fraction) Rate)] × 100 Conversion rate of monomer in rubber-reinforced thermoplastic resin (%) = C Rubber polymer content (polymerization charge value) (%) = R Rubber weight in rubber-reinforced thermoplastic resin converted to conversion rate Combined content (%) = {R / [R + (100−R) × C / 100]} × 100 Graft rate (%) = [(insoluble content-converted rubber polymer content) / converted rubber Polymer content] x 100

(3) Viscosity The viscosity of the epoxy resin composition in which the rubber-reinforced thermoplastic resin (B) is dispersed in the epoxy resin (A) is TOKIMEC.
It was measured using a BH type viscometer manufactured by INIC Corporation. The measurement was performed at 25 ° C.

(4) Dissolution and dispersibility The state of the epoxy resin composition in which the rubber-reinforced thermoplastic resin (B) was dissolved and dispersed in the epoxy resin (A) was visually judged according to the following criteria. A: Completely dissolved and dispersed. ：: Some undissolved parts (bubbles) X: Half or more insoluble parts (bubbles) are present.

(5) Evaluation of Physical Properties of Cured Epoxy Resin Composition Flexural strength: Measured according to JIS K6911. Flexural modulus: Measured according to JIS K6911. Fracture toughness coefficient: Measured according to JIS K6911. Heat cycle test: Measured according to JIS K6911. Five cycles (n = 5) were performed for one sample, and the number of cycles was 21 times. The number of cycles when any one of the five cracks occurred was shown.

2. Preparation of Rubbery Polymer As the rubbery polymers (a) to (c), polybutadiene latex shown in Table 1 was used.

[0036]

[Table 1]

3. Preparation of Rubber-Reinforced Thermoplastic Resin (B) In a separable flask having an internal volume of 10 liters equipped with a dropping bottle, a condenser, a nitrogen inlet, and a stirrer, 65 parts of the above rubbery polymer in terms of solid content, and rosin as an emulsifier 0.1 part of potassium acid and 100 parts of water
When the temperature reached 65 ° C., 0.2 parts of sodium pyrophosphate, 0.25 parts of glucose, and ferrous sulfate 0.0
1 part, followed by 0.2 parts of cumene hydroperoxide, 28 parts of methyl methacrylate, and 1 part of styrene.
Two parts, 20 parts of water and 1 part of potassium rosinate were added dropwise over 5 hours. The polymerization conversion was 97.5%. The obtained polymer is coagulated with sulfuric acid, and the coagulated product is thoroughly washed with water and then dried to obtain a powdery rubber-reinforced thermoplastic resin (B-
1) was obtained (see Table 2). Similarly, as shown in Table 2,
Type of rubbery polymer, amount of chain transfer agent, compounding ratio,
By changing the polymerization temperature, the polymerization time and the like, rubber-reinforced thermoplastic resins (B-2) to (B-6) were obtained. Table 2 also shows the graft ratio of each rubber-reinforced thermoplastic resin.

[0038]

[Table 2]

4. Examples 1 to 3 and Comparative Examples 1 to 4 100 parts by weight of the following epoxy resin (A) was stirred with a homomixer at a rotation speed of 500 rpm, and a rubber-reinforced thermoplastic resin (B1 to 6) was gradually added. After that, the rotation speed 6,0
After raising to 00 rpm, the mixture was stirred for 2 hours. After defoaming under reduced pressure, 80 parts by weight of the following curing agent and 1.2 parts by weight of a curing accelerator described below were added and stirred at room temperature, and the epoxy resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 were added. (See Table 3). This resin composition was measured for viscosity and visually evaluated for dissolution and dispersibility. Next, this was poured into a mold and heat-cured under the conditions of 90 ° C./2 hours and 120 ° C./1 hour to obtain a cured product of the epoxy resin composition, and various evaluations were made. Table 3 shows the evaluation results. (1) Epoxy resin; Epicoat 828 (manufactured by Yuka Shell Epoxy), viscosity: 12 to 15 Pa · s, epoxy equivalent: 184 to 194 (2) Curing agent: ADEKA HARDNER H3326 (manufactured by Asahi Denka Co.) (3) Curing accelerator Ankamin K-54 [AC
(I Japan)

[0040]

[Table 3]

From the results shown in Table 3, in Comparative Example 1, the viscosity of the epoxy resin composition was high because there was no particle of 180 nm or more in the particle size distribution of the rubbery polymer. In Comparative Example 2, in the particle size distribution of the rubbery polymer, since there was no particle smaller than 180 nm, the heat cycle property of the cured epoxy resin was reduced. In Comparative Example 3, since the graft ratio was less than 10%, the particles were agglomerated and the dispersion state was reduced. As a result, the heat cycle property also deteriorated. In Comparative Example 4, since the graft ratio exceeded 200%, the rubber efficiency was low, and the bending strength was low. Furthermore, since the graft ratio is high, the interaction between the particles is strengthened by the graft chain, and as a result, the viscosity is increased. In addition, the dispersibility was poor, and the heat cycle property was also reduced. On the other hand, the epoxy resin compositions of Examples 1 to 3 and the cured products thereof were all soluble and dispersible in the epoxy resin (A) of the rubber-reinforced thermoplastic resin (B) and the epoxy resin composition [(A) + ( B)], the cured product had excellent mechanical strength and heat cycleability. In particular, if the particle size of the rubbery polymer falls within the range of the present invention, the composition exhibits a low viscosity of 30 to 35 Pa · s, and the flexural strength of the cured product is about 30% higher than that of the comparative example. . Furthermore, in the heat cycle test, no crack generation was observed at all, and it was found that thermal stability was excellent.

[0042]

The epoxy resin composition of the present invention is excellent in dissolution and dispersibility of the rubber-reinforced thermoplastic resin (B) in the epoxy resin (A) and viscosity (low viscosity). Excellent heat cycle properties. Therefore, using its properties, for example, undercoat paints for metals, powder paints, structural adhesives for civil engineering and construction, sealing agents, adhesives for electrical and electronic materials, adhesives for printed wiring,
It can be used in a wide range of fields such as adhesives for laminates and sealing materials for electronic materials. In particular, since it has excellent heat cycle properties, it is suitable for use in an environment where temperature changes from low to high are severe.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ryoichi Motoshige 1-18-1 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. F-term (reference) 4J002 BN14X BN14Y CD01W CD02W CD05W CD06W CD10W CD13W FD140 GQ05

Claims (6)

[Claims] 1. An epoxy resin composition containing an epoxy resin (A) and a rubber-reinforced thermoplastic resin (B), wherein (B) is a particle having a particle diameter of 50 nm or more and less than 180 nm; In the presence of a rubbery polymer having a distribution in which the content of particles having a diameter of from 180 nm to less than 1800 nm is at least 80% by weight of all the particles, An epoxy resin composition obtained by polymerizing at least one monomer compound selected from the group of compounds and having a graft ratio of 10 to 200%. 2. The rubbery polymer particles having a particle diameter of 50 n
The weight ratio of the particles having a particle diameter of 180 nm or more to less than 1800 nm is 1 to 90/99.
The epoxy resin composition according to claim 1, which is from 10 to 10. 3. An epoxy resin composition containing an epoxy resin (A) and a rubber-reinforced thermoplastic resin (B), wherein (B) is a powder having a particle diameter of 50 nm or more and less than 180 nm, and 80% by weight. % Of the first rubbery polymer (b
A first rubber-reinforced thermoplastic resin (B1) obtained by polymerizing at least one monomer compound selected from the group of vinyl compounds in the presence of 1) and having a graft ratio of 10 to 200%; Particles having a particle diameter of 180 nm or more and less than 1800 nm
At least one monomer compound selected from the group of vinyl compounds is polymerized in the presence of the second rubbery polymer (b2) containing not less than 10% by weight, and the graft ratio is 10%.
The second rubber reinforced thermoplastic resin (B2) which is up to 200%
And an epoxy resin composition comprising: 4. A weight ratio (b1 / b2) between the first rubbery polymer (b1) and the second rubbery polymer (b2).
The epoxy resin composition according to claim 3, wherein is from 1 to 90/99 to 10. 5. A particle having a particle diameter of 50 nm or more and less than 180 nm and a particle having a particle diameter of 180 nm or more and less than 1800 nm, wherein the content of particles having a particle diameter of 50 nm or more and less than 1800 nm is 80% by weight or more. A rubber-reinforced thermoplastic resin (B) in which at least one monomer compound selected from the group of vinyl compounds is polymerized in the presence of a rubbery polymer having a distribution, and the graft ratio is 10 to 200%.
, And blending the rubber-reinforced thermoplastic resin (B) and the epoxy resin (A). 6. A first rubbery polymer (b) containing 80% by weight or more of particles having a particle diameter of 50 nm or more and less than 180 nm.
In the presence of 1), at least one monomer compound selected from the group of vinyl compounds is polymerized to have a graft ratio of 10
A first rubber-reinforced thermoplastic resin (B1) having a particle size of from 180 nm to less than 1800 nm and containing at least 80% by weight of a second rubbery polymer (b2).
Is polymerized in the presence of at least one monomer compound selected from the group of vinyl compounds to have a graft ratio of 10 to 2
A second rubber-reinforced thermoplastic resin (B2), which is 100%, is manufactured. Thereafter, the first rubber-reinforced thermoplastic resin (B1), the second rubber-reinforced thermoplastic resin (B2), and the epoxy resin (A) are mixed. A method for producing an epoxy resin composition, which is blended.