JPH0715041B2 - Epoxy resin composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition which is tough and has excellent heat resistance and adhesiveness, and a method for producing the same.

[0002]

2. Description of the Related Art Epoxy resins have a well-balanced performance in terms of thermal, mechanical and electrical properties, so adhesives, paints, electric / electronic component materials, civil engineering and construction materials, etc. Widely used in various fields. However, epoxy resin has the disadvantage of being hard but brittle, so as a method for improving it, a method of incorporating a plasticizing component,
Alternatively, a method of reducing the crosslink density by using a monofunctional epoxy compound in combination has been investigated.

However, these methods have another drawback that the heat resistance is remarkably lowered due to the presence of the plasticizing component, and they have not been a fundamental solution. What has been considered there is a method of modifying an epoxy resin with rubber-like particles having a low glass transition temperature (hereinafter referred to as Tg). For example, it is a method in which a rubber having a functional group having reactivity with an epoxy resin or a functional group having reactivity with an epoxy resin curing agent introduced into the molecule is allowed to coexist in a curing reaction system of the epoxy resin and reacted.

According to this method, the toughness of the epoxy resin is considerably improved, and in some cases a cured product having good heat resistance can be obtained, but it is dispersed depending on the type of curing agent used and curing conditions. The toughness improving effect may not be effectively exhibited because the shape of the rubber particles may change.
There is a problem that a part or all of the rubber particles are compatible with the epoxy resin and heat resistance is deteriorated.

A method is also known in which modifying rubber particles obtained by emulsion polymerization are added to an epoxy resin. In this method, the modifying shape of the modifying rubber particles due to curing conditions and the like and the epoxy resin are changed. Since the compatibilization does not occur, the above problem does not occur. For example, JP-A-52
-36198 discloses a composition obtained by adding a curing agent to a mixture of an emulsion-type elastomer and a liquid or emulsion-type epoxy resin. JP-A-53-78237 discloses an acrylic emulsion and an epoxy. A coating composition comprising a resin and an anticorrosion pigment is disclosed. In these compositions,
Although the shape of the modifying rubber particles does not change and the modifying effect is not impaired during the curing reaction of the epoxy resin, both the epoxy resin and the modifying rubber particles are aqueous dispersions, so the scope of application is Is significantly limited.

On the other hand, Japanese Patent Publication No. 51-44973, Japanese Patent Publication No. 61-69827, Japanese Patent Publication No. 62-50361, Japanese Patent Publication No. 62-275149 and Japanese Patent Publication No. 62-22849. JP-A-62-22850, JP-A-2-80483, JP-A-2-117948, and the like disclose compositions in which modifying rubber particles are directly dispersed in an epoxy resin. There is.

However, these contain the modifying rubber particles obtained by so-called core / shell polymerization,
Since it is a method of once extracting as powder and mixing with epoxy resin, not only the process is complicated, but also the shell component that does not directly contribute to the improvement of toughness is included, so the modifying effect is relative to the addition amount. In the method of dispersing and polymerizing the polymerizable monomers that make up the poor rubber in an epoxy resin, the molecular weight of the rubber component does not rise sufficiently, and the amount of the rubber component dissolved in the epoxy resin increases and the heat resistance deteriorates. When emulsion is synthesized by emulsion polymerization, since a water-soluble emulsifier that is not compatible or reactive with the epoxy resin is used, the toughness of the obtained epoxy resin composition is lowered and the water absorption rate is increased. is there.

[0008]

SUMMARY OF THE INVENTION The present invention has been made by paying attention to the above-mentioned circumstances, and the purpose thereof is that the rubber particles which are substantially incompatible with the epoxy resin are the curing conditions of the epoxy resin and the like. Distributed evenly without being affected by
It is intended to provide an epoxy resin composition which exhibits excellent toughness, moisture resistance, water resistance and adhesiveness as a whole and can be widely used as various molding materials, adhesives, paints, sealants and the like.

[0009]

The composition of the epoxy resin composition of the present invention which has been able to solve the above-mentioned problems is a polyamine compound having two or more primary and / or secondary amino groups in the molecule. (A) has the general formula R- (OX) _n- Y (B) (wherein R represents a hydrocarbon group having 4 or more carbon atoms, X represents a lower alkylene group, and n represents 0 or 1 to 30). Of the modified polyamine [I] and / or a salt thereof obtained by reacting a compound (B) represented by the formula (1), and Y represents an atomic group having a functional group capable of reacting with an amino group. A (meth) acrylic acid ester-based polymer particle [II] having a glass transition temperature of 20 ° C. or lower, which is obtained by emulsion polymerization of a (meth) acrylic acid ester-based monomer (C) using a surfactant as an emulsifier, When dispersed in an epoxy resin And it has a gist to the filtrate.

[0010]

The present inventors pay attention to the above-mentioned problems of the prior art, and as a toughness improving component (meta) in the epoxy resin.
The inventors have earnestly studied a composition in which acrylic acid ester-based (hereinafter sometimes simply referred to as acrylic) polymer particles are dispersed. As a result, the acrylic polymer particles obtained by emulsion polymerization using a polyamine-based reactive surfactant having an amino group introduced into the surfactant are:
It has been clarified that it can be easily dispersed in an epoxy resin and that the toughness can be greatly improved without impairing other properties, and the present invention has been completed.

Further, by adding a polymerizable unsaturated group to the reactive surfactant, an amino group can be introduced into the acrylic polymer particles themselves, so that a covalent bond with the epoxy resin is formed. It was also clarified that a stable epoxy resin composition formed was obtained.

The constituents of the present invention centering on the reactive surfactant and the acrylic polymer particles will be described in detail below.

The modified polyamine [I] used in the present invention is a polyamine compound (A) having two or more primary and / or secondary amino groups in the molecule, and is represented by the general formula R- (OX) _n-. A compound (B) represented by Y (R, X, Y, and n have the same meanings as described above) and, if necessary, a compound represented by the general formula R'-Y (R 'and Y have the same meanings as described above) ( It is obtained by reacting D).

The polyamine compound (A), which is a main constituent of the reactive surfactant, is an amine having two or more primary and / or secondary amino groups in the molecule or a derivative thereof, such as ethylene. Polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines such as polyethyleneimine obtained by polymerization of imines; (poly) alkylenepolyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; poly Polyamide polyamine obtained by condensation of alkyleneimine and / or (poly) alkylenepolyamine with polybasic acid such as adipic acid; polyalkyleneimine and / or (poly) alkylenepolyamine and / or alkyle And polyamide polyester polyamine obtained by copolymerization of an acid anhydride such as alkylene imine with phthalic acid, and the like; polyurea polyamines obtained by the reaction of imine with urea.

Examples of the polyamine derivative include alkylene oxides such as ethylene oxide and propylene oxide, (meth) acrylates such as butyl acrylate and methyl methacrylate, and α, β-unsaturated acid amide compounds such as acrylamide. And the like.

As the polyamine compound (A), it is preferable to use polyethyleneimine or a derivative thereof in order to obtain excellent surface activity. Further, in consideration of the solubility of the reactive surfactant to be obtained in water, the viscosity of the solution, and the surfactant activity, it is preferable to use polyethyleneimine having a molecular weight of 5000 or less.

The general formula R- (OX) _n used in the present invention is as follows.
In the compound (B) represented by —Y (R, X, Y and n have the same meanings as described above), the hydrocarbon group having 4 or more carbon atoms, which corresponds to R in the formula, preferably has 4 to 28 carbon atoms. Examples thereof include a linear or branched alkyl group, a (alkyl) aryl group, a (alkyl) hydrogenated aryl group, and a (alkyl) aralkyl group.

Examples of the lower alkylene group corresponding to X in the formula include ethylene group, propylene group, isobutylene group and the like. Examples of the functional group capable of reacting with an amino group in an atomic group having a functional group capable of reacting with an amino group corresponding to Y in the formula include an epoxy group, an isocyanate group, a halogenated alkyl group, a hydroxyl group, and (meth) acryloyl Group, carboxyl group and the like.

Examples of the compound (B) include n-octyl polyoxyalkylene glycidyl ether, n-nonyl polyoxyalkylene glycidyl ether, in which the number of added moles of alkylene oxide such as ethylene oxide, propylene oxide and isobutylene oxide is 1 to 30. Primary alkyl polyoxyalkylene glycidyl ethers such as lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, 2-ethylhexyl polyoxyalkylene glycidyl ether;

A mixture of secondary alcohols having 12 to 14 carbon atoms with 1 to 30 moles of alkylene oxide added thereto and further glycidyl etherification, and a mixture of secondary alcohols having 10 to 12 carbon atoms with 1 to alkylene oxide. Secondary alkyl polyoxyalkylene glycidyl ethers such as those obtained by adding 30 mol and further converting to glycidyl ether;

Alkylphenyl poly, such as octylphenyl polyoxyalkylene glycidyl ether, nonylphenyl polyoxyalkylene glycidyl ether, lauryl phenyl polyoxyalkylene glycidyl ether, stearyl phenyl polyoxyalkylene glycidyl ether, etc., in which the number of moles of added alkylene oxide is 1 to 30. Oxyalkylene glycidyl ethers;

Octyl cyclopentyl polyoxyalkylene glycidyl ether, octyl cyclohexyl polyoxyalkylene glycidyl ether, nonyl cyclopentyl polyoxyalkylene glycidyl ether, nonyl cyclohexyl polyoxyalkylene glycidyl ether having 1 to 30 added moles of alkylene oxide.
Alkylcycloalkyl polyoxyalkylene glycidyl ethers such as lauryl cyclopentyl polyoxyalkylene glycidyl ether, lauryl cyclohexyl polyoxyalkylene glycidyl ether, stearyl cyclopentyl polyoxyalkylene glycidyl ether, stearyl cyclohexyl polyoxyalkylene glycidyl ether;

Alkylbenzyl polyalkyl ethers such as octylbenzyl polyoxyalkylene glycidyl ether, nonylbenzyl polyoxyalkylene glycidyl ether, lauryl benzyl polyoxyalkylene glycidyl ether and stearyl benzyl polyoxyalkylene glycidyl ether having an addition mole number of alkylene oxide of 1 to 30. Oxyalkylene glycidyl ethers;

Octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, 2
-Glycidyl ethers of higher alcohols such as ethylhexyl glycidyl ether;

Glycidyl ethers of alkylphenols such as octylphenyl glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether and stearyl phenyl glycidyl ether;

Glycidyl ethers of alkyl cycloalkanols such as octyl cyclopentyl glycidyl ether, octyl cyclohexyl glycidyl ether, nonyl cyclopentyl glycidyl ether, nonyl cyclohexyl glycidyl ether, lauryl cyclopentyl glycidyl ether, lauryl cyclohexyl glycidyl ether, stearyl cyclopentyl glycidyl ether, stearyl cyclohexyl glycidyl ether. Kind;

Glycidyl ethers of alkylbenzyl alcohol such as octylbenzyl glycidyl ether, nonylbenzyl glycidyl ether, lauryl benzyl glycidyl ether and stearyl benzyl glycidyl ether;

1,2-epoxyalkanes such as α-olefin epoxide having 12 or 14 carbon atoms and α-olefin epoxide having 16 or 18 carbon atoms;

Alkyl isocyanates such as octyl isocyanate, decyl isocyanate and octadecyl isocyanate; obtainable by reaction of alcohols such as octanol, lauryl alcohol and stearyl alcohol or alkylene oxide adducts of these alcohols with diisocyanates such as tolylene diisocyanate Monoisocyanate compounds used;

Halogen compounds in which alcohols such as octanol, lauryl alcohol and stearyl alcohol or alkylene oxide adducts of these alcohols are substituted with terminal hydroxyl groups by halogen atoms such as chlorine, bromine and iodine;

Saturated fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and eleostearic acid; 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid esters such as lauryl (meth) acrylate and stearyl (meth) acrylate; and the like can be mentioned, and one or more selected from these groups can be used. The amount of the compound (B) used is not particularly limited, but in order to exhibit sufficient surface activity, 0.01 to 0.9 molecule of the compound (B) per active amine hydrogen of the polyamine compound (A) is used. Is preferably used.

Polymerization in the atomic group corresponding to R'in the formula in the compound (D) represented by the general formula R'-Y (R ', Y has the same meaning as above) optionally used in the present invention. As the unsaturated group, a (meth) acryloyl group,
Examples thereof include (meth) allyl group and vinyl group.
Further, Y in the formula includes the same atomic group as in the case of the compound (B).

The compound (D) has a group capable of reacting with an amino group in the molecule such as 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate ( (Meth) acrylic acid esters; vinyl ethers such as chloroethyl vinyl ether;

(Meth) acrylic acid chloride, (meth)
Allyl bromide, (meth) allyl isothiocyanate, allyl (meth) acrylate, half-esters of (meth) allyl alcohol and dicarboxylic acid anhydride such as phthalic anhydride or succinic anhydride, and (meth) allyl glycidyl ether ( (Meth) allyl compounds;

Styrene derivatives having a group capable of reacting with an amino group in the molecule such as chloromethylstyrene and α-methylchloromethylstyrene; a vinyl ester of an acid having a group capable of reacting with an amino group in the molecule such as vinyl chloroacetate. Kind;
And the like, and one or more selected from these groups can be used. Preferred examples of the compound (D) include vinyl ethers,
(Meth) allyl compounds, styrene derivatives, vinyl esters of organic acids are mentioned. The amount of the compound (D) used is preferably 0.01 to 0.9 molecule per active amine hydrogen of the polyamine compound (A).

Polymerization reactivity is introduced into the reactive surfactant by adding the compound (D) to the polyamine compound (A) together with the compound (B). Therefore, this is used as an emulsifier for the (meth) acrylic acid ester-based monomer. The polymer obtained by polymerizing the monomer (C) is a polymer in which the (meth) acrylic acid ester-based polymer particles [II] and the modified polyamine [I] which is an emulsifier are integrated by a chemical bond.

Further, since the modified polyamine [I] has reactivity with the epoxy resin, each interface of polymer particles [II] / modified polyamine [I] and modified polyamine [I] / epoxy resin is linked by a covalent bond. To be done. In order to obtain an epoxy resin composition that is tough and has excellent heat resistance and adhesiveness,
Using compound (D) is a preferred embodiment.

In the present invention, modified polyamine [I]
The reaction conditions for obtaining the compound are not particularly limited, and include, for example, the polyamine compound (A), the compound (B) and the compound (D) as they are or, if necessary, diluted with a solvent at room temperature to 2
It can be synthesized by reacting at a temperature of 00 ° C, preferably 50 to 100 ° C. In this case, the solvent optionally used is one capable of dissolving the polyamine compound (A), the compound (B) and the compound (D),
And it is preferable that they are inactive against them. Also,
During the reaction, it is possible to use a catalyst for promoting the reaction.

The modified polyamine [I] thus obtained can be mixed with an acid to form a salt. It is preferable to use a salt because the solubility in water is improved. Examples of acids that can be added include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, acetic acid, lactic acid and (meth) acrylic acid. Can be mentioned. However, when the halogen atom in the cured epoxy resin becomes a problem, it is better not to use hydrochloric acid.

Next, as the monomer (C) used for producing the (meth) acrylic acid ester-based polymer particles [II], methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2- Carbon number 1 such as ethylhexyl, lauryl, stearyl or cyclohexyl
To 18 (meth) acrylic acid esters, which are ester compounds of linear or branched aliphatic alkyl alcohols or alicyclic alkyl alcohols with (meth) acrylic acid; hydroxyethyl (meth) acrylate, (meth ) Hydroxypropyl acrylate, unsaturated monomers containing hydroxyl group such as monoester of (meth) acrylic acid and polypropylene glycol or polyethylene glycol; unsaturated monomers containing epoxy group such as glycidyl (meth) acrylate ;

Aziridinyl group-containing unsaturated monomers such as (meth) acryloylaziridine and (meth) acryloyloxyethylaziridine; 2-isopropenyl-2-
Oxazoline group-containing unsaturated monomers such as oxazoline and 2-vinyl-2-oxazoline; (meth) acrylic acid and ethylene glycol, 1,3-butylene glycol,
Polyfunctionality (meth) containing two or more polymerizable unsaturated groups in the molecule such as ester with polyhydric alcohol such as 1,6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane Acrylic acid esters; allyl (meth) acrylate; and the like. These can be used alone or in combination of two or more kinds, and further, other copolymerizable monomers, For example, styrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, divinylbenzene, diallyl phthalate and the like can be copolymerized in appropriate amounts.

In producing the (meth) acrylic acid ester-based polymer particles [II], the monomer (C) is so adjusted that the glass transition temperature of the obtained polymer particles [II] is 20 ° C. or lower. It is necessary to consider the type and combination of. If the glass transition temperature of the polymer particles [II] is higher than 20 ° C., a sufficient toughness improving effect cannot be obtained. The lower the glass transition temperature is, the higher the toughness improving effect is, but the glass transition temperature of the polymer particles [II] obtained by polymerizing a commercially available (meth) acrylic acid ester-based monomer is −80 ° C.
It is difficult to get lower. When a monomer (C) having a functional group capable of reacting with an amino group is used as the (meth) acrylic acid ester-based monomer (C), the above-mentioned emulsifier having an amino group and (meth) acrylic are used. Since the acid ester polymer particles [II] are bonded more firmly, the toughening effect on the epoxy resin is further enhanced. As such a monomer (C), among those exemplified as the above-mentioned monomer (C), epoxy group-containing polymerizable monomers, aziridinyl group-containing polymerizable monomers, oxazoline group-containing polymerizable monomers Monomers are preferred.

Introducing an appropriate cross-linking structure into the (meth) acrylic acid ester type polymer particles [II] is effective in enhancing the toughness of the epoxy resin. As the polymerizable monomer (C) capable of introducing such a crosslinked structure, among the monomers exemplified as the monomer (C), a polyfunctional compound having two or more polymerizable unsaturated groups in the molecule. (Meth) acrylic acid ester, divinylbenzene,
Preferred examples include diallyl phthalate and allyl (meth) acrylate. However, the amount used is 0.
It should be suppressed to about 5 to 10 parts by weight, and if it exceeds 10 parts by weight, the toughening effect tends to decrease, which is not preferable.

There are no particular restrictions on the emulsion polymerization method,
Any conventionally known emulsion polymerization method can be applied. For example, the aforementioned modified polyamine [I] acting as an emulsifier
Of the above polymerizable monomer (C), the polymerization catalyst and water, and polymerizing them together, or a so-called monomer dropping method, pre-emulsion method, and further seed polymerization method,
The (meth) acrylic acid ester-based polymer particles [II] can be synthesized by a method such as a multistage polymerization method. The polymerization is usually carried out at 0 to 100 ° C, preferably 50 to 80 ° C,
A polymerization time of about 1 to 10 hours is sufficient.

The amount of the modified polyamine [I] used as an emulsifier is not particularly limited, but is preferably 0.5 to 10 parts by weight, more preferably 1 to 100 parts by weight of the polymerizable monomer (C). It is in the range of 3 parts by weight. When a large amount of an emulsifier is used, foaming may occur when water is distilled off in the production process of an epoxy resin composition as described below, but the amount of the modified polyamine [I] used is limited to 3 parts by weight or less. If so, an epoxy resin composition can be easily obtained without causing foaming at the time of dehydration without using an antifoaming agent that causes deterioration of physical properties of the cured epoxy resin.

As the polymerization catalyst used in the emulsion polymerization, all known catalysts can be used, but if there is a possibility that an alkali metal, chloride ion, etc. may adversely affect the cured epoxy resin, hydrogen peroxide, peracetic acid, diamine, etc. It is desired to use a polymerization catalyst such as -t-butyl peroxide and 4,4'-azobis (4-cyanopentanoic acid).

There are no particular restrictions on the epoxy resin used in the present invention, and any known epoxy resin can be appropriately selected and used according to its application and required characteristics. For example, bisphenol A, bisphenol F, phenol novolac, cresol novolac, brominated bisphenol A
Glycidyl ethers of phenols such as; glycidyl ethers of alcohols such as butanol, butanediol, polyethylene glycol, polypropylene glycol;
Examples thereof include glycidyl esters of acids such as hexahydrophthalic acid and dimer acid. These can be used alone or in combination of two or more.

In producing the epoxy resin composition according to the present invention, the emulsion of the (meth) acrylic acid ester-based polymer particles [II] is mixed with the above-mentioned epoxy resin for the purpose of simplifying the process and preventing contamination of impurities. A method of directly mixing with the above and removing water while stirring under normal pressure or reduced pressure is preferable.

In the methods proposed so far, a coagulant containing a metal is added, or the cloud point of a nonionic emulsifier is used to coagulate and precipitate the rubber particles in an emulsion form, and then the epoxy resin is dried and then dried. It requires a plurality of steps of dispersing in a resin, and not only the steps are complicated, but also metal ions may be mixed in the composition to deteriorate the physical properties of the cured epoxy resin.

However, when the above-mentioned production method defined in the present invention is adopted, a resin composition in which (meth) acrylic acid ester-based polymer particles [II] are uniformly dispersed in an epoxy resin,
It can be easily obtained in only one step. In this case, if an ordinary low-molecular weight emulsifier is used as an emulsifier and a similar dispersion is to be obtained, bubbles are significantly generated when water is removed and overflows from the container, so that dehydration becomes substantially impossible. .

The reason why the above-mentioned simple production method can be realized in the present invention is that the modified polyamine [I] used as an emulsifier has a high molecular weight and is strongly bound to the polymer particles [II]. As a result, the modified polyamine [I] has less bubbles in the dehydration step, and since the modified polyamine [I] has reactivity with the epoxy resin, the dispersibility of the (meth) acrylate polymer particles [II] is improved. it is conceivable that.

In producing the epoxy resin composition,
The emulsion of the epoxy resin and the (meth) acrylic acid ester-based polymer particles [II] is put into a container equipped with a stirrer and a water removal port, and the mixture is heated at 0 to 150 ° C, preferably 50 to 1
At 30 ℃, under reduced pressure of 1mmHg-760mmHg or under normal pressure,
It is preferable to remove water while stirring under reduced pressure of 30 mmHg to 600 mmHg.

The amount of the (meth) acrylic acid ester-based polymer particles [II] dispersed in the epoxy resin is preferably 1 part by weight to 50 parts by weight in terms of solid content, more preferably 100 parts by weight of the epoxy resin. Is 2 to 30 parts by weight. (Meth) acrylic ester polymer particles [II]
If the amount is less than 1 part by weight, the toughening effect is hardly obtained, while if it exceeds 50 parts by weight, the viscosity of the epoxy resin composition becomes too high and the original properties of the epoxy resin are impaired.

In the thus obtained epoxy resin composition of the present invention, quartz glass powder, silica,
It is, of course, possible to add fillers such as clay, calcium carbonate, kaolin, talc, titanium oxide and aluminum hydroxide, pigments and the like.

The epoxy resin composition of the present invention can be used for various purposes by combining it with various curing agents. Examples of the curing agent include diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Linear aliphatic amines such as diethylaminopropylamine; various polyamides with different amine values; alicyclic amines such as menthenediamine, isophoronediamine, bis (4-aminocyclohexyl) methane; m-xylenediamine, diamino Aromatic amines such as diphenylmethane, diaminodiphenylsulfone, and m-phenylenediamine; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, dodecyl Succinic anhydride, pyromellitic dianhydride,
Acid anhydrides such as methylcyclohexene tetracarboxylic anhydride, trimellitic anhydride, polyazelaic anhydride, and the like; phenolic hydroxyl group-containing compounds such as phenol novolac and cresol novolac; polymercaptans; 2,4,6-tris Anionic polymerization catalysts such as (dimethylaminomethyl) phenol and 2-ethyl-4-methylimidazole; Cationic polymerization catalysts such as BF ₃ monoethylamine complex; Dicyandiamide, amine adduct,
Hydrazide, amidoamine, blocked isocyanate,
Examples thereof include latent curing agents represented by carbamates, ketimines, aromatic diazonium salts, and the like, and one or more of them can be used.

[0056]

The epoxy resin composition of the present invention comprises (meth) acrylic acid ester-based polymer particles uniformly dispersed in an epoxy resin, and has a conventional toughness obtained by adding a dissolution / reaction deposition type rubber. As in the case of the epoxy resin composition, the toughening effect does not vary depending on the curing conditions, and the rubber component dissolved in the epoxy resin is substantially zero, so that the heat resistance is also good. Moreover, as compared with the core / shell type rubber particle emulsion, since no shell component is present, a small amount of the compound exhibits an excellent toughening effect. Furthermore, by using a modified polyamine having a specific structure as an emulsifier, foaming during dehydration during the production of an epoxy resin composition is suppressed, and the production of the composition is significantly simplified.
Further, the modified polyamine used as an emulsifier has reactivity with the epoxy resin and is chemically bonded to the epoxy resin, so that the obtained epoxy resin composition is tough, and has water resistance (moisture resistance) and adhesion. It has excellent properties and can be effectively used as an adhesive, a molding material, a paint, a sealant, and the like.

[0057]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the examples, "%" and "parts" mean "% by weight" and "parts by weight" unless otherwise specified.
Shall mean.

Reference Example 1 (Production of emulsifier-modified polyamine) Polyethyleneimine (Epomin SP) was placed in a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
-006, manufactured by Nippon Shokubai Co., average molecular weight of about 600) 45 parts, 14.7 parts of a mixture of α-olefin epoxides having 12 and 14 carbon atoms (AOE-X24, manufactured by Daicel Chemical Co., Ltd.) were charged and while gently blowing nitrogen gas. The mixture was heated to 80 ° C. and reacted for 4 hours to obtain modified polyamine [Ia].

Reference Examples 2 to 3 (Production of Emulsifier-Modified Polyamine) In Reference Example 1, the polyamine compound, compound (B) and compound (C) shown in Table 1 were used, and the reaction time was shown in Table 1. Modified polyamines [Ib] and [Ic] were obtained in the same manner as in Reference Example 1 except for the above changes.

[0060]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 7 (1) Production of (meth) acrylic acid ester-based polymer A flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser was pure. 63 parts of water was charged and heated to 70 ° C. while gently blowing nitrogen gas. On the other hand, 85 parts of ethyl acrylate, 10 parts of methyl methacrylate, 5 parts of glycidyl methacrylate, 2 parts of the modified polyamine [Ia] obtained in Reference Example 1, 0.75 parts of acetic acid, and 36 parts of ion-exchanged water were well stirred in advance, It was charged into the dropping funnel as a fully emulsified pre-emulsion.

Next, 3 parts of a 10% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride was poured into the flask, and the above pre-emulsion was added dropwise from the dropping funnel over 3 hours and 30 minutes. did. After the dropping was completed, the dropping funnel was washed with 10 parts of ion-exchanged water so that the pre-emulsion did not remain, and the washing solution was added into the flask. During the dropping of the pre-emulsion, the temperature was maintained at 70 to 75 ° C., and after the dropping was completed, the mixture was stirred at the same temperature for 1 hour to terminate the polymerization,
Non-volatile 47.0% (meth) acrylic acid ester-based polymer emulsion (hereinafter referred to as acrylic emulsion)
Obtained [1].

An acrylic emulsion [2] was prepared in the same manner as above except that the modified polyamine used as an emulsifier and the polymerizable monomer component were changed to those shown in Table 2.
-[5] and comparative emulsions [C1]-[C]
4] was obtained.

<Glass Transition Temperature> After water was dispersed from the emulsion, the glass transition temperature of the (meth) acrylic acid ester polymer particles was measured using DSC7 manufactured by PERKIN-ELMER.

[0065]

[Table 2]

(2) Production of Epoxy Resin Composition Acrylic emulsion obtained in the above (1) [1] to [5]
The emulsions [C1] to [C4] for comparative examples were placed in a flask equipped with a stirrer, a nitrogen introducing tube, and a condenser, and ion-exchanged water was added to adjust the nonvolatile content concentration to 30%. A predetermined amount of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) was added and stirred to obtain a uniform viscous liquid. Then, the temperature was raised to 70 ° C., and finally the pressure was reduced to 50 mmHg to remove water while gradually increasing the degree of pressure reduction. Thereafter, the mixture was heated to 130 ° C. to completely remove water, and the amino group in the emulsifier (modified polyamine) was preliminarily reacted with the epoxy resin.

The constitution of the obtained epoxy resin composition (the measuring method is as follows) is shown in Table 3. In addition, in the case of using the emulsions [C1] to [C4] for comparative examples, since foaming during dehydration is so strong that water cannot be removed to the end, 0.3 part of San Nopco 8034L (manufactured by San Nopco) was added as an antifoaming agent. The same operation was performed from.

<Water content in epoxy resin composition> Karl-F
The water content in the epoxy resin composition was measured using an ischer Moisture Meter (KYOTO ELECTRONICS MKS-3p).

<Epoxy equivalent> HCl / THF was reacted and excess HCl was measured by back titration.

(3) Properties of Cured Product of Epoxy Resin Composition <Adhesion Test> The epoxy resin composition obtained in (2) above was mixed with a curing agent in the ratio shown in Table 3 to perform an adhesion test.
As the adherend, a cold-rolled steel plate having a thickness of 1.5 mm (0.5 mm in the T-type peel test) was polished with # 100 sandpaper, washed with acetone and degreased. The adhesive was cured by heating at 80 ° C. for 1 hour and then at 150 ° C. for 0.5 hour to measure the following adhesive strength.

Tensile shear strength : Performed according to JIS K 6850. Tensile speed: 10 mm / min Hot water resistance : After soaking in hot water at 80 ° C for 24 hours,
The tensile shear strength was measured at room temperature (23 ° C). Tension rate: 10 mm / min T-type peeling strength : Performed according to JIS K 6854. Pulling speed: 50mm / min

[0072]

[Table 3]

As is clear from Table 3, the epoxy resin composition of the present invention shows little decrease in tensile shear strength after immersion in hot water at 80 ° C. and is also very excellent in T-type peel strength. I understand.

Examples 6 to 12 and Comparative Examples 8 to 12 Table 4 was prepared in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 7.
An epoxy resin composition having the constitution shown in was produced. The obtained epoxy resin composition was mixed with the curing agent in the compounding ratio shown in Table 4 and then molded, and various physical properties of the molded product were tested. The results are also shown in Table 4. Incidentally, the curing of the molded product is 85
After heating at ℃ for 3 hours, it was performed by further heating at 150 ℃ for 3 hours.

<Fracture toughness value> A test piece of the size shown in FIG. 1 was prepared, and a starter crack was formed at the tip of the central cutout with a razor, and a load-time curve was obtained at a pulling speed of 10 mm / min (FIG. 2). The load at break (Pc),
The fracture toughness value was calculated from the crack length (a) and the like by the following formula.

[0076]

[Equation 1]

F (x) is a form factor expressed by the following equation, and x = a / w. f (x) = 1.93-3.07x + 14.53x 2 - 25.11x 3 + 25.80x 4

<Deflection temperature under load> In accordance with JIS K 7207,
It was measured using Toyo Seiki's HDT & VSPT TESTER.

<Water Absorption> The water absorption of a test piece having a thickness of 3 mm was immersed in warm water at 80 ° C. for 24 hours, and the water absorption was determined by the following formula. (Weight after immersion in warm water-Weight before immersion in warm water) x 100 / Weight before immersion in warm water = Water absorption rate (%)

[0080]

[Table 4]

As is clear from Table 4, the epoxy resin composition of the present invention has an increased fracture toughness value without lowering the deflection temperature under load, and has an excellent water absorption rate as compared with the conventional method. It turns out that Further, as is clear from a comparison between Example 11 and Comparative Example 9, when compared at the same deflection temperature under load, the cured product of the epoxy resin composition according to the present invention is an epoxy that is toughened by CTBN rubber. It can be seen that the fracture toughness value is twice or more that of the resin composition.

[Brief description of drawings]

FIG. 1 is a dimensional explanatory diagram of a fracture toughness value measurement sample used in Examples.

FIG. 2 is a graph showing a load-time relationship when measuring a fracture toughness value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08L 33/10 LJE (72) Inventor Masashi Izumibayashi 5-8 Nishimitabicho Suita City Osaka Prefecture Central Research Laboratory, Nippon Shokubai Co., Ltd. (56) Reference JP-A-2-14095 (JP, A) JP-A-63-57605 (JP, A) JP-A-58-206604 (JP, A) JP-A-58- 206603 (JP, A)

Claims (5)

[Claims] 1. A polyamine compound (A) having two or more primary and / or secondary amino groups in the molecule has the general formula R- (OX) _n -Y (B) (wherein R is A compound represented by a hydrocarbon group having 4 or more carbon atoms, X is a lower alkylene group, n is 0 or an integer from 1 to 30, and Y is an atomic group having a functional group capable of reacting with an amino group. A modified polyamine [I] obtained by reacting B) and / or a salt thereof is used as an emulsifier to obtain a (meth) acrylic acid ester monomer (C) by emulsion polymerization. An epoxy resin composition comprising (meth) acrylic acid ester-based polymer particles [II] having a glass transition temperature of 20 ° C. or lower dispersed in an epoxy resin. 2. The modified polyamine [I] comprises the polyamine compound (A), the compound (B) and the general formula R′—Y (D) (wherein R ′ is an atomic group having a polymerizable unsaturated group, Y). Is obtained by reacting a compound (D) represented by an atomic group having a functional group capable of reacting with an amino group). 3. The epoxy resin composition according to claim 1, wherein the (meth) acrylic acid ester-based polymer particles [II] have a crosslinked structure. 4. The epoxy resin composition according to claim 1, wherein the (meth) acrylic acid ester-based polymer particles [II] have a functional group capable of reacting with an amino group in the molecule. object. 5. The method according to claim 1, wherein the emulsion of the (meth) acrylate polymer particles [II] according to any one of claims 1 to 4 is uniformly mixed with an epoxy resin, and then water is removed. Method for producing epoxy resin composition.