JP2005255822A - Rubber-reinforced epoxy resin product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin product obtained by curing a reinforced epoxy resin composition, by overcoming various problems which are possessed by conventional techniques and caused when an epoxy resin is reinforced. <P>SOLUTION: This rubber-reinforced epoxy resin product contains a cured material obtained by curing an epoxy resin composition (C) in which a core-shell polymer (B) is dispersed in the epoxy resin (A) in a state of existing as primary particles by a curing agent (D), wherein the epoxy resin product comprises at least one kind selected from a group comprising a glass fiber-reinforced composite material, a carbon fiber-reinforced composite material, an adhesive, a coating material, a laminated sheet, and a semiconductor sealing agent. The epoxy resin product has, in more detail, such a structure that the core-shell polymer (B) is dispersed in the state of existing as the primary particles, even after the resin composition is cured by the curing agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a rubber-reinforced epoxy resin product using a rubber-reinforced epoxy resin composition. More specifically, the present invention relates to a rubber-reinforced epoxy using an epoxy resin composition in which a core-shell polymer is dispersed in a primary particle state in an epoxy resin. It relates to resin products.

  As a method for enhancing toughness by adding a modifier to an epoxy resin, a method of adding a rubber component or a thermoplastic resin to the epoxy resin composition is known.

  As a method of adding a rubber component, a method of adding a reactive liquid rubber (such as CTBN) or a nitrile rubber (for example, see Patent Document 1) is known. However, since the reactive liquid rubber undergoes a process of once dissolving in the epoxy resin and then phase-separating at the time of curing, the morphology of the cured product changes depending on the type of epoxy resin to be blended and the curing conditions. In addition to the fact that the modification effect cannot be obtained or there is a problem in the reproducibility of the quality, the rubber component partially dissolves and remains in the cured epoxy resin phase. (Hereinafter, also referred to as Tg) has been lowered, resulting in a problem that the quality of the epoxy resin product is lowered. Furthermore, when the epoxy resin product itself becomes large and the curing temperature for producing the epoxy resin product varies depending on the site, the quality may vary depending on the site.

  As a method for solving the problem of morphological change and its control due to the addition of the rubber component, a composition in which rubber-like particles are dispersed in the epoxy resin is obtained by polymerizing monomers such as acrylate esters in the epoxy resin. The obtaining method is known (for example, refer to Patent Document 2). However, even by the above method, it is unavoidable that a part of the rubber component is dissolved in the cured epoxy resin phase, and the glass transition temperature may be lowered, which is not sufficient in quality.

  On the other hand, as a method for adding a thermoplastic resin, it is well known that a thermoplastic resin having a high glass transition temperature (so-called super engineering plastic or the like) is used. In this method, it is possible to impart a certain degree of toughness while maintaining the glass transition temperature and heat resistance of the cured product.However, since a large amount of addition is generally required, there is a problem in handling with an increase in the viscosity of the system. And complicated processes such as dissolution are necessary, and morphological control is necessary, and it cannot be said to be a sufficient level.

In addition, the epoxy resin composition containing rubber-like polymer particles insoluble in the epoxy resin prevents the heat resistance (glass transition temperature) from decreasing because the rubber component does not dissolve in the cured epoxy resin phase. Can do. The rubber-like polymer particles in this case are not polymerized in the epoxy resin, but are prepolymerized and mixed with the epoxy resin. As such rubber-like polymer particles, a so-called core-shell polymer is representative (see, for example, Patent Document 3 or Patent Document 4). Moreover, these core-shell polymers are widely marketed under product names such as Kane Ace (manufactured by Kaneka Chemical Co., Ltd.) and Paraloid (manufactured by Rohm and Haas). However, these are commercially available as an aggregate (aggregate) of primary particles, for example, in the form of powder of several tens to several hundreds of microns, and when mixed with an epoxy resin, these can be finely powdered to less than 10 μm, Furthermore, if the mixture is not carefully mixed with a kneader such as a heated stirrer, high-speed shear stirrer, hot roll, intermixer, kneader, or triple roll at a temperature of 50 to 200 ° C., the mixed core-shell polymer easily precipitates or floats. There is a problem of separation. Even after careful mixing and kneading for several hours, the mixed core-shell polymer is agglomerated without being dispersed with primary particles, and depending on the type of epoxy resin, the mixed core-shell polymer is easy to separate, etc. This problem is unsatisfactory because of this problem and the need to add a dispersion stabilizer. Furthermore, since the size of the core-shell polymer actually dispersed in the epoxy resin is not the primary particles, there is a problem that it is difficult to optimize the design of the core-shell polymer particles. Under these circumstances, commercially available powdery core-shell polymers do not have sufficient performance as epoxy resin reinforcing agents.
Japanese Patent Publication No.62-34251 JP 59-138254 A U.S. Pat. No. 3,322,852 US Pat. No. 3,496,250

  The object of the present invention is to provide an epoxy resin product obtained by curing the reinforced epoxy resin composition having high toughness, overcoming various problems in the epoxy resin reinforcement of the prior art as described above. It is in.

  The present invention contains a cured product obtained by curing an epoxy resin composition (C) in which a core-shell polymer (B) is dispersed in a state of primary particles in an epoxy resin (A) with a curing agent (D). A rubber-reinforced epoxy resin product, characterized in that it is at least one selected from the group consisting of a glass fiber reinforced composite material, a carbon fiber reinforced composite material, an adhesive, a coating material, a laminate, and a semiconductor encapsulant. The present invention relates to a rubber-reinforced epoxy resin product.

  In a preferred embodiment, the rubber-reinforced epoxy is characterized in that the core-shell polymer (B) is dispersed in the form of primary particles even after the epoxy resin composition (C) is cured with the curing agent (D). It relates to resin products.

  In a preferred embodiment, the epoxy resin composition (C) containing the epoxy resin (A) and the core-shell polymer (B) mixes the aqueous latex containing the core-shell polymer (B) with an organic solvent, and then separates the aqueous phase. And an epoxy resin composition produced by mixing the dispersion (E) obtained by removing the core-shell polymer (B) dispersed in an organic solvent with the epoxy resin (A). The rubber-reinforced epoxy resin product according to any one of the above.

  In a preferred embodiment, the epoxy resin composition (C) containing the epoxy resin (A) and the core-shell polymer (B) mixes an aqueous latex containing the core-shell polymer (B) with an organic solvent, and further contains a water-soluble electrolyte or After adding an aqueous latex and an immiscible organic solvent, the dispersion (E) obtained by dispersing the core phase polymer (B) in the organic solvent obtained by separating and removing the aqueous phase is converted into an epoxy resin (A). The rubber-reinforced epoxy resin product described above, wherein the rubber-reinforced epoxy resin product is manufactured by mixing with a rubber.

  In a preferred embodiment, in the production of the epoxy resin composition (C), prior to mixing the dispersion (E) with the epoxy resin (A), the dispersion (E) is contacted with water or an aqueous solution of a water-soluble electrolyte. The rubber-reinforced epoxy resin product according to any one of the above, wherein the operation of separating the aqueous phase is performed at least once.

  A preferred embodiment is characterized in that the solubility in water at 25 ° C. of the organic solvent first mixed with the aqueous latex containing the core-shell polymer (B) is 5% by weight or more and 40% by weight or less. The present invention relates to a rubber reinforced epoxy resin product.

  Preferred embodiments are selected from curing accelerators, inorganic fillers, organic or polymer fillers, flame retardants, antistatic agents, conductivity imparting agents, lubricants, slidability imparting agents, surfactants, and colorants. The rubber-reinforced epoxy resin product according to any one of the above, characterized by containing at least one kind of additive.

  The epoxy resin product of the present invention is an epoxy resin using a conventional rubber-reinforced epoxy resin by using a rubber-reinforced epoxy resin composition in which rubber polymer particles, particularly preferably a core-shell polymer is stably dispersed in a primary particle state. Excellent fracture toughness, crack resistance, rigidity, heat resistance, heat shock resistance, adhesion, and fatigue resistance can be shown compared to resin products.

  The present invention relates to an epoxy resin product obtained by curing a reinforced epoxy resin composition in which rubber-like polymer particles, particularly preferably core-shell polymers are stably dispersed in a primary particle state, with a curing agent.

  First, the reinforced epoxy resin used in the present invention will be described.

  The epoxy resin (A) used in the present invention is not particularly limited as long as it is a compound having an epoxy group, but is preferably a prepolymer having an epoxy group. The epoxy resin that can be used in the present invention is preferably an epoxy resin also called a polyepoxide. For example, diglycidyl ether of bisphenol A, novolac type epoxy resin, tri- or tetrafunctional epoxy resin, and high molecular weight epoxy resin (for example, diglycidyl ether of bisphenol A high molecular weight with bisphenol A), or Examples thereof include homopolymers or copolymers obtained by polymerizing unsaturated monoepoxides (for example, glycidyl (meth) acrylate, allyl glycidyl ether).

  Examples of the polyepoxide that can be used in the present invention include glycidyl ethers, polyglycidyl amines, polyglycidyl amides, polyglycidyl imides, polyglycidyl hydantoins, polyglycidyl thioethers, epoxidized fatty acids or epoxidized drying oils of polyhydric alcohols and polyhydric phenols. , Epoxidized polyolefins, epoxidized unsaturated polyesters, and mixtures thereof. Many polyepoxides synthesized from polyhydric phenols are disclosed, for example, in US Pat. No. 4,431,782. Polyepoxides are synthesized from monovalent, divalent and trivalent phenols and also include novolak resins. In addition to epoxidized cycloolefin, polyepoxides include polyepoxides based on polymers or copolymers of glycidyl (meth) acrylate and allyl glycidyl ether. Further examples of suitable polyepoxides include U.S. Pat. Nos. 3,804,735, 3,892,819, 3,948,698, 4,014,771, and " What is disclosed in "Epoxy resin handbook" (Nikkan Kogyo Shimbun, 1987) is mentioned.

  Examples of the polyepoxide used in the present invention include those described above. Generally, those having an epoxy equivalent weight (Epoxy Equivalent Weight) of 80 to 2000 are exemplified. These polyepoxides can be obtained by a well-known method. For example, a commonly used method is obtained by reacting an excess amount of epihalohydrin in the presence of a base with a polyhydric alcohol or polyhydric phenol.

  The polyepoxide may contain a monoepoxide as a reactive diluent, for example, an aliphatic glycidyl ether such as butyl glycidyl ether, or phenyl glycidyl ether or cresyl glycidyl ether. As is generally known, the monoepoxide affects the stoichiometry of the polyepoxide formulation, but this can be adjusted by the amount of hardener or other known methods.

  The epoxy resin (A) component may contain a curing agent and / or a curing accelerator of the above epoxy group-containing compound, but is substantially unintentional curing as an epoxy resin under the production conditions according to the present invention. It is desirable not to cause a reaction. As this hardening | curing agent and / or hardening accelerator, what satisfy | fills the requirements mentioned above in the above-mentioned epoxy resin handbook can be used.

  The core-shell polymer (B) that can be used in the present invention is composed of a core part (B-1) made of a polymer mainly composed of an elastomer or a rubber-like polymer, and a shell layer made of a polymer component graft-polymerized thereto ( It is preferable that it is a polymer comprised from B-2). The shell layer can cover a part or the whole of the surface of the core part by graft polymerization of the monomer constituting the graft component onto the core component.

  The polymer constituting the core part (B-1) is cross-linked and may swell in a good solvent of the polymer constituting the core part, but does not substantially dissolve and is insoluble in the epoxy resin. preferable. The gel content of the core part is preferably 60% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more. Since the polymer constituting the core portion preferably has rubber properties, the glass transition temperature (Tg) is preferably 0 ° C. or lower, and preferably −10 ° C. or lower.

  The polymer constituting the core part (B-1) is composed of a monomer containing 50% by weight or more of one or more monomers selected from conjugated diene monomers and (meth) acrylic acid ester monomers, Or it is preferable to use polysiloxane rubber or these together. In the present invention, (meth) acryl means acryl and / or methacryl.

  Examples of the conjugated diene monomer constituting the core part (B-1) include butadiene, isoprene, chloroprene, and the like. However, they can be obtained at low cost, and the properties of the resulting polymer as rubber are good. Butadiene is particularly preferred from the viewpoint of easy polymerization. Examples of the (meth) acrylic acid ester-based monomer include butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and the like. From the viewpoint that the properties of the resulting polymer are good and polymerization is easy. , Butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. These can be used alone or in combination of two or more. The amount of the conjugated diene monomer or (meth) acrylic acid ester monomer used is preferably 50% by weight or more, more preferably 60% by weight or more based on the weight of the entire core part. If it is less than 50% by weight, the ability to impart toughness to the epoxy resin may be reduced.

  Furthermore, when the polymer which comprises the said core part (B-1) uses the above-mentioned conjugated diene type monomer or the (meth) acrylic acid ester type monomer as a main component, it is 1 or more types copolymerizable with these. It may be a copolymer with a vinyl monomer. Examples of such monomers include alkyl (meth) acrylates other than the aforementioned alkyl (meth) acrylates, vinyl aromatic monomers, vinylcyan monomers, and the like. For example, (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl methacrylate, vinyl aromatic monomers, for example, styrene, α-methyl styrene, vinyl cyan monomers Examples thereof include (meth) acrylonitrile and substituted acrylonitrile. These can be used alone or in combination of two or more. The amount of these used is preferably less than 50% by weight, more preferably less than 40% by weight based on the total weight of the core part (B-1).

  Moreover, you may use a polyfunctional monomer as a component which comprises the said core part (B-1), in order to adjust a crosslinking degree. Examples of the polyfunctional monomer include divinylbenzene, butanediol di (meth) acrylate, triallyl (iso) cyanurate, allyl (meth) acrylate, diallyl itaconate, diallyl phthalate, and the like. The amount of these used is 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less based on the total weight of the core part. If it exceeds 10% by weight, the properties of the core as an elastomer are impaired, which is not preferable.

  Furthermore, it is also possible to use polysiloxane rubber as the core part (B-1) instead of the vinyl polymerizable polymer as described above or in combination with these. When polysiloxane rubber is used as the core part (B-1), for example, a polysiloxane rubber composed of alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, etc. Can be used. When using such a polysiloxane rubber, if necessary, partially use a polyfunctional alkoxysilane compound during polymerization, or radically react a silane compound having a vinyl reactive group. It is more preferable to introduce a crosslinked structure in advance, for example.

  The shell part (B-2) has a function of giving affinity to the epoxy resin so that the core-shell polymer (B) is stably dispersed in the state of primary particles in the epoxy resin. The polymer constituting the shell part (B-2) is graft-polymerized to the polymer constituting the core part (B-1) and is substantially bonded to the polymer constituting the core part (B-1). It is preferable. Specifically, the polymer constituting the shell part (B-2) is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more bonded to the core part (B-1). It is desirable that The shell part (B-2) preferably has swelling, compatibility or affinity for the organic solvent and epoxy resin (A) described later. The shell part (B-2) has reactivity with the epoxy resin (A) or a curing agent blended at the time of use depending on the necessity at the time of use, and the epoxy resin (A) reacts with the curing agent. Then, it may have a function of chemically reacting with these under the conditions of curing and generating a bond.

  The polymer constituting the shell part (B-2) can be obtained at a low cost, and can have both good graft polymerizability and affinity for the epoxy resin. A polymer or copolymer obtained by polymerizing or copolymerizing at least one component selected from a group vinyl compound and a vinyl cyanide compound is preferable. Further, in particular, when chemical reactivity at the time of curing the epoxy resin of the shell portion is required, in addition to the above-mentioned monomers, it has reactive side chains such as hydroxyalkyl (meth) acrylate and epoxyalkyl (meth) acrylate (meta ) From a monomer group consisting of acrylic acid esters, epoxy alkyl vinyl ether, (meth) acrylamide (including N-substituents), α, β-unsaturated acid, α, β-unsaturated acid anhydride, maleimide derivatives, etc. A copolymer obtained by copolymerizing at least one selected component is more preferable. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, styrene, α-methylstyrene, (meth) acrylonitrile, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, Examples thereof include glycidyl (meth) acrylate, glycidyl vinyl ether, (meth) acrylamide, maleic anhydride, maleic imide and the like, but are not limited thereto. These can be used alone or in combination of two or more.

  The preferred core part (B-1) / shell part (B-2) ratio (weight ratio) of the core-shell polymer (B) in the present invention is preferably in the range of 50/50 to 95/5, more preferably. 60/40 to 90/10. When the ratio of the core part (B-1) / shell part (B-2) (weight ratio) exceeds 50/50 and the ratio of the core part (B-1) decreases, the toughness improving effect on the epoxy resin (A) is improved. There is a tendency to decrease. On the other hand, if the ratio of the shell part (B-2) is reduced beyond 95/5, aggregation may easily occur during handling in the present invention, causing problems in operability and possibly preventing the expected physical properties from being obtained.

  There is no restriction | limiting in particular about manufacture of such a core shell polymer (B), For example, it can manufacture by a well-known method, for example, emulsion polymerization, suspension polymerization, micro suspension polymerization, etc. Among these, the production method by emulsion polymerization is particularly suitable.

  The particle diameter of the core-shell polymer (B) that can be used in the present invention is not particularly limited, and any core-shell polymer (B) that can be stably obtained in the form of an aqueous latex can be used without any problem. From the viewpoint of industrial productivity, those having a volume average particle diameter of about 0.03 to 1 μm are more preferable in terms of easy production. The volume average particle diameter can be measured using Microtrac UPA (manufactured by Nikkiso Co., Ltd.).

  The epoxy resin composition (C) used in the epoxy resin product of the present invention is preferably obtained by a specific production method. Specifically, the core-shell polymer (B) obtained in the state of an aqueous latex is mixed with an organic solvent, the core-shell polymer (B) is taken out into the organic phase, and a dispersion in which the core-shell polymer (B) is dispersed in the organic solvent ( After obtaining E), a method of mixing with the epoxy resin (A) can be mentioned. As such a method, for example, the method described in Japanese Patent Application No. 2003-107882, Japanese Patent Application No. 2003-164416, or Japanese Patent Application No. 2003-326711 is preferably used.

  More specifically, a dispersion in which the core-shell polymer (B) is dispersed in the organic solvent by mixing the aqueous latex containing the core-shell polymer (B) with a specific organic solvent and separating and removing the aqueous phase ( In the process of obtaining E), preferably, after mixing the aqueous latex of the core-shell polymer (B) with a specific organic solvent, and further adding a water-soluble electrolyte or an aqueous latex and an immiscible organic solvent, the aqueous phase is separated. It is preferable to remove and obtain a dispersion (E) in which the core-shell polymer (B) is dispersed in an organic solvent. By mixing this with the epoxy resin (A) and removing volatile components including an organic solvent as required, the epoxy resin composition (C) used in the epoxy resin product of the present invention can be produced. More preferably, after the dispersion (E) is brought into contact with water or a water-soluble electrolyte aqueous solution, the operation of separating and removing the aqueous phase is performed once or more and then mixed with the epoxy resin (A). Can do.

  Examples of the specific organic solvent mixed with the aqueous latex containing the core-shell polymer (B) include esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone. Ketones, alcohols such as ethanol, (iso) propanol, butanol, ethers such as tetrahydrofuran, tetrahydropyran, dioxane, diethyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, etc. One or more organic solvents selected from halogenated hydrocarbons or the like, or a mixture thereof, and those having a solubility in water at 20 ° C. of preferably 5% by weight or more and 40% by weight or less are preferable. When the water solubility is less than 5% by weight, mixing with the aqueous latex containing the core-shell polymer (B) tends to be somewhat difficult. Conversely, when it exceeds 40% by weight, the water-soluble electrolyte or It tends to become increasingly difficult to efficiently separate and remove the aqueous phase after adding an aqueous latex and an immiscible organic solvent.

  Moreover, a well-known organic solvent can be used as an organic solvent immiscible with aqueous latex. For example, esters such as ethyl acetate, propyl acetate and butyl acetate, ketones such as diethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether and butyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, hexane, etc. And one or more organic solvents selected from aliphatic hydrocarbons such as aliphatic hydrocarbons such as methylene chloride and chloroform, or a mixture thereof, preferably those having a water solubility of less than 5% by weight. The When the water solubility is 5% by weight or more, the effect of efficiently separating the aqueous phase is reduced when added to a mixture of the aqueous latex containing the core-shell polymer (B) and the specific organic solvent. There is a tendency.

  Further, the water-soluble electrolyte is not particularly limited in structure, composition, and the like, and can be used without limitation as long as it has a water-solubility that does not precipitate during operation and become a contamination source. Specific examples include water-soluble alkali metal salts, alkaline earth metal salts, ammonium salts, and more specifically sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, Examples thereof include magnesium sulfate, sodium phosphate, potassium phosphate, calcium phosphate, ammonium sulfate, and inorganic acids such as hydrochloric acid and sulfuric acid. When the aqueous latex and the non-mixable organic solvent are not added to the mixture of the aqueous latex and the specific organic solvent, and such a water-soluble electrolyte is not added, the aqueous phase is efficiently removed from the mixture. It may be relatively difficult to separate and remove.

  More preferably, prior to mixing the dispersion (E) of the core-shell polymer (B) thus obtained in an organic solvent with the epoxy resin (A), the dispersion (E) is water or water-soluble. By performing the operation of separating the aqueous phase one or more times after contacting with the aqueous electrolyte solution, water-soluble impurities such as emulsifiers or dispersants used in preparing the aqueous latex containing the core-shell polymer (B) are further reduced or It is also possible to remove it.

  As a method for removing volatile components including an organic solvent from the mixture containing the epoxy resin composition (C) thus obtained, a known method can be applied. For example, the mixture is charged into a tank (depressurized) and distilled. Use a batch-type method to leave, a method in which a dry gas and the mixture are brought into countercurrent contact in a tank, a continuous method using a thin film evaporator, an extruder equipped with a devolatilizer, or a continuous stirring tank. The method etc. are mentioned. Conditions such as temperature and required time for removing the volatile component can be appropriately selected within a range in which the epoxy resin (A) does not react or deteriorate the quality. Further, such a volatile component removal operation can be carried out after blending a curing agent (D) or an additive according to the various uses for convenience of various uses.

  The epoxy resin product of the present invention is an epoxy resin composition (C) obtained as described above, or a reinforced epoxy resin in which (C) and an appropriate epoxy resin are combined, depending on the needs of each industrial field. Curing agents, crosslinking agents, fillers, pigments, coupling agents, leveling agents, antioxidants, solvents, dispersion stabilizers, reactive diluents, adhesion-imparting agents, antifoaming agents, lubricants, perfumes, heat An additive such as a plastic resin, a promoter, a thixotropic agent, and a compounding agent are appropriately blended, and can be obtained by molding and curing. Hereinafter, the epoxy resin product of the present invention will be specifically described.

(1) Coating material In addition to having high toughness and impact resistance, the coating material using the reinforced epoxy resin of the present invention is excellent in corrosion resistance and chemical resistance because it does not impair the degree of crosslinking of the resin. Any coating material of solvent-based, water-based, or solvent-free (powder paint) is useful. Moreover, it can be used for any of primer, intermediate coating and top coat.

  Curing agents include acid anhydrides, polyamines, novolac type phenol resins, tertiary amines, triphenylphosphine, imidazole compounds, dibasic acid hydrazides, N, N′-dialkylurea derivatives, alkylaminophenol derivatives, melamine, guanamine, etc. One or more of these can be used.

  Moreover, a thermoplastic resin can also be added to a suitable grade. Examples of the thermoplastic resin include acetal resins such as phenoxy resin, polyvinyl butyral, and polyvinyl formal, polyethersulfone (PES), polysulfone (PSF), polyetherimide (PEI), polyarylate, polyamide, and polyimide. Examples thereof include polyamide, styrene acrylonitrile copolymer, acrylic resin, polyester and the like (these may have a functional group). Moreover, a phenol resin can also be mix | blended.

  Examples of the crosslinking agent include polyamine, polyaminoamide, polycarboxylic acid, acid anhydride, polyhydrazide and the like.

  As fillers, talc powder, crystalline silica powder, fused silica powder, calcium carbonate powder, magnesia powder, calcium silicate powder, hydrated alumina powder, alumina powder, zircon powder, graphite, barium sulfate, clay, mica powder, barite, Examples include diatomaceous earth, calcium silicate, aluminum silicate, barium carbonate, and magnesium carbonate.

  If necessary, additives such as pigments, coupling agents, and leveling agents can be blended. As pigments, extender pigments such as titanium white, talc, calcium carbonate and silica can be blended.

  Moreover, polyisocyanate can be mix | blended as needed. Polyisocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), isophorone disocyanate (IPDI), hydrogenated TDI, hydrogenated Known polyisocyanates such as XDI can be used. These isocyanates may be blocked isocyanates reacted with a blocking agent. Examples of the blocking agent include hydroxyl group-containing compounds and preferred examples, and examples thereof include compounds such as phenols, lactams, oximes, imides, and alcohols. Commercially available blocked isocyanates or blocked isocyanate-containing urethane-modified epoxy resins can also be used.

  Moreover, antioxidant can also be mix | blended as needed. Examples of the antioxidant include phenolic, phosphorus-based and sulfur-based compounds. Specifically, phosphorus-based antioxidants such as tris (2,4-di-tert-butylphenyl) phosphite and tris (nonylphenyl) phosphite, and sulfur-based compounds such as dilauryl-3,3′-thiodipropionate Examples thereof include phenolic antioxidants represented by antioxidants, IR-245, IR-1076 (all manufactured by Ciba Specialty Chemicals) and the like. The antioxidant needs to be blended so as not to interfere with the necessary reaction between the epoxy resin and other blends.

  In solvent-based paints, an organic solvent is usually used to make a paint. However, the reinforced epoxy resin according to the present invention is stable in the core-shell polymer even when dissolved in a solvent generally used in solvent-based paints. Therefore, the characteristics of the reinforced epoxy resin are not impaired. The organic solvent used for coating is toluene, xylene, sorbeso, ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, isophorone, methyl solosolve, butyl solosolve, ethylene glycol monoacetate, etc. Chosen.

  In a water-based paint, a known method, that is, using an emulsifier, a dispersion stabilizer or the like, an epoxy resin is dispersed in water with mechanical shearing force to obtain a water-based epoxy resin. An aqueous dispersion can be prepared. Alternatively, the reinforced epoxy resin according to the present invention can be obtained by adding a primary or secondary amine to a modified amine-modified epoxy resin, and then neutralizing with an acid and dispersing in water. Even when the reinforced epoxy resin used in the present invention is used as an aqueous dispersion, the contained core-shell polymer (B) is stably dispersed in the epoxy resin phase and does not dissolve in the aqueous layer. Can strengthen the membrane.

  The reinforced epoxy resin of the present invention is also useful for water-based electrodeposition coating compositions. For example, a resin composition for cationic electrodeposition coating can be obtained from the reinforced epoxy resin of the present invention. It can be obtained according to a known method for obtaining an aqueous dispersion of an epoxy resin composition for ordinary cationic electrodeposition coating. That is, a modified epoxy resin in which a part of an epoxy group is ring-opened by a reaction with an alkylphenol, a monocarboxylic acid, or a hydroxycarboxylic acid as necessary, and an ionic group is introduced by a reaction of the remaining epoxy group with an amine, etc. To do. By coating and curing this with a known method using a known blocked isocyanate or melamine, a coating film can be obtained.

  If necessary, a reactive diluent, an adhesion-imparting agent, an antifoaming agent, a lubricant, a fragrance, and the like can be added. As a coating method, a known method such as roll coating, curtain flow coating, spray coating or electrostatic spray coating can be used.

  For powder coatings, the reinforced epoxy resin of the present invention is mixed with a predetermined amount of a curing agent, a crosslinking agent, a filler, an additive and the like by a mixer and melted and kneaded by a known method such as an extruder, a kneader, or a roll. Then, it is obtained by pulverizing with a pulverizer. In addition, additives for powder coatings such as a fluidity adjusting agent, a surface adjusting agent, and a slipperiness imparting agent can be blended. The obtained powder coating can be applied by a general powder coating method such as an electrostatic spray method, a hot spray method, a fluidized immersion method, an electrostatic fluidized immersion method, a rolling method, or a sprinkling method. After coating, it can be cured under known conditions, for example, a coating thickness of about 20 to 400 μm and a range of 110 to 230 ° C. The powder coating with the reinforced epoxy resin of the present invention is excellent in corrosion resistance, solvent resistance, chipping resistance, and other mechanical properties, and can be used for industrial materials, tanks, pipes, vehicles, building materials, home appliances and the like. . The softening point of the powder coating according to the present invention is in the range of 50 to 160 ° C.

(2) Adhesive The adhesive using the reinforced epoxy resin according to the present invention has high toughness and impact resistance, is excellent in the strength of the base material, and has the heat resistance (glass transition temperature) of the adhesive base material. It has the characteristic of not lowering. It is possible to obtain an adhesive with very little Tg decrease under wet conditions and very little Tg change in Dry / Wet. Utilizing one or more of these features, in addition to civil engineering and construction, automobiles (hemming, weld bonds, reinforcing agents, adhesion between resin parts and steel plates), metal-to-metal bonding, composite bonding, honeycomb It can also be used as an adhesive for assembling materials, an adhesive for electric and electronic parts, or an adhesive used in water.

  After a hardening agent, an additive, etc. are mix | blended with the reinforced epoxy resin which concerns on this invention, it is made to harden | cure on predetermined conditions and adherends are adhere | attached. Curing agents include latent curing agents such as dicyandiamide (DICY), isophthalic acid dihydrazide, N, N′-dialkylurea derivatives, N, N′-dialkylthiourea derivatives, aromatic diamines such as diaminodiphenylmethane, and other imidazoles. Can be illustrated.

  This adhesive can be blended with a thermoplastic resin or filler as used in a conventional epoxy adhesive within a range that does not impair the requirements of the present invention. Examples of the thermoplastic resin include polyethersulfone (PES), polysulfone (PSF), polyetherketone (PEK), polyamide, styrene acrylonitrile copolymer, acrylic resin, and polyester. These may have a reactive functional group that reacts with an epoxy resin, a curing agent, or the like. Further, acetal resins such as phenol resin, phenoxy resin, polyvinyl butyral, and polyvinyl formal can be blended.

  As the filler, it is possible to use known fillers such as fine particle silica (Fumed Silica), calcium carbonate, barium sulfate, calcium metasilicate, titanium oxide, carbon filler, glass chop, glass beads, and those obtained by surface treatment thereof. it can.

  Blocked isocyanates can also be added, such as tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), isophorone disocyanate (IPDI), hydrogenated TDI, Well-known polyisocyanates such as hydrogenated XDI can be used. These isocyanates may be blocked isocyanates reacted with a blocking agent. Examples of the blocking agent include hydroxyl group-containing compounds and preferred examples, and examples thereof include compounds such as phenols, lactams, oximes, imides, and alcohols. Commercially available blocked isocyanates or blocked isocyanate-containing urethane-modified epoxy resins can also be used.

  Further, in order to increase the interfacial adhesion strength with the adherend, a soft component, a promoter, or the like can be added.

  The epoxy resin product of the present invention has an adhesive as a structural adhesive (assembly of primary / secondary structural materials for vehicles and vehicle bodies, civil engineering, construction), heat resistant adhesive (for aircraft and other applications that require heat resistance), It can be used for an adhesive having excellent low-temperature characteristics (an adhesive requiring cold resistance). Moreover, as a form, it can provide in the shape of a well-known epoxy adhesive, such as a paste form and a film form.

(3) Electrical and electronic materials The epoxy resin product of the present invention in the electrical and electronic field can be used for epoxy cast insulation, powder coating insulation, laminates, and the like.

  The range in which the reinforced epoxy resin of the present invention can be used as an epoxy cast insulator may include casting, encapsulation, potting, and sealing. These insulators by the reinforced epoxy resin according to the present invention are mechanical properties such as bending strength, compressive strength, impact strength, glass transition temperature, thermal properties such as heat distortion temperature and heat resistance, heat resistance during water absorption, In addition to excellent water absorption, there are few internal voids, surface voids and cracks, internal stress can be reduced and cracks can be suppressed, and creep characteristics, dimensional accuracy and dimensional stability are excellent. It also has excellent properties of suppressing shrinkage and reducing sink marks (low shrinkage). The epoxy resin preferably has an epoxy equivalent of 150 to 800 g / eq, and bisphenol A type can be exemplified as a typical one, but other functional epoxy, novolak epoxy, cycloolefin epoxy, etc. are used to increase heat resistance. However, dimethylhydantoin type epoxy, imide-containing epoxy, epoxy-isocyanate, triazine epoxy, triglycidyl isocyanurate (TGIC) and the like can also be used. Further, a known reactive diluent, polymer liquid glycol, liquid polysulfide, or the like may be added. As the curing agent, aliphatic amine, aromatic amine, modified amine, polyamide amine, acid anhydride, boron series, imidazole series, latent curing agent, and the like can be used. In view of high temperature mechanical strength and creep, it is preferable to use an acid anhydride. As the acid anhydride, at least one of phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic acid, methyl hymic anhydride and the like can be used. Well-known fillers can be used, and examples thereof include silica, fused quartz, calcium carbonate, hydrated alumina, alumina, zircon, glass chop, asbestos, talc, mica and pentonite.

  In order to use the reinforced epoxy resin of the present invention as powder coating insulation, the electrical and electronic parts that are to be insulated are applied as a coating method, such as fluidized immersion method, electrostatic spray method, electrostatic fluidized immersion method, powder spray method, etc. By the exemplified method, it is preferably applied with a thickness of 0.05 to 5 mm. Examples of the epoxy resin include use of bisphenol A type, novolac type, and halogenated epoxy resin. Examples of the curing agent include aromatic amines, acid anhydrides, imidazoles, hydrazide adducts, dicyandiamide (DICY), and the like. A filler can also be used, and examples thereof include silica powder, calcium carbonate, fused quartz, and aluminum hydroxide.

  In order to use the epoxy resin according to the present invention as a semiconductor sealant, a tipping method, a potting method, a casting method called casting, a method of heating and melting a B-stage epoxy resin, a powder coating as described above And transfer molding.

  Examples of the epoxy resin include novolak type epoxy, cresol novolak type epoxy, and brominated epoxy. Preferable curing agents include phenol resins, modified aromatic amines, acid anhydrides and the like, effect accelerators are also used, and imidazoles are exemplified.

  Laminate is produced by adding one or more epoxy resins, curing agents, additives, etc. to the epoxy resin composition according to the present invention as needed to produce varnish, which is made of paper, glass cloth, synthetic fiber cloth, carbon fiber It can be obtained by molding a prepreg prepared by applying and impregnating a cloth or the like. The laminated board made of the reinforced epoxy resin of the present invention has heat resistance, delamination, mesling resistance, crazing, blistering, Tg change at Dry / Wet, smear resistance, through-hole reliability, finished appearance, etc. Excellent.

  Preferred epoxy resins include DGBEA type, novolak type, bisphenol A novolak type, halogenated bisphenol A type, and halogenated novolac type epoxy resins. As epoxy resin, in addition to bisphenol A type resin with epoxy equivalent of 180-1000, other functional epoxy such as novolac type epoxy, glycidylamine, triglycidyl isocyanurate (TGIC), and brominated bisphenol A type epoxy are used. it can.

  You may add a flame retardant in the range which does not impair the requirements of this invention as needed.

  Curing agents include amine curing agents such as dicyandiamide (DICY), diaminodiphenylmethane, diaminodiphenylsulfone, acid anhydrides such as hexahydrophthalic anhydride, aliphatic polyamines, aromatic polyamines, acid anhydrides, phenol novolac resins, etc. Phenolic curing agents, imidazoles, tertiary amines, polyamides, polymercaptans, melamine resins, and the like.

  The glass cloth used as the substrate is preferably E glass from the viewpoint of electrical characteristics, and can be exemplified by a glass cloth made from 2 to 15 μm glass fiber. Also to improve the adhesion with epoxy. Surface treatment is performed with a silane compound or a chromium compound. As a result, the resistance to measling can be improved.

  Using the resin composition according to the present invention, a highly multilayer laminate can be obtained. The laminate obtained by using the resin composition according to the present invention has excellent thermal characteristics, solder heat resistance, heat shock resistance, drilling workability, and dimensional stability.

  As the filler, silica powder, titanium oxide, alumina powder, silicon nitride powder, aluminum nitride powder, glass fiber, whisker or the like can be used.

  Phosphorus flame retardants typified by condensed phosphates as flame retardants, inorganic flame retardants, natural waxes, synthetic waxes and esters as release materials, carbon blacks as colorants, inorganic fillers such as silane coupling agents Treatment agents and the like can be added and blended as appropriate.

  Examples of the storage stabilizer include alkyl phenyl sulfonates such as methyl p-toluene sulfonate, ethyl p-toluene sulfonate, methyl p-chlorobenzene sulfonate, and halogenated alkyl phenyl sulfonate. 0.001 to 10 parts by weight can be used.

  In addition, the reinforced epoxy resin composition according to the present invention can be used as a stress reducing agent, and is excellent in reducing stress such as relaxation of thermal shock due to solder immersion or repeated heating, which is a problem particularly in electronic materials, Utilizing such characteristics, it can be used for the above-mentioned sealant and laminated plate.

(4) Composite material As a composite material, a resin composition is produced by adding a curing agent, an additive, and, if necessary, a plurality of epoxy resins to the reinforced epoxy resin used in the present invention, and this is made into a glass by a well-known method. A prepreg can be obtained by applying and impregnating cloth, carbon cloth or the like. It can be applied and impregnated by a solvent method or a hot melt method. Also. The composite material of the present invention can also be obtained by pultrusion, fragmentation winding, layup, resin transfer molding, resin injection molding, or the like. The prepreg can be processed into a useful shape as an epoxy resin product by a known method, layup method, vacuum back method, transfer molding, wrapping tape method, press molding method, autoclave molding method, internal pressure molding method, and the like. The obtained prepreg can also be used as a material for a honeycomb panel.

  The composite material made of the reinforced epoxy resin according to the present invention is excellent in the impact resistance and delamination property of the composite material obtained because the resin itself is excellent in impact resistance. In the present invention, unlike the conventional technique of dissolving a rubber component in an epoxy resin, the heat resistance (Tg) is not lowered, the water resistance is not lowered, and the elastic modulus is lowered while minimizing the decrease in the elastic modulus. Impact can be improved. Accordingly, the compressive strength important in CFRP, which tends to depend on the elastic modulus of the matrix resin, is characterized by excellent compressive strength particularly under high temperature and high humidity by the epoxy resin composition of the present invention. Moreover, it is excellent in interlaminar toughness, residual compression strength (compression after impact), and fatigue resistance. In addition, vibration characteristics, internal energy loss (Tan δ), and the like can be realized easily and with high reproducibility by changing the design of the core-shell polymer.

  Preferred epoxy resins include DGEBA type, polyfunctional epoxy resin glycidylamine type (including those derived from aminophenol, xylylenediamine, diaminodiphenylmethane, etc.), triglycidyl cyanurate, and novolak type. Curing agents include aromatic amines, latent curing agents (such as DICY), polyamidoamines, acid anhydrides, phenol novolac resins, cresol novolac resins, aminobenzoates, amine adduct imidazoles, and polycarboxylic anhydrides. Etc. Moreover, as a hardening accelerator, well-known things, such as a urea derivative, a tertiary amine, and imidazole, can be used.

  Examples of the fiber reinforcing agent include known fiber reinforcing agents such as glass fiber, carbon fiber, boron fiber, silicon carbide fiber, aramid fiber, silicon carbide fiber, alumina fiber, and polyethylene fiber. A combination of two or more kinds of reinforcing fibers can be used in addition to unidirectional alignment of fibers, woven fabric, and unemployed fabric.

  Moreover, inorganic fillers, such as a silica, a thixotropic agent, a pigment, etc. can also be added as needed.

  If necessary, the thermoplastic resin can be added to an appropriate level from the viewpoint of impregnation into the reinforcing fiber, reactivity, heat resistance, and the like. Examples of the thermoplastic resin include acetal resins such as phenoxy resin, polyvinyl butyral, and polyvinyl formal, polyethersulfone (PES), polysulfone (PSF), polyetherimide (PEI), polyarylate, polyamide, and polyimide.

  As a resin impregnation rate of a prepreg, the range of 10 to 40 weight% is mentioned as a preferable range.

  The composite material of the present invention can be used as epoxy resin products for pipes, tanks, panels, hulls / body bodies of ships and automobiles, primary / secondary structural agents for aircraft, and sporting goods (shafts, frames, panels, etc.) It is.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

(Production example of core-shell polymer (B) latex)
A 3 L glass container was charged with 440 g of pure water and 1300 g of rubber latex and stirred at 70 ° C. while purging with nitrogen. This rubber latex contains 420 g of rubber-like polymer particles obtained by copolymerizing 75% by weight of butadiene and 25% by weight of styrene, and the volume average particle diameter of the particles is 0.1 μm. It contains 1.5% by weight of sodium dodecylbenzenesulfonate with respect to the solid content of. After 1.2 g of azobisisobutyronitrile (AIBN) was added to this rubber latex, the following mixture was added as a graft copolymer component over 3 hours for graft polymerization.
Styrene: 54 g, methyl methacrylate: 72 g, acrylonitrile: 36 g, glycidyl methacrylate: 18 g
After completion of the addition, the reaction was further stirred for 2 hours. The obtained latex was used as it was.

(Production Example 1 of Reinforced Epoxy Resin)
Into a 1 L mixing tank at 25 ° C., 340 g of methyl ethyl ketone was introduced, and 252 g of the aqueous latex of the core-shell polymer (B) obtained in the above production example was added while stirring. After uniformly mixing, 126 g of water was added, 30 g of 5 wt% aqueous sodium sulfate solution was added with stirring, and then the separated and separated aqueous layer was discharged. 90 g of methyl ethyl ketone was added to the organic layer containing the core-shell polymer (B) in the mixing tank and mixed uniformly. While stirring, 176 g of water was added and mixed uniformly, and then 126 g of water was further added. While stirring, 30 g of a 5 wt% aqueous sodium sulfate solution was added, and the mixture was allowed to stand. The separated aqueous layer was drained. Again, 120 g of methyl ethyl ketone was added to the organic layer containing the core-shell polymer (B) in the mixing tank, and 176 g of water was added while uniformly mixing and stirring. After adding 30 g of 5 wt% sodium sulfate aqueous solution, the mixture was allowed to stand. The separated aqueous layer was drained. Further, 252 g of water was added to the organic layer, stirred gently for 20 minutes, allowed to stand for 20 minutes, and then the aqueous layer was discharged. Thereafter, the organic layer is separated, and 204 g of DGEBA type epoxy resin (epoxy value 186) is added thereto. After mixing, methyl ethyl ketone is distilled off under reduced pressure, and a reinforced epoxy resin (reinforced DGEBA type epoxy resin) composition containing a core-shell polymer is prepared. I got a thing. This reinforced DGEBA type epoxy resin is transparent, and a cured product obtained by curing 100 parts by weight of this reinforced epoxy resin composition with a catalytic amount of piperidine (5 parts by weight) (120 ° C./16 h) is transparent, and the core shell The polymer was dispersed in a state of primary particles, and the aggregate was not substantially observed, and it was confirmed that the core-shell polymer (B) was uniformly dispersed without aggregation.

(Production example 2 of reinforced epoxy resin)
350 g of methyl ethyl ketone was added to a 1 L mixing tank maintained at 25 ° C., and 250 g of the aqueous latex of the core-shell polymer (B) obtained in the above production example was mixed while stirring with a three-stage paddle blade. Stirring was stopped and 250 g of water was added. Stirring was resumed, and after adding 340 g of methyl isobutyl ketone, stirring was stopped again, and only the separated aqueous phase was discharged after 30 minutes. After adding 250 g of water to the organic phase containing the core-shell polymer remaining in the mixing tank, the mixture was stirred for 3 minutes, after which stirring was stopped and only the aqueous layer separated after standing for 20 minutes was discharged. After adding 250 g of water to the organic phase containing the rubber-like polymer particles remaining in the mixing tank and stirring for 3 minutes, stirring was stopped and only the aqueous layer separated after standing for 20 minutes was discharged. The obtained organic phase containing the core-shell polymer is mixed with ELM-120 (manufactured by Sumitomo Chemical Co., Ltd., triglycidyl m-aminophenol), which is a glycidylamine type epoxy resin, and the solvent is distilled off under reduced pressure to obtain a core-shell polymer. A reinforced glycidylamine type epoxy resin composition containing (B) was obtained. This reinforced epoxy resin composition was transparent, and a cured product obtained by curing 100 parts by weight of this reinforced epoxy resin composition with a catalytic amount of piperidine (5 parts by weight) (120 ° C./16 h) was transparent, and the core shell The polymer was dispersed in the form of primary particles, and substantially no aggregates were observed.

(Example 1)
55 parts by weight of bisphenol A type epoxy resin (epoxy equivalent 1100, softening point 100 ° C.), 25 parts by weight of carboxyl group-terminated polyester resin ER8101 (Japanese ester), reinforced DGEBA type epoxy obtained in Production Example 1 of the above reinforced epoxy resin After mixing 20 parts by weight of resin, 15 parts by weight of titanium oxide JR603 (manufactured by Teika), and Curazole C17Z (manufactured by Shikoku Kasei Co., Ltd., imidazole curing agent), melt and knead with an extruder, finely pulverize after cooling, and 150 mesh Filtration gave a powder paint. The powder coating was electrostatic powder coated on a zinc phosphate-treated galvanized steel sheet to a film thickness of 60 μm, and then baked at 180 ° C. for 30 minutes to obtain a cured coating film.

(Example 2)
40 parts by weight of reinforced DGEBA type epoxy resin containing the core-shell polymer obtained in Example 1, 25 parts by weight of DGEBA type epoxy resin (epoxy equivalent 186), 35 parts by weight of bisphenol A type epoxy resin (epoxy equivalent 650), 5% by weight of dicyandiamide 3 parts by weight of Diuron [3- (3,4-dichlorophenyl) -1,1-dimethylurea] and 4 parts by weight of fine particle silica (CAB-O-Sil TS-720) were mixed and removed under reduced pressure. Foaming was performed to obtain an adhesive composition. These are applied to an adherend (galvanized steel sheet), glass beads having a diameter of 0.25 mm are used as spacers, a T-peel specimen (1/32 galvanized steel sheet) and a Lap-Shear specimen (1/16 steel sheet). ) Was cured at 180 ss / 30 minutes. The T-peel intensity was 30 Pli, and the Lap-Shear intensity was 4000 Psi.

(Example 3)
Brominated epoxy resin (epoxy equivalent 440, bromine content 48%) 33 parts by weight, reinforced epoxy resin 20 parts by weight obtained in Example 1, DGEBA type epoxy resin (epoxy equivalent 186) 37 parts by weight, phenol novolac epoxy 15 parts by weight of a resin (epoxy equivalent 190) was mixed, and methyl ethyl ketone was added to obtain an 85% by weight methyl ethyl ketone solution. To this was added a dimethylformamide 20% by weight solution of 4 parts by weight of dicyandiamide and a 10% by weight methyl ethyl ketone solution of 2-methyl-4-imidazole (0.1 part by weight), and stirred well to prepare a varnish solution. This was impregnated and applied to a glass substrate and dried at 150 ° C. to obtain a prepreg. Eight more sheets were stacked, 18 μm copper foils were stacked on both sides, and heat-press integrated molding was performed at 170 ° C. for 90 minutes to obtain a laminated sheet having a thickness of 1.6 mm.

Example 4
Reinforced epoxy resin 28 parts by weight of the reinforced epoxy resin obtained in Production Example 1, 14 parts by weight of DGEBA type epoxy resin (epoxy equivalent 186), 55 parts by weight of bisphenol A type epoxy resin (epoxy equivalent 460), phenol novolac type epoxy A resin composition for prepreg was prepared by mixing 10 parts by weight of a resin (epoxy equivalent 180), 5 parts by weight of dicyandiamide, 3 parts by weight of Diuron, and 5 parts by weight of polyethersulfone (PES5003P from Victrex). After applying this resin composition on a release paper to form a film, carbon fibers arranged in one direction by a hot melt method are overlapped with two resin films from both sides and impregnated with resin by heating and pressurization. A unidirectional prepreg with a weight of 34% by weight was made.

Further, 20 sheets were laminated and molded by autoclaving at 140 ° C. for 2 hours at 0.30 MPa to obtain a fiber-reinforced composite material plate. The Charpy impact test value of this composite material plate was 180 kJ / m ² .

(Example 5)
16 parts by weight of reinforced epoxy resin obtained in Production Example 2 of reinforced epoxy resin, 13 parts by weight of DGEBA type epoxy resin (epoxy equivalent 186), 20 parts by weight of reinforced epoxy resin obtained in Production Example 1 of reinforced epoxy resin, A prepreg resin composition was prepared by mixing 60 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 460), 5 parts by weight of dicyandiamide, 3 parts by weight of Diuron, and 7 parts by weight of a polyvinyl formal resin. A fiber reinforced composite material plate was obtained in the same manner as in Example 4. The Charpy impact test value of this composite material plate was 180 kJ / m ² .

Claims (7)

  Rubber-reinforced epoxy containing a cured product obtained by curing an epoxy resin composition (C) in which a core-shell polymer (B) is dispersed in a state of primary particles in an epoxy resin (A) with a curing agent (D) A rubber product characterized in that it is a resin product and is at least one selected from the group consisting of a glass fiber reinforced composite material, a carbon fiber reinforced composite material, an adhesive, a coating material, a laminate, and a semiconductor encapsulant. Epoxy resin products.   The rubber-reinforced epoxy resin according to claim 1, wherein the core-shell polymer (B) is dispersed in the form of primary particles even after the epoxy resin composition (C) is cured with the curing agent (D). Product.   After the epoxy resin composition (C) containing the epoxy resin (A) and the core-shell polymer (B) is mixed with the organic solvent with the aqueous latex containing the core-shell polymer (B), the aqueous phase is separated and removed. The epoxy resin composition manufactured by mixing the dispersion (E) in which the core-shell polymer (B) is dispersed in the obtained organic solvent and the epoxy resin (A) is contained. Or the rubber reinforced epoxy resin product of 2.   The epoxy resin composition (C) containing the epoxy resin (A) and the core-shell polymer (B) mixes the aqueous latex containing the core-shell polymer (B) with an organic solvent, and further does not mix with the water-soluble electrolyte or aqueous latex. The dispersion (E) in which the core-shell polymer (B) is dispersed in the organic solvent obtained by separating and removing the aqueous phase after adding the organic solvent is mixed with the epoxy resin (A). The rubber-reinforced epoxy resin product according to claim 3, which is manufactured.   In the production of the epoxy resin composition (C), prior to mixing the dispersion (E) with the epoxy resin (A), the aqueous phase is separated after contacting the dispersion (E) with water or an aqueous solution of a water-soluble electrolyte. The rubber-reinforced epoxy resin product according to claim 3 or 4, wherein the operation is performed at least once.   6. The solubility in water at 20 ° C. of the organic solvent first mixed with the aqueous latex containing the core-shell polymer (B) is 5% by weight or more and 40% by weight or less. The rubber-reinforced epoxy resin product described in Crab.   One or more additives selected from curing accelerators, inorganic fillers, organic or polymer fillers, flame retardants, antistatic agents, conductivity imparting agents, lubricants, slidability imparting agents, surfactants, and colorants The rubber-reinforced epoxy resin product according to claim 1, comprising: