Epoxy resin composition and cured product thereof

Abstract

To provide: an epoxy resin composition capable of yielding a cured product excellent in the heat resistance and the elastic modulus; and the cured product thereof.SOLUTION: An epoxy resin composition comprises at least (A) and (B) in the following: (A) an epoxy resin having a structure represented by general formula (1) (where R1 to R4 may be the same or different and each represents a hydrogen atom or a hydrocarbon group, which may include a heteroatom, and R1 to R4 may also be bonded to each other to form a ring, provided that at least one of R1 to R4 is a hydrocarbon group); and (B) at least one epoxy resin curing agent selected from the group consisting of amine compounds, amide compounds, phenolic compounds, acid anhydride compounds, and imidazoles.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an epoxy resin composition and a cured product thereof. [Background technology]

[0002] Epoxy resins are mainly used as coating materials because of their excellent electrical properties, adhesiveness, heat resistance, and moldability. It is used in many fields such as food, civil engineering, electrical engineering, and sports. However, glycidylamine type epoxy resins have low molecular weights and are multifunctional, making them hard. It is widely used because of its excellent heat resistance. A matrix of carbon fiber reinforced plastic (CFRP) that takes advantage of good wettability with the base fiber. It is a suitable material for resin.

[0003] In recent years, SiC semiconductors have become more and more popular in the power semiconductor field, replacing Si semiconductors. The dielectric breakdown field strength of SiC is about 10 times higher than that of Si, so the Schottky barrier Even in device structures such as diodes and MOSFETs, the thickness of the depletion layer can be increased while maintaining the voltage resistance. As a result, SiC power devices have high voltage resistance, high-speed switching characteristics, and In addition, SiC has a smaller band gap than Si, which allows the device to achieve low on-resistance and low power dissipation at the same time. This makes it possible to provide a power device that can operate even at high temperatures. The epoxy resin used as the raw material for semiconductor encapsulation is also mixed with a hardener and hardened. The cured product obtained by the above process is required to have excellent heat resistance in anticipation of use in high-temperature environments. In addition to the electrical and electronic applications described above, fiber reinforced plastics (F There is a high demand for high heat resistance in a variety of applications, including RP.

[0004] Patent Document 1 describes an epoxy resin using an aromatic glycidylamine type epoxy resin. It is disclosed that the composition gives a cured product having high heat resistance. This type of tetrafunctional glycidylamine epoxy resin has excellent heat resistance and toughness after curing. It has been proposed that: On the other hand, in the field of CFRP, it is used as a base material for aircraft and automobiles, so The elastic modulus is also required. In order to increase the glass transition temperature of the cured product, an epoxy with a rigid molecular structure is used. Generally, epoxy resins or multifunctional epoxy resins are used. In some cases, even if a multifunctional epoxy resin is used, the elastic modulus may not increase, and There has been a demand for an epoxy resin composition that can achieve both a high transition temperature and a high elastic modulus. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2010-254955 A Summary of the Invention [Problem to be solved by the invention]

[0006] Thus, in the conventional technology, it was not possible to obtain an epoxy resin composition having both a high glass transition temperature and a high elastic modulus. In order to solve the above problems, the present invention provides a cured product having good heat resistance and elastic modulus. The present invention aims to provide an epoxy resin composition capable of obtaining the above-mentioned formula (1) and a cured product thereof. . [Means for solving the problem]

[0007] As a result of intensive research to solve the above problems, the present inventors have discovered that The epoxy resin composition containing an amine-type epoxy resin and a curing agent in any ratio is highly glass-compatible. The present invention was completed by discovering that the cured material has both a transition temperature and a high elastic modulus. That is, the gist of the present invention is as follows: [1] to [6]. That is, the present invention has the following features.

[0008] [1] An epoxy resin composition comprising at least (A) and (B). (A) An epoxy resin having a structure represented by general formula (1).

[0009] [ka]

[0010] (In formula (1), R1 to R4 may be the same or different, and each represents a hydrogen atom or a hydrocarbon atom.) R1 to R4 are each a radical that may contain a heteroatom, and R1 to R4 are bonded to each other to form a ring. At least one of R1 to R4 is a hydrocarbon group.) (B) Amine compounds, amide compounds, phenol compounds, acid anhydride compounds, imines At least one epoxy resin hardener selected from the group consisting of ethylenediamines. [2] The epoxy resin composition according to claim 1, wherein the formula (1) is the following formula (2):

[0011] [ka]

[0012] [3] Claims further comprising (C) an aromatic epoxy resin having a glycidyl ether group. Epoxy resin composition according to 1. [4] The component (C) is a bisphenol type epoxy resin, a phenol novolac type epoxy resin, The epoxy resin according to claim 3, which is at least one epoxy resin selected from the group consisting of epoxy resins. Resin composition. [5] The weight ratio of the epoxy resin of component (A) to the epoxy resin of component (C) is 1 4. The epoxy resin composition according to claim 3, wherein the ratio of the alkoxysilane ratio to the epoxy resin ratio is 99:99 to 99:1. [6] A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 5. thing. Effect of the Invention

[0013] According to the present invention, it is possible to obtain an epoxy resin having both high heat resistance and high elastic modulus. In addition, in order to achieve these excellent effects, the composition is useful for coating materials, electric and electronic materials, and the like. The present invention can be suitably used in the fields of adhesives, FRP, etc. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following description. However, the present invention can be modified and implemented in any manner without departing from the spirit and scope of the present invention. In this specification, when "~" is used to express a numerical value or a physical property value, In this specification, the numerical range is used to include the values ​​before and after the numerical range. When the lower and upper limits are separately stated, the numerical range can be determined by any lower limit of those. and any upper limit value.

[0015] [Epoxy resin composition] An epoxy resin composition according to one embodiment of the present invention (hereinafter simply referred to as "epoxy resin composition") The epoxy resin composition (A) may be a terpolymer of the epoxy resin composition (B) described below. It is an object.

[0016] [Component (A)] The component (A) contained in the epoxy resin composition is an epoxy resin represented by the following formula (1): Hereinafter, this may be referred to as "epoxy resin A". By including the component (B) described later, a cured product having excellent heat resistance and a high elastic modulus can be obtained. It is possible to obtain an epoxy resin composition which can

[0017] [ka]

[0018] In the above formula (1), R 1 ~R 4 may be the same or different, and each represents a hydrogen atom or a carbon atom. R is a hydrogen atom, which may contain a heteroatom; 1 ~R 4 are bonded together to form a ring It's okay to do that;R 1 ~R 4 At least one of the groups is a hydrocarbon group. Hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, t Examples of R include a butyl group, a phenyl group, and a trifluoromethyl group. 1 ~R 4 are connected to each other When these hydrocarbon groups are bonded together to form a ring, the structure in which these hydrocarbon groups are bonded together to form a ring is an example. From the viewpoint of availability, methyl, isopropyl, phenyl, or trifluoro Among these, the methyl group is particularly preferred from the viewpoint of increasing the thermal decomposition temperature. Preferred.

[0019] Heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, phosphorus, silicon, fluorine, Examples of the atom include chlorine, bromine, and iodine. R 1 ~R 4The number of hydrocarbon groups among From the viewpoint of breaking the conjugated system and improving the reactivity during production by shifting the dihedral angle of From the viewpoint of obtaining raw materials with stable quality and improving manufacturing stability, 1 ~ R 4 The number of hydrocarbon groups among these is preferably 2 or 4, and particularly preferably 2. Specifically, for example, R 1 ~R 4 All of R are hydrocarbon groups, or 2 and R 4 but is a hydrocarbon group, R 1 and R 3 is preferably a hydrogen atom, and R 1 and R 4 but is a hydrocarbon group, R 2 and R 3 An embodiment in which is a hydrogen atom is particularly preferred.

[0020] The structure represented by the above formula (1) is preferable from the viewpoint of improving reactivity during production and from the viewpoint of low thermal decomposition temperature. From the viewpoint of reducing the amount of carbon black, a structure represented by the following formula (2) is preferred.

[0021] [ka]

[0022] In the formula (2), Me represents a methyl group.

[0023] [Physical properties and characteristics of epoxy resin A] The lower limit of the epoxy equivalent of epoxy resin A is preferably 50 g / eq or more, and 70 g / eq or more. It is more preferable that the epoxy equivalent is q or more, and particularly preferable that the epoxy equivalent is 100 g / eq or more. By satisfying the above requirements, it is possible to ensure a suitable viscosity, and as a result, it is possible to improve the viscosity of the epoxy resin. This improves compatibility with the curing agent.

[0024] On the other hand, the upper limit of the epoxy equivalent of the epoxy resin A is preferably 500 g / eq or less, 00g / eq or less is more preferable, 200g / eq or less is even more preferable, and 150g / eq or less is even more preferable. q or less is particularly preferred, and 125 g / eq or less is even more particularly preferred. By keeping the viscosity below the limit, it is possible to reduce the viscosity when heated to high temperatures, improving handling properties. It can be made good.

[0025] The upper limit of the viscosity of epoxy resin A at 50°C is preferably 500,000 mPa·s or less. Preferably, 200,000 mPa·s or less is more preferable, and 130,000 mPa·s or less is even more preferable. More preferably, the viscosity at 50°C is 120,000 mPa·s or less, and particularly preferably 120,000 mPa·s or less. If the content is equal to or less than the upper limit, it becomes easy to mix uniformly, and a hardened product of uniform quality can be produced. It is possible.

[0026] On the other hand, the lower limit of the viscosity of epoxy resin A at 50°C is preferably 100 mPa·s or more. Preferably, the viscosity is 500 mPa·s or more, more preferably 1,000 mPa·s or more. The viscosity at 50°C is the lower limit value or more, and particularly preferably 10,000 mPa·s or more. If the mixture is mixed in a mixing container, it can be mixed by applying shear, making it easier to mix uniformly. The upper limit of the viscosity of epoxy resin A at 150°C is preferably 100 mPa·s or less. , 80 mPa·s or less is more preferable, 70 mPa·s or less is even more preferable, and 60 mPa·s or less is even more preferable. It is particularly preferable that the viscosity at 150°C is equal to or less than the upper limit above. This makes it easier to produce cured products of uniform quality.

[0027] On the other hand, the lower limit of the viscosity of epoxy resin A at 150°C is preferably 1 mPa·s or more. The viscosity is preferably 10 mPa·s or more, and more preferably 20 mPa·s or more. If the viscosity at the time is equal to or higher than the lower limit above, mixing can be performed by applying shear, and the mixture can be mixed uniformly. This makes it easier to The epoxy equivalent of epoxy resin A, its viscosity at 50°C, and its viscosity at 150°C are shown below. It is measured by the method described in the Examples section.

[0028] [Method of manufacturing epoxy resin A] The method for producing the epoxy resin of the present embodiment is not particularly limited. For example, the epoxy resin may be produced by reacting the epoxy resin represented by the following formula (3): A method for producing the compound represented by the formula (I) comprising reacting an amine compound represented by the formula (I) with epihalohydrin. Preferably, these compounds are subjected to an addition reaction in the absence of a catalyst, and then an alkali metal hydroxide is added to the reaction product. Specifically, the method described in the Examples below can be used. It is possible.

[0029] [ka]

[0030] In formula (3), R 11 ~ 14 is R in the above formula (1). 1 ~R 4 and and those conditions can be applied as well. As the epihalohydrin, epichlorohydrin or epibromohydrin is usually used. However, in this embodiment, epichlorohydrin is preferred from the viewpoint of economic efficiency. The amount of epihalohydrin used is usually 1. 0 to 30.0 equivalents, particularly 3.0 to 20.0 equivalents, and more particularly 8.5 to 15.0 equivalents When the amount of epihalohydrin is equal to or more than the lower limit, the high molecular weight The polymerization reaction is easy to control, the viscosity of the resulting epoxy resin is reduced, and it is easy to mix during compounding. On the other hand, if the amount of epihalohydrin is less than the upper limit, the production efficiency is This is preferable because it tends to improve.

[0031] The amount of alkali metal hydroxide added in the ring-closing reaction is determined by the amount of active hydrogen of the raw amine compound. Per equivalent, an amount of aryl is usually 0.5 to 2.0 equivalents, preferably 0.9 to 1.6 equivalents. The reaction is carried out by adding an alkali metal hydroxide in the form of a solid or an aqueous solution. For example, in the case of the amine compound of the above formula (3), If the amount of alkali metal hydroxide added is more than the lower limit, the reaction may not proceed smoothly. The hydroxyl groups of the reaction product do not easily react with the resulting epoxy resin, making it easier to control the polymerisation reaction. In addition, if the amount of the alkali metal hydroxide added is less than the above upper limit, side reactions may occur. The alkali metal hydroxide used here is preferably such that impurities such as ammonium nitrate are not easily generated. Typically, sodium hydroxide or potassium hydroxide is used.

[0032] This reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is preferably 20 to 15 If the reaction temperature is higher than the lower limit, the reaction This is preferred because the reaction is easy to proceed and easy to control. When the amount is equal to or less than the upper limit, side reactions are unlikely to proceed, and in particular, oligomer components are easily reduced, and the amount of the reaction product is easy to be reduced. This is preferable because it gives an epoxy compound with a viscosity that is easy to handle.

[0033] The step of reacting the amine compound with epichlorohydrin is carried out continuously, and the total The lower limit of the time required is preferably more than 90 minutes, more preferably more than 100 minutes, and more preferably more than 120 minutes. The reaction time is more preferably 150 minutes or more, and particularly preferably more than 150 minutes. By doing so, the addition reaction and the ring-closing reaction can be carried out separately, and the amount of oligomer components can be reduced. This reduces the viscosity of the epoxy resin, thereby obtaining a low-viscosity epoxy resin.

[0034] On the other hand, the upper limit is preferably 1200 minutes or less, more preferably 600 minutes or less, and more preferably 50 It is particularly preferable that the time is 0 minutes or less. If the time is equal to or less than the upper limit, the production efficiency tends to be improved. Preferred. In this reaction, tetramethylammonium chloride or tetraethyl quaternary ammonium salts such as ammonium bromide; benzyldimethylamine, or Tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol; 2-ethyl -Imidazoles such as 4-methylimidazole or 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; or triphenylphosphonium Catalysts such as phosphines, etc. may be used. There is no limitation as long as the compound can increase the reaction rate of the halohydrin and the amine compound. stomach.

[0035] The epoxy resin produced as described above is reacted again with an alkali to remove the residual The ring-closing reaction of the 1,2-halohydrin derivatives, the recrystallization method, and the distillation method are The purification may be carried out by a method such as those described above. These methods may be used in combination. From the viewpoint of economy, purification by reaction with an alkali is preferred. A solvent may be used in the reaction step or purification step for producing the present epoxy resin. The solvent may be any solvent that dissolves the raw material. Although the organic solvent is used, water may also be used.

[0036] Examples of the organic solvent include alcohol solvents, aromatic solvents, ketone solvents, and amide solvents. solvents, glycol ether solvents, and the like. Specific examples of the alcohol solvent include methanol, ethanol, and isopropanol. Examples include ru. Specific examples of aromatic solvents include benzene, toluene, and xylene. .

[0037] Specific examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. ton, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone Examples of the solvent include xanone and acetylacetone. Specific examples of amide solvents include formamide, N-methylformamide, and N,N-diphenylmethane. Methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide amide, 2-pyrrolidone, or N-methyl-2-pyrrolidone.

[0038] A specific example of the glycol ether solvent is ethylene glycol monomethyl ether. , Ethylene glycol monoethyl ether, Ethylene glycol mono-n-butyl ether Ethylene glycol dimethyl ether, Ethylene glycol monoethyl ether acetate diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl Diethylene glycol monoethyl ether acetate, propylene glycol propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, or propylene ethylene glycol monomethyl ether acetate, etc. The above-mentioned solvents may be used alone or in any combination and ratio of two or more. It may be used.

[0039] [Component (B)] The component (B) contained in the epoxy resin composition is an amine compound, an amide compound, a phenanthroline compound, or the like. At least one enolate selected from the group consisting of alcohol compounds, acid anhydride compounds, and imidazoles. Among these, epoxy resin hardener is the most effective for improving the elastic modulus. It is preferable that the compound contains any one of an amine compound, an amide compound, and an acid anhydride compound. In addition, the curing agent is a compound that is effective in crosslinking and / or chain extension reactions between epoxy groups of epoxy resins. In this disclosure, the term "curing accelerator" is used. However, they do not contribute to the crosslinking reaction and / or chain extension reaction between the epoxy groups of the epoxy resin. If it is of a similar quality, it will be considered a hardener.

[0040] The content of component (B) in the epoxy resin composition is the total epoxy resin composition as solid content. The amount is preferably 0.1 to 1000 parts by weight per 100 parts by weight of the mixture. The content of component (B) is preferably 500 parts by weight or less, and more preferably 300 parts by weight or less. By making the content equal to or less than the upper limit of the above range, hardening due to remaining component (B) during the hardening reaction is prevented. In addition, the content of component (B) is equal to or higher than the lower limit of the above range. This allows for sufficient cross-linking during the curing reaction, resulting in excellent mechanical and thermal properties. A cured product can be obtained.

[0041] In this disclosure, "solid content" refers to the components excluding the solvent, and is the solid epoxy resin. In addition, it also includes semi-solid and viscous liquid substances. "The total of epoxy resin A, epoxy resin C (described later), and other epoxy compounds" means... The curing agent may be used alone or in combination of two or more kinds. When using two or more types in combination, mix them together to prepare a mixed hardener before use. Alternatively, when mixing the components of the curable resin composition, each component of the curing agent may be mixed separately. may be added and mixed at the same time.

[0042] Examples of amine compounds (excluding tertiary amines) include aliphatic amines, polyamines, Examples of the amines include triether amines, alicyclic amines, aromatic amines, and amine adducts. do. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, Aminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, Trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine , bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepenta amine, pentaethylenehexamine, N-hydroxyethylethylenediamine, or tetraethylamine Examples include ra(hydroxyethyl)ethylenediamine.

[0043] Polyetheramines include triethylene glycol diamine, tetraethylene glycol Lithylene glycol bis(propylamine), polyoxypropylene Examples of the amine include polyoxypropylene diamines and polyoxypropylene triamines. Alicyclic amines include isophorone diamine, methacene diamine, and N-aminoethyl Piperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl (ethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetramethylcyclohexane Examples include laoxaspiro(5,5)undecane, norbornene diamine, and the like.

[0044] Aromatic amines include tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine Phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4- Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino -1,2-diphenylethane, 2,4-diaminodiphenyl sulfone, 4,4'-diamino Nodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyl diamine Methylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methyl benzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4- Aminophenyl)-p-diisopropylbenzene, m-tolidine, or Mitsubishi Chemical Corporation An example is JER Cure WA manufactured by JER.

[0045] The amine adducts include those containing an amine compound and an isocyanate compound or a urea compound. or a reaction product of an amine compound and an epoxy compound. Amine compounds may be used alone or in any combination of two or more types in any ratio. Among the amine-based curing agents, the most popular are those with high heat resistance and mechanical properties. It is preferable to use an alicyclic amine or an aromatic amine.

[0046] The amine compound is a compound that is capable of reducing the amount of epoxy groups in the total epoxy resin component contained in the epoxy resin composition. It is preferable to use the curing agent so that the equivalent ratio of the functional groups in the curing agent to the functional groups in the curing agent is in the range of 0.8 to 1.5. If the amount falls within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain. This is preferable. The amide-based compound is dicyandiamide or a derivative thereof, or a polyamide resin. The amide compounds may be used alone or in any combination of two or more. In the case of using an amide-based curing agent, the epoxy resin composition may be mixed with the amide-based curing agent in the above ratio. The amount of amide-based hardener is 0.1 to 2% of the total epoxy resin components and amide-based hardeners in the It is preferable to use it so that the content is 0% by weight.

[0047] Specific examples of phenolic compounds include bisphenol A, bisphenol F, and bisphenol B. Phenol S, Bisphenol A, Hydroquinone, Resorcinol, Methylresorcinol, Bisphenol A Phenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl Nyl ethers, thiodiphenols, phenol novolac resins, cresol novolac Resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin Fat, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A Novolac resin, trisphenol methane type resin, naphthol novolac resin, brominated biphenyls Various polyhydric phenols such as phenol A or brominated phenol novolac resins ;Various phenols and benzaldehyde, hydroxybenzaldehyde, crotonaldehyde Polyfunctional fluorescein is obtained by condensation reaction with various aldehydes such as aldehydes or glyoxal. Polyphenol resins obtained by the condensation reaction of xylene resins with phenols. Grease; Co-condensation resin of heavy oil or pitch with phenols and formaldehyde; Phenol Polycondensation product of phenol, benzaldehyde and xylylene dimethoxide; Polycondensation product of phenol, benzaldehyde, 4,4'-dichlorobenzene; Methoxide biphenyl polycondensate; or phenol-benzaldehyde-4,4'-di Examples of the resin include various phenolic resins such as halide biphenyl polycondensates.

[0048] These phenolic compounds may be used alone or in any combination of two or more. They may be used in combination at a given mixing ratio. The amount of the phenolic compound blended is 100% by weight of the total epoxy resin components in the epoxy resin composition. The amount is preferably 0.1 to 1,000 parts by weight, more preferably 500 parts by weight. parts by weight or less, more preferably 300 parts by weight or less, and particularly preferably 100 parts by weight or less.

[0049] Examples of the acid anhydride compound include acid anhydrides and modified products of acid anhydrides. Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. Anhydride, Benzophenonetetracarboxylic acid anhydride, Dodecenylsuccinic anhydride, Polyazide Pinic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyl octadecyl ether) Poly(phenylhexadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic acid free Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexa Hydrophthalic anhydride, methylhimic anhydride, trialkyltetrahydrophthalic acid Anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarbo ethylene glycol bistrimellitate dianhydride, heptane anhydride, nadidine Nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanic acid (3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarbonyl 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 1 -Methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dibasic Examples include water.

[0050] Examples of modified acid anhydrides include those modified with glycols. Examples of glycols that can be used for modification include ethylene glycol. Alkylene glycol such as propylene glycol or neopentyl glycol or polyethylene glycol, polypropylene glycol, or poly Polyether glycols such as tramethylene ether glycol, etc. A copolymer of two or more of these glycols and / or polyether glycols is used. A triether glycol may also be used.

[0051] In the case of modified acid anhydrides, the amount of glycol modified is 0.4 moles or less per mole of acid anhydride. When the amount of modification is equal to or less than the upper limit, the viscosity of the epoxy resin composition is The temperature does not become too high, and workability tends to be good. In addition, the hardening reaction with the epoxy resin is Speed ​​also tends to be good. The acid anhydride compounds may be used alone or in any combination of two or more kinds in any amount. It may also be used in combination.

[0052] When an acid anhydride compound is used, the epoxy resin composition is The equivalent ratio of the functional group in the curing agent to the oxy group should be in the range of 0.8 to 1.5. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain. It is preferable to become.

[0053] Imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methyl Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole Imidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-une Decyl imidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium phosphate Limeritate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl 2,4-diamino-6-[2'-ethyl-4'-methylimidazoline 2,4-diamino-6-[2'-methylimide Dazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl Midazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazo 2-phenyl-4-methyl-5-hydroxymethylimidazole, or epoxy Examples include adducts of resins and the above imidazoles. Note that imidazoles have catalytic activity. Since it has the above properties, it can generally be classified as a curing accelerator, but in this disclosure, it is not classified as a curing agent. The classification shall be made as follows.

[0054] Imidazoles may be used alone or in any combination and ratio of two or more. When imidazoles are used, the total epoxy resin components in the epoxy resin composition may be The imidazole is used in an amount of 0.1 to 20% by weight relative to the total weight of the imidazole. It is preferable that

[0055] [Component (C)] Component (C) contained in the epoxy resin composition (hereinafter referred to as “epoxy resin C”) ) is an aromatic epoxy resin having a glycidyl ether group, and epoxy resin B By including the epoxy resin, the viscosity can be easily controlled within an appropriate range. The tackiness of prepregs containing the olefin resin composition can be easily adjusted. When producing reinforced plastics, etc., it is possible to obtain molded products with fewer voids.

[0056] Epoxy resin C is a bisphenol A resin that can be cured to have excellent bending strength. At least one selected from the group consisting of phenolic epoxy resins, phenolic novolac epoxy resins, and phenolic novolac epoxy resins. Epoxy resins are preferred. Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins. Bisphenol F type epoxy resin, bisphenol C type epoxy resin, bisphenol S epoxy resins and the like.

[0057] The bisphenol A type epoxy resin is, for example, commercially available jER825. , jER827, or jER828 (trade names, all manufactured by Mitsubishi Chemical Corporation) and the like. can be. The bisphenol F type epoxy resin is, for example, commercially available Epicron 8. 30 (product name, or manufactured by DIC Corporation), jER806, jER807 (product name, the above, three (manufactured by Ryo Chemical Co., Ltd.)

[0058] The phenol novolac type epoxy resin is, for example, a phenol novolac type epoxy resin. Resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resins, naphthol novolac type epoxy resins, etc. The epoxy resin C may be a monofunctional epoxy resin, or a bifunctional or higher (multifunctional) epoxy resin. The epoxy resin may be of the above formula:

[0059] The epoxy resin C may be used in one type (one product) or in a combination of two or more types. It can also be used. The epoxy equivalent of the epoxy resin C is not particularly limited, but may be selected within a range that provides a good viscosity. From the viewpoint of improving the handling property, the range of 150 to 300 g / eq is preferable. It is preferable that the viscosity is in the range of 160 to 200 g / eq.

[0060] The weight ratio of epoxy resin A to epoxy resin C is 1:99 to 99:1. is preferable, 5:95 to 80:20 is more preferable, 10:90 to 70:30 is even more preferable. It is even more preferable that: By setting the content of epoxy resin C to the upper limit or less of the above range, the elastic modulus and A well-balanced cured product can be obtained. In addition, the content of epoxy resin B is high. By being equal to or higher than the lower limit of the above range, a cured product having an excellent balance with heat resistance can be obtained. do.

[0061] [Other hardeners] In the epoxy resin composition of the present embodiment, other curing agents may be used in addition to the component (B). Other examples of the epoxy resin composition that can be used in the present embodiment include There are no particular limitations on the hardener, and any hardener generally known as an epoxy resin hardener can be used. These other curing agents can be used alone or in combination of two or more. This is also fine.

[0062] [Other epoxy resins] The epoxy resin composition of the present embodiment further comprises, in addition to the epoxy resin A and the epoxy resin C, other By including other epoxy resins, the present embodiment The stress resistance, moisture absorption resistance, flame retardancy, etc. of the epoxy resin composition can be improved. Other epoxy resins that can be used in the curable resin composition of the present embodiment include epoxy resins. All resins except for resin A and epoxy resin C are applicable. Tannic acid type epoxy resin, anthracene type epoxy resin, phenol-modified xylene resin type epoxy resin Epoxy resin, bisphenol cyclododecyl type epoxy resin, bisphenol diisopropyl Epoxy resins of methyl hydroquinone type, methyl hydroquinone type Dibutylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcinol type epoxy resin , methylresorcinol type epoxy resin, biphenol type epoxy resin, tetramethylbiphenyl Nol type epoxy resin, dihydroxydiphenyl ether type epoxy resin, thiodiphenyl ether type epoxy resin Epoxy resins derived from alcohols, dihydroxynaphthalene type epoxy resins, dihydronaphthalene type epoxy resins xyanthracene type epoxy resin, dihydroxydihydroanthracene type epoxy resin, Dicyclopentadiene type epoxy resins, epoxy resins derived from dihydroxystilbenes resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, Biphenyl aralkyl type epoxy resin, terpene phenol type epoxy resin, dicyclopentadiene Polybutadiene-phenol type epoxy resin, condensation of phenol and hydroxybenzaldehyde Epoxy resin derived from phenol-crotonaldehyde condensation product epoxy resins derived from condensation products of phenol and glyoxal; Derived from co-condensation resins of heavy oil or pitch, phenols and formaldehydes. epoxy resins derived from diaminodiphenylmethane, aminopheno epoxy resins derived from methyl alcohol, epoxy resins derived from xylylene diamine, Epoxy resins derived from hexahydrophthalic acid or dimer acid Examples of the resin include epoxy resin.

[0063] These may be used alone or in any combination of two or more in any ratio. stomach. When the epoxy resin composition of the present embodiment contains another epoxy resin, the content of the other epoxy resin may vary depending on the composition. It is preferably 0.01 to 60 parts by weight based on 100 parts by weight of the total epoxy resin components in the composition. More preferably, the amount is 40 parts by weight or less, further preferably, 30 parts by weight or less, and particularly preferably, 2 It is preferably 0 part by weight or less, and more preferably 1 part by weight or more.

[0064] [Cure accelerator] The epoxy resin composition of the present embodiment preferably contains a curing accelerator. By including the copolymer, it is possible to shorten the curing time and lower the curing temperature, making it easier to obtain the desired cured product. It can be done quickly. The curing accelerator is not particularly limited, but specific examples include organic phosphines or phosphines. Phosphorus compounds such as sulfonium salts, tetraphenylboron salts, organic acid dihydrazides, halogens boron fluoride amine complexes, aromatic ureas, etc.

[0065] Phosphorus compounds that can be used as curing accelerators include triphenylphosphine, diphenylphosphine, Nyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkylphenyl)phosphine (alkyl alkoxyphenyl)phosphine, tris(alkyl alkoxyphenyl)phosphine, Tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, Tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine , tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl) aryl)phosphine, trialkylphosphine, dialkylarylphosphine, or aryl Organophosphines such as alkyldiarylphosphines; these organophosphines and organoboron or complexes with maleic anhydride, 1,4-benzoquinone, , 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6 -Dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2 ,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc. compounds, or compounds obtained by adding a compound such as diazophenylmethane, etc. .

[0066] Among the curing accelerators, organic phosphines or phosphonium salts are preferred. Fins are most preferred. The curing accelerator may be used alone or in combination of two or more. They may be mixed and used in any combination and ratio. Aromatic ureas include 3-(3,4-dichlorophenyl)-1,1-dimethylurea ( DCMU), 3-(4-chlorophenyl)-1,1-dimethylurea, phenyldimethylurea Examples of the urea-based compounds include toluenebisdimethylurea and urea-based compounds such as toluenediaminetetraacetate and toluenebisdimethylurea.

[0067] Aromatic urea may be used alone or in any combination and ratio of two or more. Good too. The curing accelerator is 0.05 parts by weight based on 100 parts by weight of the total epoxy resin components in the epoxy resin composition. It is preferable to use it in the range of 0.1 to 20 parts by weight. More preferably, it is 0.5 parts by weight. parts by weight or more, more preferably 1 part by weight or more, while more preferably 15 parts by weight or less, More preferably, the content of the curing accelerator is 10 parts by weight or less. On the other hand, when the content is equal to or less than the upper limit, the desired curing properties can be obtained. is preferred because it is easy to obtain

[0068] [Inorganic filler] The epoxy resin composition of the present embodiment may contain an inorganic filler. Examples of the material include fused silica, crystalline silica, glass powder, alumina, and calcium carbonate. , calcium sulfate, talc, or boron nitride. These may be used in any combination and in any ratio of two or more. Among them, when used for semiconductor encapsulation, crushed and / or spherical, melted and / or Crystalline silica powder filler is preferred.

[0069] By using an inorganic filler, the epoxy resin composition can be used as a semiconductor encapsulant. When semiconductor encapsulation is used, the thermal expansion coefficient of the semiconductor encapsulation material should be made closer to that of the internal silicon chip and lead frame. This also reduces the amount of moisture absorbed by the entire semiconductor encapsulation material, making it ideal for solder-resistant cladding. This can improve the durability.

[0070] The average particle size of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, and more preferably If the average particle size is more than the lower limit, the melt viscosity becomes high. It is preferable that the average particle size is not too large, so that the flowability is not easily reduced. This makes it difficult for the filler to clog the narrow gaps in the mold during molding, which improves the filling ability of the material. It is preferable to become. When an inorganic filler is used in the epoxy resin composition of the present embodiment, the inorganic filler is It is preferable that the amount of the fat is in the range of 60 to 95% by weight of the total fat composition.

[0071] [Release agent] A mold release agent may be blended into the epoxy resin composition of the present embodiment. For example, natural wax such as carnauba wax, synthetic wax such as polyethylene wax, etc. higher fatty acids such as stearic acid or zinc stearate or their metal salts, Alternatively, a hydrocarbon-based release agent such as paraffin or the like can be used. Alternatively, two or more of them may be used in any combination and in any blend ratio.

[0072] When a release agent is blended in the epoxy resin composition of the present embodiment, the blending amount of the release agent is determined based on the curing property. Preferably, the amount is 0.1 to 5.0 parts by weight based on 100 parts by weight of the total epoxy resin components in the resin composition. The amount of the release agent is preferably 0.5 to 3.0 parts by weight. and the epoxy resin composition can exhibit good releasability while maintaining the curing characteristics of the epoxy resin composition. Therefore, it is preferable.

[0073] [Coupling agent] It is preferable to add a coupling agent to the epoxy resin composition of the present embodiment. It is preferable to use a coupling agent in combination with an inorganic filler. This improves the adhesion between the epoxy resin matrix and the inorganic filler. The coupling agent may be a silane coupling agent or a titanate coupling agent. Examples include:

[0074] Examples of silane coupling agents include γ-glycidoxypropyltrimethoxysilane. silane, γ-glycidoxypropyltriethoxysilane, or β-(3,4-epoxysilane Epoxy silanes such as cyclohexyl)ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane Ethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N- β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Trimethoxysilane or aminosilanes such as gamma-ureidopropyltriethoxysilane ;Mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; p-Styryltri Methoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane vinyltrimethoxysilane, vinyltriethoxysilane, or γ-methacryloyl vinyl silanes such as dipropyltrimethoxysilane; or epoxy, amino or Examples of the silane include vinyl-based polymeric silanes.

[0075] Examples of titanate coupling agents include isopropyl triisostearoyl titanate. Isopropyl tri(N-aminoethyl aminoethyl) titanate, diisopropyl Pyrubis(dioctylphosphate) titanate, tetraisopropylbis(dioctyl) phosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate Tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosph Pyrophosphate Titanate, Bis(dioctylpyrophosphate)oxyacetate Titanate or bis(dioctylpyrophosphate)ethylene titanate.

[0076] The coupling agent may be used alone or in any combination and ratio of two or more kinds. A mixture of these may also be used. When a coupling agent is used in the epoxy resin composition of the present embodiment, the amount of the coupling agent is The amount is preferably 0.1 to 3.0 parts by weight based on 100 parts by weight of the epoxy resin component. If the amount of the coupling agent is equal to or more than the lower limit, the matrix caused by the addition of the coupling agent is reduced. The effect of improving the adhesion between the epoxy resin, which is the base material, and the inorganic filler tends to be improved. On the other hand, if the amount of the coupling agent is less than the above upper limit, the coupling agent may not be present in the resulting cured product. This is preferable because the adhesive is less likely to bleed out.

[0077] [Other ingredients] The epoxy resin composition of the present embodiment may contain components other than those described above (in the present disclosure, "other Other ingredients may be included. Examples of additives include flame retardants, plasticizers, reactive diluents, thermoplastic resins, thixotropic agents, cores, etc. Examples of toughening agents include shell rubber and pigments, which can be mixed as needed. However, the epoxy resin composition of the present embodiment may contain components other than those listed above. There is nothing to prevent the blending of the two.

[0078] [Check the ingredients] The curable resin composition according to this embodiment may further include the epoxy resin according to the first embodiment of the present invention. After separation and purification of the curable resin composition, it is possible to determine whether other ingredients are included. Qualitative analysis and / or Quantitative analysis can be performed and confirmed.

[0079] [Cured product] By curing the epoxy resin composition according to this embodiment, a cured product can be obtained. Here, "curing" refers to intentionally hardening the epoxy resin by heat and / or light, etc. The degree of hardening can be controlled depending on the desired physical properties, applications, etc. stomach.

[0080] The curing method for curing the epoxy resin composition according to the present embodiment to form a cured product is Although it varies depending on the components and amounts of the components in the epoxy resin composition, the shape of the compound, etc., it is usually 50 The heating conditions are 50 to 160°C for 5 seconds to 20 hours. - 3 hours of primary heating, then 1 minute at 90-200℃, 40-120℃ higher than the primary heating temperature. A two-stage process with a secondary heating for 8 hours is preferable in that it reduces poor curing. .

[0081] When manufacturing a cured product as a semi-cured product, the epoxy resin is cured to such an extent that it can maintain its shape by heating, etc. In the case where the epoxy resin composition contains a solvent, the curing reaction of the epoxy resin composition is allowed to proceed. Most of the solvent can be removed by heating, reducing pressure, or air drying. The solvent may remain in the composition at up to 5% by weight. The fact that the cured product contains the epoxy resin according to the first embodiment of the present invention means that After decomposing the material in an appropriate manner, nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy, or various crystallographic techniques are used. By analyzing the cured product by an appropriate analytical method such as chromatography, the first This can be confirmed by identifying the epoxy resin according to the embodiment.

[0082] The lower limit of the glass transition temperature of the cured product is preferably 150° C. or higher, and more preferably 190° C. or higher. The glass transition temperature of the cured product is preferably equal to or lower than the lower limit mentioned above, and particularly preferably equal to or higher than 200°C. In this case, the elastic modulus of the cured product may decrease at the actual use temperature. On the other hand, the upper limit of the glass transition temperature is The glass transition temperature of the cured product is preferably 450° C. or lower, and more preferably 400° C. or lower. When producing a cured product with a value exceeding the upper limit, the curing temperature and composition of the cured product must be the same as those of the current general process. may not be compatible with the

[0083] The lower limit of the storage modulus of the cured product is preferably more than 2.0 GPa, and more preferably more than 2.5 GPa. When the storage elastic modulus is equal to or greater than the lower limit, rigidity sufficient for practical use can be ensured. The upper limit of the storage modulus is preferably 10 GPa or less, and more preferably 8 GPa or less. It is preferable that the storage modulus is 5 GPa or less, and particularly preferable that the storage modulus is 5 GPa or less. In some cases, the curing temperature and composition of the cured product may not be compatible with current general processes.

[0084] The lower limit of the flexural modulus of the cured product is preferably 3.0 GPa or more, more preferably 3.2 GPa or more. The flexural modulus is preferably equal to or greater than the lower limit, and more preferably equal to or greater than 3.5 GPa. The upper limit of the bending elastic modulus is 10 GP. The bending strength is preferably a or less, more preferably 8 GPa or less, and particularly preferably 5 GPa or less. When preparing a cured product having an elastic modulus of more than the upper limit, the curing temperature and the composition of the cured product are generally There is a risk that it may not be compatible with current processes.

[0085] The lower limit of the bending strength of the cured product is preferably 100 MPa or more, and more preferably 150 MPa or more. Preferably, the bending strength is 160 MPa or more, more preferably 160 MPa or more, and particularly preferably 180 MPa or more. When the flexural modulus is equal to or greater than the lower limit, rigidity sufficient for practical use can be ensured. The upper limit of the flexural modulus is preferably 5000 MPa or less, more preferably 1000 MPa or less. It is preferable that the flexural modulus is equal to or less than the upper limit of the above range, and particularly preferably equal to or less than 500 MPa. If such a process is used, the curing temperature and composition of the cured product may not be compatible with current general processes.

[0086] [Application] The above-mentioned epoxy resin composition is excellent in mechanical properties and transparency. Since the epoxy resin composition and its cured product have these excellent effects, they are widely used in coatings, electrical and electronic Materials, adhesives, and fiber-reinforced plastics (FRP) such as carbon fiber reinforced plastics (CFRP) Specifically, the epoxy resin according to this embodiment can be suitably used in the fields of The resin composition is suitable for use in coatings, adhesives, prepregs, laminates, semiconductor sealants, etc. The cured product of the resin composition can be used for coating films, joints, fiber reinforced plastics (FRP), etc. It is preferable that the composition is contained in an organic EL element; a semiconductor encapsulant; an electric / electronic material; etc. EXAMPLES

[0087] The present invention will be described in more detail below with reference to examples. In addition, various manufacturing conditions and evaluation results in the following examples are not limited to the above. The values ​​are meant as preferred upper or lower limits in the embodiment of the present invention. The preferred range is the upper or lower limit value described above and the value in the following examples or between the examples. The range may be defined by a combination of the above.

[0088] [Synthesis of epoxy resin A] A separable flask equipped with a Dimroth condenser, a nitrogen inlet tube, and a thermocouple was charged with m-tolidine ( 4,4'-Diamino-2,2'-dimethylbiphenyl, Seika Co., Ltd. Company m-TB-HG) 250g (1.15mol), epichlorohydrin 1199g (12.95 mol), 584 g of isopropyl alcohol, and 910 g of water were added and heated to 30°C. The temperature was then raised to 65°C over 90 minutes under normal pressure, and then The addition reaction was completed by holding at 5 for 90 minutes. During the ring-closing reaction, the temperature in the system did not exceed 65°C. Similarly, 466 g of 48% sodium hydroxide solution was added dropwise over 120 minutes. After the addition, the temperature was raised to 65°C. The reaction was continued for 60 minutes at RT, and the organic phase was washed with water and then concentrated to obtain the crude product. Redissolve in methyl isobutyl ketone (500 g) and add 48% sodium hydroxide solution (1 Add 4.3g) and stir at 60℃ for 1 hour to complete the ring closure of the 1,2-chlorohydrin compound. The reaction was carried out to obtain a high level of purification. The organic phase was washed until the aqueous phase became neutral, and then concentrated to obtain epoxide. The epoxy resin A had an epoxy equivalent of 115 g / eq.

[0089] <Epoxy equivalent> The epoxy equivalent of epoxy resin is based on JIS K 7236, and is calculated by the ratio of glycidylamine to The measurements were carried out by potentiometric titration using the correction method. Specifically, modified glycidylamine Add 0.1 mol / L perchloric acid / acetic acid solution to the chloroform solution of epoxy resin. This produces a salt of amine and perchloric acid, and the titer V2 at the end point of the titration is obtained. After that, tetraethylammonium bromide was added to the system, and 0.1 mol / L perchloric acid and acetic acid were added. Continue dropping the solution, and calculate the epitaxial growth rate based on the difference between the titration volume V1 and the titration volume V2 at the end of the titration. The oxy equivalent was calculated.

[0090] [Raw materials, etc.] In the following examples and comparative examples, the following raw materials etc. were used. 604: Diaminodiphenylmethane type epoxy compound (Mitsubishi Chemical Corporation jE R(registered trademark) 604) 630: Triglycidyl p-aminophenol (Mitsubishi Chemical Corporation, jER (Registered) Registered trademark)630 1032H60: Trisphenolmethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation) jER(registered trademark) 1032H60) 828: Bisphenol A type liquid epoxy resin (Mitsubishi Chemical Corporation jER (Registered) Registered trademark)828) WA: Aromatic amines (jER Cure (registered trademark) WA, manufactured by Mitsubishi Chemical Corporation) PSM4261: Phenol compound (manufactured by Gun-ei Chemical Industry Co., Ltd.) MH700: Acid anhydride compound (Rikacid (registered trademark) MH700, manufactured by New Japan Chemical Co., Ltd.) 2E4MZ: Imidazoles (Curesol 2E4MZ, manufactured by Shikoku Chemical Industries, Ltd.) TPP: Triphenylphosphine (Hokuko Chemical Industry Co., Ltd., Hokuko TPP) DICY: Dicyandiamide (jER Cure (registered trademark) DI, manufactured by Mitsubishi Chemical Corporation) CY7) DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea (Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) 4,4'-DDS: 4,4'-diaminodiphenyl sulfone (Tokyo Chemical Industry Co., Ltd.) )

[0091] [Production and Evaluation of Curable Resin Composition and Cured Product] [Example 1] Component (A) is epoxy resin A, and component (B) is a modified aromatic amine-based hardener (Mitsubishi Chemical The epoxy resin composition was mixed with ER Cure (registered trademark) WA (manufactured by JER Cure Co., Ltd.) in the ratio shown in Table 1. This epoxy resin composition was preheated at 120°C for 2 hours, and then heated at 175°C for 2 hours. The mixture was heated at 40°C for 6 hours to harden it, and a 3 mm thick plate of the hardened material was prepared. The heat resistance and storage modulus were measured, and the results are shown in Table 1.

[0092] [Example 2] Component (B) is a phenolic compound (product name "PSM4261": manufactured by Gun-ei Chemical Industry Co., Ltd.), hardening Triphenylphosphine (trade name "Hokuko TPP": manufactured by Hokko Chemical Industry Co., Ltd.) is used as a catalyst. An epoxy resin composition was prepared in the same manner as in Example 1, except that the ingredients were kneaded in the ratio shown in Table 1. Plates of the cured products were prepared and the heat resistance and storage modulus were measured according to the methods described below. The measurement results are shown in Table 1.

[0093] [Example 3] Component (A) is epoxy resin A, and component (B) is acid anhydride compound ("Rikacid (registered trademark) )MH700" (manufactured by Shin Nippon Rika Co., Ltd.) and imidazoles ("2E4MZ" (manufactured by Shikoku Kasei Corporation) ) were mixed in the ratio shown in Table 1 to prepare an epoxy resin composition. The composition was preheated at 100°C for 3 hours, then heated at 140°C for 3 hours to cure. A 3 mm thick plate of the cured product was prepared, and the heat resistance and storage modulus were measured according to the methods described below. The results of these measurements are shown in Table 1.

[0094] [Example 4] Component (A) is epoxy resin A, and component (B) is dicyandiamide (Mitsubishi Chemical Corporation DICY7), hardening accelerator: 3-(3,4-dichlorophenyl)-1,1-dimethyl Urea (Tokyo Chemical Industry Co., Ltd.), component (C) (bisphenol A type liquid epoxy resin (Mitsubishi The mixture was mixed in the ratio shown in Table 1 using JER828 (manufactured by JER Chemical Co., Ltd.) and then subjected to an extrusion process. An epoxy resin composition was prepared. This epoxy resin composition was preheated at 80°C for 1 hour. After that, the mixture was heated at 130°C for 1.5 hours to harden it, and a 3 mm thick plate of the hardened material was prepared. The heat resistance and storage modulus were measured according to the method described above. The results are shown in Table 1.

[0095] [Example 5] Component (A) is epoxy resin A, and component (B) is 4,4'-DDS (Tokyo Chemical Industry Co., Ltd. Component (C) (bisphenol A type liquid epoxy resin (Mitsubishi Chemical Corporation) ER (registered trademark) 828) was used to prepare an epoxy resin composition by kneading in the ratio shown in Table 1. This epoxy resin composition was heated at 180°C for 120 minutes to harden it, and a hardened sheet of 3 mm thick was formed. The heat resistance and storage modulus of the oxide were measured according to the methods described below. The results are shown in Table 1.

[0096] [Comparative Example 1] Component (A) is a diaminodiphenylmethane type epoxy compound (manufactured by Mitsubishi Chemical Corporation). The same procedure as in Example 1 was repeated except that the ethylenediaminetetraacetate (E.J.ER.TM. 604) was used and mixed in the proportions shown in Table 1. An epoxy resin composition was prepared in the above manner, a plate of the cured product was produced, and the heat-resistant The results of these measurements are shown in Table 1.

[0097] [Comparative Example 2] Component (A) is trisphenolmethane type epoxy resin (Mitsubishi Chemical Corporation jE Example 2 was performed using the same composition as in Example 2, except that the cellulose acetate ester (registered trademark 1032H60) was used and kneaded in the ratio shown in Table 1. An epoxy resin composition was prepared in the same manner as in the above, a plate of the cured product was prepared, and the plate was then cured according to the method described below. The heat resistance and storage modulus were measured, and the results are shown in Table 1.

[0098] [Comparative Example 3] Component (A) is triglycidyl p-aminophenol (JER manufactured by Mitsubishi Chemical Corporation). The same procedure was carried out as in Example 3, except that 630 (registered trademark) was used and kneaded in the proportions shown in Table 1. An epoxy resin composition was prepared by the above procedure, and a plate of the cured product was prepared. The heat resistance, storage stability, and other properties of the composition were evaluated according to the methods described below. The storage modulus was measured, and the results are shown in Table 1.

[0099] [Comparative Example 4] Component (A) is a diaminodiphenylmethane type epoxy compound (manufactured by Mitsubishi Chemical Corporation). The same procedure as in Example 4 was repeated, except that the ethylenediaminetetraacetate (E.J.ER.TM. 604) was used and mixed in the proportions shown in Table 1. An epoxy resin composition was prepared in the above manner, a plate of the cured product was produced, and the heat-resistant The results of these measurements are shown in Table 1.

[0100] <Heat resistance> The heat resistance in the examples and comparative examples was measured using a dynamic viscoelasticity tester manufactured by Seiko Instruments Inc. Using the performance measurement device "DMS6100", the temperature was raised from 30 to 300°C at a rate of 5°C / min. The measurement was performed. The deformation mode was double-support bending, and the measurement frequency was 1 Hz. The glass transition temperature ( Tg) is the temperature at which the loss tangent tanδ (= loss modulus E'' / storage modulus E') reaches its maximum The higher the glass transition temperature, the better the heat resistance. do.

[0101] <Storage modulus> The elastic modulus in the examples and comparative examples was measured using a dynamic viscoelasticity tester manufactured by Seiko Instruments Inc. Using the performance measurement device "DMS6100", the temperature was raised from 30 to 300°C at a rate of 5°C / min. The deformation mode was double-support bending, and the measurement frequency was 1 Hz. The storage modulus was measured The storage modulus E' at a constant temperature of 40°C was used as an index.

[0102] Evaluation Criteria [Heat resistance] 〇: Glass transition temperature is 200℃ or higher ×: Glass transition temperature is less than 200°C

[0103] Evaluation Criteria Elasticity Modulus ◎: Storage modulus is 3.0 GPa or more. 〇: Storage modulus is 2.5 GPa or more. ×: The storage modulus is less than 2.5 GPa.

[0104] [Table 1]

[0105] [Evaluation Results] As can be seen from the present examples and comparative examples, the epoxy resin containing component (A) and component (B) The cured product obtained from the resin composition exhibits excellent performance, achieving both heat resistance and elastic modulus. I found out.

Claims

1. An epoxy resin composition comprising at least (A) and (B). (A) An epoxy resin having a structure represented by general formula (1). 【Chemistry 1】 In formula (1), R1 to R4 may be the same or different, and each represents a hydrogen atom or a hydrocarbon. R1 to R4 are each a radical that may contain a heteroatom, and R1 to R4 are bonded to each other to form a ring. At least one of R1 to R4 is a hydrocarbon group.) (B) Amine compounds, amide compounds, phenol compounds, acid anhydride compounds, imines At least one epoxy resin hardener selected from the group consisting of ethylenediamines.

2. The epoxy resin composition according to claim 1, wherein the formula (1) is the following formula (2): 【Chemistry 2】

3. The epoxy resin according to claim 1, further comprising (C) an aromatic epoxy resin having a glycidyl ether group. The epoxy resin composition described above.

4. The component (C) is a bisphenol type epoxy resin, a phenol novolac type epoxy resin, The epoxy resin according to claim 3, which is at least one epoxy resin selected from the group consisting of epoxy resins. composition.

5. The weight ratio of the epoxy resin of component (A) to the epoxy resin of component (C) is 1:

99. The epoxy resin composition according to claim 3, wherein the ratio of the epoxy resin content to the epoxy resin content is 99:1 or less.

6. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 5.

Images