JPH03290471A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of providing useful electronic part materials having excellent impact and beat resistance and mechanical strength with hardly any deterioration in electrical insulating properties by blending a thermosetting resin with a specific hydrogenated copolymer rubber. CONSTITUTION:A thermosetting resin composition is obtained by blending (A) 100 pts.wt. thermosetting resin with (B) 1-100 pts.wt. hydrogenated copolymer rubber, composed of a random copolymer robber composed of 30-70mol% acrylate and/or alkoxy-substituted alkyl acrylate, 20-70mol% conjugated diene and 0-10mol other ethylenically unsaturated compounds copolymerizable with the aforementioned two components. Ethylenically unsaturated compounds containing 0.1-20mol% functional groups selected from carboxy, amino, epoxy and hydroxy are used as the abovementioned ethylenically unsaturated compounds of the component (B).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention has excellent mechanical strength, impact resistance, weather resistance, electrical insulation properties, and heat resistance, and is suitable for electrical/electronic parts, automobile parts, etc. The present invention relates to a thermosetting resin composition.

[Conventional technology]

In general, thermosetting resins, especially phenolic resins and epoxy resins, have long been widely used in various molding materials and adhesive applications, taking advantage of their excellent adhesive properties, insulation properties, and heat resistance. Even with the rapid growth of the automobile industry and electrical/electronic industry in recent years, demand for it is increasing, mainly for use in various parts, taking advantage of its characteristics.

However, cured products of phenol resin and epoxy resin,
Although it is a high-strength material, it has the disadvantage of being brittle.

As a countermeasure against this problem, it has been considered to blend these resins with polar rubber or epoxy resin, or to use rubber-modified resins made by roughening phenol resins or epoxy resins and reacting them with rubber.

However, many of the conventionally used rubber materials are
By adding these to phenolic resins and epoxy resins, heat resistance may be lowered compared to when they are not added.
This was accompanied by the problem of reduced electrical insulation.

In other words, acrylonitrile-butadiene rubber (NBR), which has relatively good compatibility with phenolic resins and epoxy resins, has been used for a long time to improve the brittleness of phenolic resins and epoxy resins. Publication No. 55-33732, Special Publication No. 57-30133
NBR has been used in which various functional groups, mainly carboxyl groups, which are expected to react with thermosetting resins, have been introduced as seen in the above publication. However, the addition of these polar rubbers deteriorates the properties inherent to thermosetting resins, such as heat resistance, weather resistance, and electrical insulation.

Moreover, recent technological advances mainly in the electronics and information industries have led to demands for even better thermosetting resin materials. Conventionally, as mentioned above, polar rubber, which has relatively good compatibility, was added to thermosetting resin as a modifier, but although this method improved impact resistance, it reduced electrical insulation. It was usual. Accordingly, there has been a demand for materials that exhibit less deterioration in electrical insulation properties and that are highly effective in improving impact resistance.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned problems of the prior art, and provides an excellent thermosetting resin composition that exhibits little deterioration in electrical insulation properties and has excellent impact resistance, mechanical strength, and heat resistance. The purpose is to

[Means to solve the problem]

The present invention comprises: (1) 100 parts by weight of a thermosetting resin;
) (A) 30 to 70 mol% of an acrylic acid alkyl ester and/or an acrylic acid alkoxy-substituted alkyl ester, (B) 20 to 70 mol% of a conjugated diene, and (C) copolymerized with the components (A) to (B) above. Possible other ethylenically unsaturated compounds 0 to 10 mol% [where (A) + (B)
consisting of a random copolymer rubber C (hereinafter referred to as r copolymer rubber J) having a polymerization composition of 10 (C)=I 00 mol%] and a weight average molecular weight of 1.000 to 5.000,000, and a conjugated diene 1 to 100 parts by weight of a hydrogenated copolymer rubber in which 90% or more of the double bonds of polymerized units are hydrogenated (hereinafter referred to as "hydrogenated copolymer rubber"), and a thermosetting resin composition having as a main component It is something that provides something.

(1) Thermosetting resins used in the present invention include phenol resins, epoxy resins, Melakn resins, unsaturated polyester resins, alkyd resins, etc., but from the viewpoint of ease of mixing, unsaturated polyester resins, phenol resin,
Epoxy resins are preferred, and phenol resins and epoxy resins are more preferred. These (1) thermosetting resins can be used alone or in combination of two or more.

On the other hand, the (II) hydrogenated copolymer rubber used in the present invention consists of components (A) to (B) or components (A) to (C), and the above (A) 1 minute is, for example, Examples include acrylic acid alkyl esters represented by the following general formula (A).

O 1 HzC C-C-0-R, (a) (Here, R1 represents an alkyl group having 1 to 18 carbon atoms.

) Examples of the acrylic acid alkyl ester represented by the general formula (a) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, and n-hexyl. Acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n
-decyl acrylate, n-dodecyl acrylate, n
-octadecyl acrylate and the like, preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, and n-butyl acrylate, particularly preferably methyl acrylate and ethyl acrylate.

Further, examples of (A) include acrylic acid alkoxy-substituted alkyl esters represented by the following general formula (b).

0 11 HzC=CCORz OR3 (b) (Here, Rz and Rs may be the same or different and represent an alkylene group or an alkyl group having 1 to 12 carbon atoms.) Represented by this general formula (b) Examples of acrylic acid alkoxy-substituted alkyl esters include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and 2-methoxyethyl acrylate.
(II-propoxy)ethyl acrylate, 2-(I
I-butoxy)ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 2-(II-propoxy)propyl acrylate,
2-(II-butoxy)propyl acrylate and the like, preferably 2-methoxyethyl acrylate, 2-(II-butoxy)propyl acrylate, etc.
-ethoxyethyl acrylate, particularly preferably 2-methoxyethyl acrylate.

These (A) forces can be used alone or in combination of two or more.

In addition, as the powerful conjugated diene (B), for example, 1
．． 3-butadiene, 1.3-pentadiene, isoprene, 2-neopentyl-1,'3-phytadiene, 1.3
-Hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, and various branched dienes. However, 1,3-butadiene and isoprene are preferred.

These (B)e and min can be used alone or in combination of two or more.

Furthermore, other ethylenically unsaturated compounds that can be copolymerized with the components (A) to (B) that are (C) e,
For example, methacrylates such as methyl methacrylate and octyl methacrylate; alkyl vinyl ketones such as methyl vinyl ketone; vinyl ethers or allyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, and allyl methyl ether; styrene, α-methylstyrene, and chlorostyrene. , vinyl aromatic compounds such as vinyltoluene, vinylbenzyl chloride; vinyl nitrile such as acrylonitrile, methacrylaterile, acrylamide, methacrylamide, N-
In addition to vinylamides such as methylol acrylamide, examples include vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl fumarates, vinyl acetate, vinyl chloroacetate, etc., but preferably methacrylates such as methyl methacrylate and octyl methacrylate; methyl vinyl ketone Alkyl vinyl ketones such as; vinyl ethers or allyl ethers such as ethyl vinyl ether and allyl methyl ether; vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene, as well as alkyl fumarates and vinyl acetate. can.

Furthermore, in the present invention, a compound containing at least one kind of functional group selected from carboxyl group, amino group, epoxy group, and hydroxyl group (hereinafter referred to as "functional group-containing compound") is used as component (C). By this,
The effects of the present invention, particularly a composition excellent in impact resistance, heat deterioration resistance, and adhesiveness, can be obtained.

Among the functional group-containing compounds (C), monomers having a carboxyl group include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc. Among these, dicarboxylic acids use acid anhydride moieties. You can also.

Among the functional group-containing compounds (C), monomers having an amino group include, for example, dimethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylbutylamino (meth)acrylate,
Examples include 4-anilinophenyl (meth)acrylate.

Further, among the functional group-containing compounds (C), examples of monomers having an epoxy group include glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, and the like.

Furthermore, among the functional group-containing compounds (C), as a monomer having a hydroxyl group, 2-hydroxyfurovir (
Examples include meth)acrylate, hydroxyethyl (meth)acrylate, and the like.

Among these functional group-containing compounds (C), monomers having a carboxyl group are preferred, and maleic anhydride is particularly preferred.

The above component (C) can be used alone or in combination of two or more.

The composition ratio of components (A), (B) and (C) in the (II) hydrogenated copolymer rubber used in the present invention is (A)
component 30 to 70 mol%, component (B) 20 to 70 mol%,
and (C) component 0 to 10 mol% [however, (C)
) When the component is a functional group-containing compound, it is 0.1 to 10 mol%, and (A) + (B) + (C) = 100
It is mole%. ) If the content of the component (A) is less than 30 mol%, the kneading properties with the thermosetting resin will be poor, which is undesirable, while if it exceeds 70 mol%, the resulting composition will have poor impact resistance. Undesirable. The content of component (A) is preferably 35 to 60 mol%.

Moreover, when the content of component (B) is less than 20 mol%, it is obtained! The mechanical strength and impact resilience of the acid are not sufficient, and on the other hand, if it exceeds 70 mol%, it becomes difficult to knead with the thermosetting resin. (B) The content of Fl; c is preferably 2
It is 5 to 50 mol%.

Furthermore, (C)1ff7. The content of component (C) is 0 to 10 mol%, and if it exceeds 10 mol%, the resulting composition will have a This is unfavorable because it disrupts the balance of impact resistance, heat resistance, compression set resistance, etc. The content of component (C) is preferably 5 mol% or less.

When the above functional group-containing compound is used as component (C), the amount of the compound used is 0.1 to 10 mol%.
Therefore, if the amount is less than 0.1 mol %, no adhesive effect will be exhibited. (C) The content of the functional group-containing compound is preferably 0.1 to 5 mol%.

The (II) hydrogenated copolymer rubber used in the present invention is (A
) to (C) components are roughly polymerized to form a copolymer rubber and then hydrogenated (method D), or (A) component and (
It can be produced by any method (Method E) in which component (C) is added to a hydrogenated copolymer of component B) and reacted.

Here, as a specific example of method D, (A) tc minute 30 to 7
0 mol%, (B) component 20-70 mol%, and (C)
A mixture of 0 to 10 mol% of the components is subjected to emulsion radical polymerization or suspension radical polymerization in an aqueous medium using a radical polymerization initiator at a polymerization temperature of 0 to 100°C, or solution radical polymerization in an organic solvent. It can be easily manufactured by

In the case of producing copolymer rubber by emulsion radical polymerization, Rusan uses methods known in boat fishing, e.g. using conventional radical initiators such as potassium persulfate, peroxides or azo compounds as polymerization initiators. Anionic, cationic, nonionic and amphoteric surfactants or a mixture thereof are used as emulsifiers, terpene compounds such as Turbinorton, mercaptans such as t-dodecyl mercaptan, halogenated hydrocarbon compounds, etc. Emulsion polymerization is carried out at a temperature of 0 to 100°C in the presence of a molecular weight regulator, and after reaching a predetermined polymerization conversion rate, N, N-
A reaction terminator such as diethylhydroxylamine is added to stop the polymerization reaction, then unreacted monomers in the resulting latex are removed by steam distillation, anti-aging agents such as phenols and amines are added, and further A copolymer rubber can be obtained by coagulating the latex by mixing it with an aqueous solution of a metal salt such as an aqueous solution of aluminum sulfate or an aqueous solution of calcium chloride, and then drying the latex.

In addition, when producing copolymer rubber by suspension radical polymerization, saponified polyvinyl alcohol is added as a dispersant, and an oil-soluble radical initiator such as azobisisobutyronitrile or benzoyl peroxide is used. A copolymer rubber can be obtained by performing polymerization and removing water after the polymerization is completed.

Furthermore, even when producing copolymer rubber by solution radical polymerization, methods known for boat fishing can be employed.

The polymerization method can be either continuous or batchwise.

Next, the hydrogenated copolymer rubber of the present invention is obtained by removing the double bonds of the conjugated diene polymer units of the copolymer rubber obtained in this way by a conventional method (for example, Japanese Patent Publication No. 45-39275,
JP-A-52-32095, JP-A-56-1332
91, etc.) by hydrogenation. Further, to explain this hydrogenation method specifically, the above-mentioned copolymer rubber is usually mixed with dicyclopentadienyl titanium halide, cobalt organic carboxylate or nickel organic carboxylate, and organic carboxylate groups 1 to 2 of the periodic table. hydrogenation catalysts consisting of organometallic compounds, nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalysts supported on carbon, silica, diatomaceous earth, alumina, etc., and cobalt, nickel, rhodium, palladium, ruthenium complexes, etc. As, 1-100
Obtained by hydrogenation under hydrogen pressurized to atmospheric pressure.

The copolymer rubber may be a hydrocarbon solvent such as hexane, heptane, cyclohexane, benzene, toluene, or ethylbenzene, a halogenated hydrocarbon solvent such as chlorobenzene or dichlorobenzene, or methyl ethyl ketone.
Hydrogenation is carried out using the hydrogenation catalyst or hydrogenation compound described above in one or more polar solvents such as ethyl acetate, ethyl ether, tetrahydrofuran, and acetone.

The hydrogenated copolymer rubber solution thus obtained is removed by steam stripping or the like or coagulated by alcohol, and then dried to obtain a solid hydrogenated copolymer rubber.

There are no particular restrictions on the specific example of method E, but for example, after copolymerizing (A) 1 minute and (B) bottom valve in advance, the conjugated diene polymerization unit is More than 90% of the bonds are hydrogenated, and C
) A method of adding a bottom valve and, if necessary, using a radical initiator similar to the above, or hydrogenated (A)
- A method of adding a radical initiator and a bottom valve (C) during kneading of a copolymer rubber consisting of component (B) using a kneading machine such as a Banbury mixer or a kneader may be optionally performed. You can choose.

By being hydrogenated, the hydrogenated copolymer rubber used in the present invention has excellent heat resistance, ozone resistance, mechanical strength, and cold resistance, and also has excellent rebound properties.

In this hydrogenated copolymer rubber, 90% or more, preferably 95% or more of the double bonds in the conjugated diene polymerized units must be hydrogenated (i.e., the unhydrogenated conjugated diene polymerized units must have 10% or more hydrogenated). %, preferably less than 5%), and less than 90%, which is undesirable because heat resistance and ozone resistance are poor.

The weight average molecular weight of the hydrogenated copolymer rubber used in the present invention in terms of polystyrene is preferably 1.000 to 5.0.
00,000, more preferably 2,000 to 1,00
0,000, and if it is less than 1.000, the effect of improving the impact resistance of the resulting composition is poor;
If it exceeds this amount, the dispersibility in the thermosetting resin will be poor and the resulting composition will have poor mechanical strength.

The mixing ratio of (1) thermosetting resin and (II) hydrogenated copolymer rubber is (1) with respect to 100 parts by weight of (I) thermosetting resin.
II) Hydrogenated copolymer rubber 1 to 100 parts by weight, preferably 1 to 30 parts by weight.

(It) If the proportion of the hydrogenated copolymer rubber is less than 1 part by weight, the effect of improving impact resistance will be poor, while if it exceeds 100 parts by weight, the high strength inherent to the thermosetting resin cannot be maintained. It disappears.

The thermosetting resin composition of the present invention has the above-mentioned (1) thermosetting resin and (II) hydrogenated copolymer rubber as main components, and may also contain anti-aging agents, stabilizers, and plasticizers as necessary. Additives such as softeners, various inorganic or organic fillers, reinforcing agents, and crosslinking agents can be added.

The thermosetting resin composition of the present invention contains (1) a thermosetting resin and (II) a hydrogenated copolymer rubber, and if necessary, other rubber components and the above-mentioned commonly used additives. It is prepared by mixing using a known mixer such as an open type mixing roll, a closed type Banbury mixer 1 extruder, or a kneader 1 continuous mixer.

When the composition of the present invention is blended with a compatibilizing agent, a composition having significantly superior mechanical properties and surface properties of a molded article can be obtained.

Various types of compatibilizers can be used, but preferred ones are mainly unsaturated compounds having an olefin unit and at least one functional group selected from the group of epoxy groups, carboxyl groups, and acid anhydride groups. Examples include polymers such as

The amount of the compatibilizer added is 0.1 to the composition of the present invention.
-40% by weight is preferred, more preferably 0.5-3
0% by weight, particularly preferably 1 to 20% by weight.

The olefin unit of the compatibilizer and at least one selected from the group of epoxy groups, carboxyl groups, and acid anhydride groups.
Examples of the olefin used in the polymer mainly composed of an unsaturated compound having various functional groups include ethylene, propylene, and butene-1, with ethylene being particularly preferred.

Examples of the epoxy group-containing unsaturated compound used for producing the main chain copolymer of this component include compounds having an epoxy group and an unsaturated group copolymerizable with an olefin in one molecule.

For example, unsaturated glycidyl esters such as glycidyl methacrylate, unsaturated glycidyl ethers, epoxy alkenes, and unsaturated epoxy compounds such as P-glycidyl styrenes can be used.

Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, and cinnamic acid.

Examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, and tetrahydrophthalic anhydride, with maleic anhydride being preferred.

The unsaturated compounds containing epoxy groups, carboxyl groups, and acid anhydride groups may be used alone or in combination of two or more. Also,
Furthermore, other copolymerizable vinyl monomers can also be copolymerized.

The weight ratio of the olefin to the unsaturated compound containing an epoxy group, a carboxyl group, or an acid anhydride group is olefin component:unsaturated compound containing a functional group=99=1 to 60:40, preferably 97:3 to 70:30. It is.

It is also possible to use a product obtained by graft polymerizing another copolymer in the presence of the above copolymer. This graft component is a polymer consisting of a radically polymerizable vinyl monomer, and examples of the radically polymerizable vinyl monomer include acrylic acid alkyl ester, methacrylic acid alkyl ester, aromatic vinyl compound, and vinyl cyanide. compounds, maleimide compounds, epoxy group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, vinyl acetate, etc., and these are used alone or in combination of two or more.

The weight average molecular weight of the grafted polymer in terms of polystyrene is preferably 5,000 to 300,000,
It is preferable that the compatibilizer itself has a multiphase structure due to these grafts.

When using a graft polymer, the preferred range of the main chain copolymer (c) and the graft component raw material (d) is (c)
:(d) (weight ratio)=95:5 to 20:80, particularly preferably 90:10 to 40:60.

The use of the thermosetting resin composition of the present invention is not particularly limited, but by making use of the above-mentioned excellent characteristics, various coating materials, casting materials,
It can be used as a molding material, adhesive, paint, vibration damping material for vibration damping copper plates, etc.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

In the examples, parts and percentages are based on weight unless otherwise specified.

In addition, in the examples, the physical properties of the obtained compositions are JIS
This is a value measured according to K2SO3.

Example 1 Monomer mixture of Northern rubber and Ox rubber 1
00 parts, 200 parts of water, 3 parts of sodium lauryl sulfate, p
- Menthane hydroperoxide 0.2 parts, sodium ethylenediaminetetraacetate 0.125 parts, ferrous sulfate 0
．． 0.05 parts of sodium formaldehyde sulfoxylate, and 0.2 parts of t-dodecyl mercaptan were placed in a nitrogen-purged iron container, and heated at 10°C for 1 to 10 minutes.
Polymerized for hours.

After polymerization, the reactant was taken out and steam was blown into it to remove unreacted monomers. The copolymer rubber latex thus obtained was coagulated by adding an aqueous calcium chloride solution, and the coagulated product was thoroughly washed with water and dried at about 90°C for 1 to 3 hours to obtain a copolymer rubber. .

After dissolving 10 parts of the obtained copolymer rubber in 90 parts of toluene, it was placed in a pressure-resistant container and heated under hydrogen pressure (40 kg/cii-G ), 1~ at a temperature of 60℃
5 hours, the carbon of the conjugated diene polymer unit of the rubber in the copolymer
A hydrogenated copolymer rubber was obtained by hydrogenating the carbon double bonds.

However, only hydrogenated copolymer rubber F uses trisphenylphosphine rhodium chloride as a hydrogenation catalyst;
C&Hs)3P)RhCII was used.

The polymer composition of the obtained hydrogenated copolymer rubber is shown in Table 1.

Using the obtained hydrogenated copolymer rubber A, it was blended with a phenol resin according to the following formulation and evaluated.

L gold removal (part) Phenol resin (novolac type, manufactured by Sumitomo Durets ■, PR50
072); 100 hydrogenated copolymer rubber A,
10 hexamethylenetetramine;
10 According to the above formulation, heat at 130'C with an electric heating roll.
After kneading for 5 minutes, the mixture was crushed and press-molded at 160'C for 10 minutes to obtain a molded plate with a thickness of 4 mm. This was processed using a milling machine according to JIS K6911 to prepare a test piece. The test results are shown in Table 2.

Examples 2 to 5, Comparative Examples 1 to 3 Phenol resin compositions were obtained in the same manner as in Example 1, except that B-H shown in Table 1 was used instead of hydrogenated copolymer rubber A. . The results are shown in Table 2.

Example 6 100 parts of hydrogenated copolymer rubber A was added to a Haake rheometer kneader and kneaded at 190°C for 5 minutes.
After adding 5 parts of maleic anhydride and kneading for 2 minutes,
,5-dimethyl-2,5-di(t-butylperoxy)
After adding 0.1 part of hexane and kneading for 5 minutes, the mixture was taken out.

Thereafter, it was dissolved in toluene, coagulated with n-hexane, and dried under vacuum after removal of unreacted functional groups.

A phenol resin composition was obtained in the same manner as in Example 1 using the obtained maleic anhydride-modified hydrogenated copolymer rubber A'. The results are shown in Table 2.

Example 7 Hydrogenated copolymer rubber E was modified with maleic anhydride in the same manner as in Example 6 to produce maleic anhydride-modified hydrogenated copolymer rubber E', which was used in Example 1. A phenol resin composition was obtained in the same manner as above. The results are shown in Table 2.

Comparative Example 5 A phenol resin composition was obtained in the same manner as in Example 1, using acrylonitrile-butadiene rubber (manufactured by Nippon Gosei Rubber, N23 OS) instead of hydrogenated copolymer rubber A. The results are shown in Table 2.

Comparative Example 6 A phenolic resin composition was obtained without using any hydrogenated copolymer rubber as an elastomer.

The results are shown in Table 2.

As is clear from Table 2, the phenol resin composition of the present invention is excellent in strength, impact resistance, and particularly in impact resistance after heat aging.

Table 2 $1) Analysis of the hydrogenated copolymer rubber was determined by measuring the residual monomer and iodine value by gas chromatography after emulsion polymerization.

*2) The unhydrogenated butadiene content was determined by the iodine value method.

Example 8 Using the hydrogenated copolymer rubber A used in Example 1, a thermosetting resin composition (epoxy resin composition) was obtained according to the following procedure.

L gold treatment (part) Cresol novolak type epoxy resin (epoxy equivalent 220, manufactured by Yuka Shell Epoxy ■, Epicoat 1B0S65);
100 phenolic resin (Novolac type, manufactured by Sumitomo Durets ■, Sumilite Resin PR5
0072); 0 Hardening agent (2-methylimidazole); 5-hydrogenated copolymer rubber A 10 These were kneaded at about 80"C using a closed type ξ mixer, and then pressed for 10 minutes at 160"C. A sample for physical property evaluation was prepared by processing the obtained molded plate using a milling machine.

The results are shown in Table 4.

Example 9 Maleic anhydride-modified hydrogenated copolymer E' used in Example 7
The epoxy resin composite acid product was evaluated in the same manner as in Example 8 except that the following was used.

The results are shown in Table 4.

Examples 10 to 13 Using the polymerization recipe shown below, a polymerization reaction was carried out at a temperature of 10°C in an autoclave having an internal volume of 61°C.

Heavy duty removal (parts) Monomer; 100 water;
200 Sodium laurate; 3 ferrous sulfate,
0.05 Sodium formaldehyde sulfoxylate; 0.2 Sodium ethylenediaminetetraacetate; 0.12 paramenthane hydroperoxide; 0.2 Terpinorton, 0.65 per 100 parts of monomer; Polymerization was stopped by adding 2 parts of N,N-diethylhydroxyamine.

Next, remove unreacted monomers by steam distillation and touch.
The latex was coagulated with an aqueous calcium chloride solution, and the obtained crumb was washed with water and dried at about 90'C for 1 to 3 hours to obtain a modified copolymer rubber.

After dissolving 10 parts of the obtained copolymer rubber in 90 parts of toluene, it was placed in a pressure container and heated under hydrogen pressure (40 kg/c111G) using 0.5 parts of nickel naphthenate and 0.15 parts of triethylaluminum as catalysts at temperature. A modified hydrogenated polymer rubber was obtained by hydrogenating the carbon-carbon double bond of the conjugated diene polymerized unit of the copolymer rubber at 60° C. for 5 hours.

Table 3 shows the results of determining the unhydrogenated butadiene content in the obtained modified hydrogenated polymer rubber from the iodine value.

Moreover, the weight average molecular weight of the obtained modified hydrogenated copolymer rubber is a polystyrene equivalent value determined by gel barbinage chromatography.

Using this modified hydrogenated copolymer rubber, an epoxy resin composition was obtained in the same manner as in Example 8 and evaluated. The results are shown in Table 4.

Comparative Examples 7 to 8 Evaluation was performed in the same manner as in Example 8, except that hydrogenated copolymer rubbers F and H shown in Table 1 were used, respectively. The results are shown in Table 4.

Comparative Example 9 Instead of hydrogenated copolymer rubber A, acrylonitrile-butadiene rubber (manufactured by Nippon Gosei Rubber, N230S) was used, and evaluation was performed in the same manner as in Example 8. 4th result
Shown in the table.

Comparative Example 10 Without using any hydrogenated copolymer rubber as an elastomer,
An epoxy resin composition was obtained in the same manner as in Example 8, and evaluated. The results are shown in Table 4.

Comparative Example 11 In Example 8, hydrogenated acrylonitrile-butadiene copolymer rubber (hydrogenated NBR1 manufactured by Nippon Zeon ■, Zentopol 2020) was used instead of hydrogenated copolymer rubber A.
) was used, but an epoxy resin composition was obtained in the same manner.

Table 4 shows the test results of the obtained epoxy resin composition.

Comparative Example 12 According to the method for preparing a copolymer rubber shown in Example 1, a copolymer rubber having a monomer composition of 24 mol% acrylonitrile, 40 mol% ethyl acrylate, and 36 mol% 1.3-butadiene was prepared. Obtained.

Further, using this copolymer rubber, hydrogenation was carried out in the same manner as in Example 1 except that palladium carbon was used as a hydrogenation catalyst to obtain a hydrogenated copolymer rubber M. The unhydrogenated butadiene content of this hydrogenated copolymer rubber M is
It was 2.9 mol%, and the weight average molecular weight was 620,000.

The epoxy resin composition was evaluated in the same manner as in Example 8 except that this hydrogenated copolymer rubber M was used.

The results are shown in Table 4.

As is clear from Table 4, the epoxy resin composition of the present invention is a composition having excellent strength, impact resistance, and heat resistance.

Table 3 *l) Analysis of the hydrogenated copolymer rubber was determined by measuring the residual monomer and iodine value by gas chromatography after emulsion polymerization.

*2) The unhydrogenated butadiene content was determined by the iodine value method.

Table 4 (Effects of the Invention) Thermosetting resin compositions using the hydrogenated copolymer rubber of the present invention have lower electrical insulation properties than thermosetting resin compositions containing conventional modifiers. Combined with its excellent impact resistance, mechanical strength, and heat resistance, it can be widely used in coating materials, casting materials, molding materials, adhesives, paints, etc. mainly for electrical/electronic parts and automobile parts. can.

Claims (2)

[Claims] (1) (I) 100 parts by weight of thermosetting resin, (II) (
A) Acrylic acid alkyl ester and/or acrylic acid alkoxy-substituted alkyl ester 30-70 mol%
, (B) 20 to 70 mol% of a conjugated diene, and (C) 0 to 10 mol% of another ethylenically unsaturated compound copolymerizable with the components (A) to (B), consisting of a random copolymer rubber, and 1 to 100 parts by weight of a hydrogenated copolymer rubber in which 90% or more of the double bonds of the conjugated diene polymerization units are hydrogenated. (2) Component (C) of the hydrogenated diene copolymer rubber (II) is a compound containing at least one functional group selected from a carboxy group, an amino group, an epoxy group, and a hydroxyl group, The thermosetting resin composition according to claim 1, wherein the content of the compound is 0.1 to 20 mol%.