KR101794366B1 - Method for producing a phosphorus-containing epoxy resin, epoxy resin composition, and cured product thereof - Google Patents

Abstract

A method for producing a phosphorus-containing epoxy resin which gives a cured product excellent in low viscosity and flame retardancy, an epoxy resin composition containing a phosphorus-containing epoxy resin obtained by the method, and a cured product thereof. (A) which is at least one of an epoxy resin (a1) represented by the general formula (1) or an epoxy resin (a2) represented by the general formula (3) or an epoxy resin (a3) represented by the general formula (4) (B) composed of an organophosphorous compound (b1) represented by the general formula (6) and / or an organophosphorus compound (B) composed of the organophosphorous compound (b2) represented by the general formula (6) to give an epoxy equivalent of 200 to 600 g / Wherein the epoxy resin (A) has a hydroxyl group concentration of 200 meq / 100 g or less, a total chlorine content of 0.4 weight% or less, an alpha -diol content of 10 meq / 100 g or less, and the weight ratio of the organic phosphorus compound (b1) / the organic phosphorus compound (b2) in the organophosphorus compound (B) is 50/50 to 100/0.

Description

A method for producing a phosphorus-containing epoxy resin, an epoxy resin composition and a cured product thereof,

The present invention relates to a novel epoxy resin useful as a curing agent for encapsulating and coating materials for electric and electronic parts, a coating material, a laminated material, a composite material and the like, which is excellent in low viscosity and is excellent in flame retardancy, The present invention relates to an epoxy resin composition using the same and a cured product thereof, and is suitably used for printed wiring boards and insulating materials for electrical and electronic fields such as semiconductor encapsulation.

BACKGROUND ART Epoxy resins have been widely used for industrial purposes, and their required performance has been increasingly advanced in recent years. For example, there is a semiconductor encapsulating material in a representative field of a resin composition subject to an epoxy resin. In recent years, along with the improvement of the degree of integration of semiconductor elements, the package size has become larger and thinner, The transition to surface mounting has progressed, and development of a material having superior solder heat resistance has been desired.

In recent years, the technology trends of high integration and high density packaging have led to the development of hybrid ICs, chip on boards, tape carrier packages, plastic pin grid arrays, plastic ball grid arrays, and the like, instead of the package by transfer molding using conventional molds A method of encapsulating and mounting a liquid material without using a mold is increasing. However, in general, a liquid material has a drawback that its reliability is lower than that of a solid material used for transfer molding. This is because the viscosity of the liquid material is limited and there is a restriction on the resin, the curing agent, the filler, and the like to be used. Further, in recent years, since the halogen-free flame retardant has been subjected to softening, there has been an increasing demand for flame retardancy in these applications that were not required when the halogen-based flame retardant was used.

Further, in the field of composites, there is an increasing demand for halogen-free, but low viscosity is essential while ensuring flame retardancy, and therefore satisfactory results have not been obtained.

In order to overcome these problems, epoxy resin and curing agent, which are the main themes, are required to have low viscosity, low moisture absorption, high internal resistance and flame retardancy. As low-viscosity epoxy resins, bisphenol A type epoxy resins and bisphenol F type epoxy resins and the like are generally known, but they are not sufficient in terms of low viscosity and have no flame retardancy. As an epoxy resin excellent in low viscosity, Patent Document 1 discloses an epoxy resin having an oxymethylene chain. However, there is room for improvement in heat resistance and moisture resistance, and no consideration is given to flame retardancy. Patent Document 2 discloses an epoxy resin having a bicyclohexyl ring, but no consideration is given to flame retardancy. Patent Document 3 discloses a phosphorus-containing epoxy resin having flame retardancy, which is problematic in that it is a phosphorus-containing epoxy resin obtained from a bifunctional epoxy resin having an aromatic skeleton and a phosphorus-containing phenol resin, and has a low viscosity. Patent Document 4 mentions flame retardancy with a phosphorus-containing epoxy resin composition, and describes that an aliphatic epoxy resin can also be used as a raw material for a phosphorus-containing epoxy resin. However, there is no description about the effect of using an aliphatic epoxy resin, Further, there is no description about the characteristics as the phosphorus-containing epoxy resin, and no consideration is given to the viscosity. Patent Document 5 discloses a composition containing a phosphorus-containing monoepoxy resin, but the use of an aliphatic diluent in combination is essential and can not be used alone.

Japanese Patent Application Laid-Open No. 4-359009 Japanese Patent Application Laid-Open No. 2006-188606 Japanese Patent Application Laid-Open No. 2001-288247 Japanese Patent Application Laid-Open No. 2002-249540 Japanese Patent Application Laid-Open No. 2001-106766 Japanese Patent Application Laid-Open No. 61-268691

Thus, it was difficult to obtain a flame retardant liquid epoxy resin. Accordingly, an object of the present invention is to provide a method for producing a phosphorus-containing epoxy resin which gives a cured product excellent in low viscosity and flame retardancy, an epoxy resin composition containing a phosphorus-containing epoxy resin obtained by the method, .

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a necessary condition for a low-viscosity epoxy resin required for producing a phosphorus-containing epoxy resin which does not significantly impair the physical properties of a cured product, The present invention has been completed on a method for producing a phosphorus-containing epoxy resin, and means for solving the above problems are as described in the claims.

(1) an epoxy resin (A) comprising at least one of an epoxy resin (a1) represented by the general formula (1) or an epoxy resin (a2) represented by the general formula (3) (B) having an epoxy equivalent of 200 to 600 g / eq and a phosphorus content of 1 to 6% by weight by reacting an organophosphorus compound (b1) represented by the formula (6) Wherein the epoxy resin (A) has a hydroxyl group concentration of 200 meq / 100 g or less, a total chlorine content of 0.4 weight% or less, an alpha -diol content of 10 meq / 100 g or less, Wherein the weight ratio of the organic phosphorus compound (b1) to the organic phosphorus compound (b2) in the organophosphorus compound (B) is 50/50 to 100/0.

In the formula, R ₁ is a hydrocarbon group having 6 to 31 carbon atoms, which may contain an oxygen atom, a nitrogen atom or a sulfur atom, having at least one aromatic ring, and G represents any one of the formula (2) or hydrogen.

In the formula, R ₂ is an aliphatic hydrocarbon group having 6 to 17 carbon atoms, which may be an oxygen atom, a nitrogen atom or a sulfur atom, having at least one cyclohexane ring which may be monocyclic or heterocyclic, G is a group represented by the formula Represents either one.

R ₃ represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, and R ₄ represents -R ₃ -OG, -R ₃ -H, or hydrogen , G represents any one of the formula (2) or hydrogen, and k represents an integer of 0 or 1.

In the formula, R ₅ and R ₆ represent hydrogen or a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic. R ₅ and R ₆ may combine to form a cyclic structure. n represents an integer of 0 or 1; Ar represents any one of benzene, biphenyl, naphthalene, anthracene, phenanthrene, and hydrocarbon substituents thereof.

In the formula, R ₇ and R ₈ represent hydrogen or a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic. R ₇ and R ₈ may combine to form a cyclic structure. and m represents an integer of 0 or 1.

(2) An epoxy resin composition comprising a phosphorus-containing epoxy resin obtained by the process for producing a phosphorus-containing epoxy resin according to (1) and a curing agent as essential components.

(3) A cured product obtained by curing the epoxy resin composition according to (2).

The epoxy resin (A) of the present invention is essentially an epoxy resin (a1) represented by the general formula (1) or an epoxy resin (a2) represented by the general formula (3) or an epoxy resin (a3) represented by the general formula (4). Even if an epoxy resin other than these is used, a phosphorus-containing epoxy resin having a low viscosity and a flame retardancy which is the object of the present invention can not be obtained.

Generally, when a new epoxy resin is synthesized by reacting an epoxy resin stream with a phenol resin stream, it is unavoidable that an epoxy resin as a raw material remains in the obtained epoxy resin. Therefore, in the case of the phosphorus-containing epoxy resin to be obtained, the influence of the epoxy resin (A) to be a raw material also needs to be considered.

Glycidyl etherification derived from an alcoholic hydroxyl group tends to have a large amount of unreacted residual hydroxyl groups because of low reactivity. The residual hydroxyl groups in the raw material epoxy resin (A) remain unremoved without participating in the reaction with the phosphorus compound, thereby lowering the terminal purity of the phosphorus containing epoxy resin. Therefore, the increase in the residual hydroxyl groups in the raw epoxy resin (A) Containing epoxy resin composition increases the hygroscopicity of the epoxy resin composition and causes a decrease in the storage stability of the acid anhydride curing agent or the microcapsule type latent curing agent. In addition, since the strength and the heat resistance of the cured product are deteriorated and the physical properties of the cured product are deteriorated, high purity of the residual hydroxyl groups of the raw material epoxy resin (A) becomes necessary. Therefore, the residual hydroxyl group concentration of the epoxy resin (A) is preferably 200 meq / 100 g or less, more preferably 100 meq / 100 g or less, and further preferably 50 meq / 100 g or less.

In addition, in order to reduce the residual hydroxyl group concentration, if the reactivity is increased by adding a catalyst or the like, the side reaction is increased in parallel and high concentration of the total chlorine contained is caused. Since the total amount of chlorine in the raw material epoxy resin (A) remains in the phosphorus-containing epoxy resin, the electrical reliability of the cured product is remarkably lowered, so that the purity of the total chlorine is also required to be high. The total chlorine content of the raw material epoxy resin (A) is preferably 0.4% by weight or less, more preferably 0.2% by weight or less, and still more preferably 0.1% by weight or less. In the case of glycidyl etherification derived from an alcoholic hydroxyl group, most of the total chlorine content is 1% by weight or more. Therefore, it is necessary to reduce the total chlorine amount by a high purification reaction, distillation operation or extraction operation. These methods are not specifically defined, but various methods currently in use can be used.

Further, the? -Diol content in the raw epoxy resin (A) remains unchanged as it is in the reaction with the phosphorus compound in the same manner as the residual hydroxyl concentration, thereby lowering the terminal purity of the phosphorus containing epoxy resin. The increase in the content of the? -Diol in the epoxy resin composition increases the hygroscopicity of the phosphorus-containing epoxy resin composition and causes a decrease in the storage stability of the acid anhydride curing agent or the microcapsule type latent curing agent. Further, since the strength of the cured product and deterioration of the properties of the cured product such as deterioration of the heat resistance are deteriorated, the content of the? -Diol in the raw material epoxy resin (A) is required to be lowered. Therefore, the alpha -diol content of the epoxy resin (A) is preferably 10 meq / 100 g or less, more preferably 5 meq / 100 g or less, and further preferably 3 meq / 100 g or less.

In the case of the epoxy resin (a3) represented by the general formula (4), if the residual hydroxyl group concentration or the? -Diol content is high, there are many bifunctional epoxy resins which do not have a cyclohexane ring The flame retardancy deteriorates, which is undesirable.

The epoxy resin (a1) represented by the general formula (1) to be reacted with the organic phosphorus compound contains at least one aromatic ring, and the -O-CH ₂ -R ₁ -CH ₂ -O- structure is essential. The aromatic ring helps improve the flame retardancy of the phosphorus-containing epoxy resin, and the -O-CH ₂ -R ₁ -CH ₂ -O- structure is effective for lowering the viscosity of the phosphorus-containing epoxy resin. When an aromatic epoxy resin having no -O-CH ₂ -R ₁ -CH ₂ -O- structure is used as a starting material, low viscosity is not sufficient. Therefore, in order to lower the viscosity of the epoxy resin composition, an aliphatic epoxy resin It is necessary to use a reactive diluting agent of a large amount, and flame retardancy can not be ensured. In addition, when the amount of the aliphatic epoxy resin used is reduced to secure the flame retardancy, the viscosity of the epoxy resin composition remarkably increases, so that it is disadvantageous to low viscosity and the intended epoxy resin composition having a low viscosity is not obtained. That is, the bifunctional epoxy resin (a1) is a glycidyl etherified product of bifunctional primary alcohols having 8 to 33 carbon atoms and containing at least one aromatic ring in the skeleton.

A specific example of R ₁ in the formula of the bifunctional epoxy resin (a1) represented by the general formula (1) is shown in the general formula (7). R ₁ may be an isomer of the group of the formula (7) or may have a substituent. R ₁ may be a single R ₁ or two or more R _{1 s} .

Each j in the formulas independently represents an integer of 0 or 1.

Each j in the formulas independently represents an integer of 0 or 1.

Among the bifunctional epoxy resin (a1) represented by the general formula (1), the glycidyl etherified product of the para-xylene glycol represented by the general formula (8) and the glycidyl ether compound of the oxymethylene biphenyl represented by the general formula (9) are preferable.

The bifunctional epoxy resin (a2) represented by the general formula (3) to be reacted with the organic phosphorus compound is required to contain at least one cyclohexane ring. The cyclohexane ring helps improve the flame retardancy of the phosphorus-containing epoxy resin, and in the case of the aliphatic epoxy resin having no cyclohexane ring, the flame retardancy can not be secured. That is, the bifunctional epoxy resin (a2) is a glycidyl etherified product of a bifunctional aliphatic primary alcohol having 6 to 17 carbon atoms and containing at least one cyclohexane ring in its skeleton.

A specific example of R ₂ in the formula of the bifunctional epoxy resin (a2) represented by the general formula (3) is shown in the general formula (10). R ₂ may be an isomer of the group of the formula (10) or may have a substituent. R ₂ may be a single R ₂ or two or more R _{2 s} .

Among the bifunctional epoxy resin (a2) represented by the general formula (3), the glycidyl etherified product of cyclohexanedimethanol represented by the general formula (11) and the glycidyl etherified product of the hydrogenated bisphenol A represented by the general formula (12) are preferable.

The polyfunctional epoxy resin (a3) represented by the formula (4) to be reacted with the organic phosphorus compound is a trifunctional epoxy resin or a tetrafunctional epoxy resin having a fat chain of 1 to 4 carbon atoms. In the case of an aliphatic epoxy resin not containing a cyclohexane ring, the flame retardancy can not be secured in the case of an aliphatic epoxy resin other than the polyfunctional epoxy resin represented by the general formula (4).

Among the polyfunctional epoxy resins (a3) represented by the general formula (4), glycidyl ether compounds of trimethylolpropane represented by the general formula (13) are preferable.

The organic phosphorus compound (B) to be reacted with the epoxy resin (A) is an organic phosphorus compound (b1) represented by the formula (5) and an organic phosphorus compound (b2) represented by the formula (6).

The organic phosphorus compound (b1) represented by the general formula (5) is an organic phosphorus compound having two active hydrogens, wherein R ₅ and R ₆ in the formula represent hydrogen or a hydrocarbon group, and each may be the same or different, R ₅ and R ₆ may combine with each other to form a cyclic structure. Specific examples of R ₅ and R ₆ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert- an octyl group, a nonyl group, a dodecyl group, an undecyl group, a benzyl group, a phenyl group, a toluyl group, a xylyl group and the like can be given. Examples of R ₅ and R ₆ which combine to form a cyclic structure include, for example, tetramethylene, cyclopentylene, cyclohexylene, cyclobutylene, cyclooctylene, cyclodecylene, norbornylene , Biphenylene group and the like. Ar is an arylene group, and specific examples thereof include a phenylene group, a toluylene group, a xylylene group, a naphthylene group and a biphenylene group. In addition, the number of n is 0 or 1.

These organophosphorus compounds (b1) can be easily obtained by reacting the organophosphorus compound (b2) of the formula (6) with a monocyclic or polycyclic quinone compound (Patent Document 6). Preferred examples of the organic phosphorus compound used in the present invention include 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (hereinafter abbreviated as DOPO) (Hereinafter abbreviated as DOPO-HQ) represented by the general formula (15), which is an addition product of 1,4-benzoquinone, or an organic phosphorus compound represented by the general formula (16) which is an addition product of DOPO and 1,4- (Hereinafter abbreviated as DOPO-NQ).

DOPO can be obtained as a trade name "HCA" (manufactured by Sankyo), and DOPO-HQ can be obtained as "HCA-HQ" (manufactured by Sanko K.K.).

Organophosphorus compounds (b2) represented by the formula (6) is an active hydrogen in the organic phosphorus compound 1 having, R _7, R ₈ in the formula represents hydrogen or a hydrocarbon group, each of which will be the same or different, a straight chain, branched Chain or cyclic structure, or R ₇ and R ₈ may combine to form a cyclic structure. Specific examples of R ₇ and R ₈ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, an octyl group, a nonyl group, a dodecyl group, an undecyl group, a benzyl group, a phenyl group, a toluyl group, a xylyl group and the like can be given. Examples of R ₇ and R ₈ bonded to form a cyclic structure include, for example, tetramethylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclodecylene, norbornylene , Biphenylene group and the like. Also, the number of m is 0 or 1. Of these, DOPO represented by the general formula (14) is preferable.

(B1) / (b2) of the organic phosphorus compound (b1) represented by the general formula (5) and the organic phosphorus compound (b2) represented by the general formula (6) among the organic phosphorus compounds used for obtaining the phosphorus- The weight ratio is 50/50 to 100/0, preferably 65/35 to 100/0, more preferably 80/20 to 100/0, further preferably 90/10 to 100/0. (b1) / (b2) is less than 0/100 to 50/50, the phosphorus content can be easily adjusted. Therefore, it is effective in improving the flame retardancy and lowering the viscosity. However, the monofunctional organic phosphorus compound b2) and the epoxy group are frequently reacted with each other, and a large amount of epoxy resin having less than one functional group is generated to lower the total epoxy number, so that the reactivity is significantly lowered. In addition, the adhesiveness of the resulting cured product is reduced, the heat resistance is lowered and the moisture resistance is lowered, and the electrical insulation reliability is remarkably lowered. If the weight ratio of (b1) / (b2) is in the range of 50/50 to 100/0, sufficient reactivity can be ensured and the physical properties of the cured product are not deteriorated. When the organic phosphorus compound (b1) represented by the general formula (5) is used in a large amount, the molecular weight can be increased and the adhesiveness can be greatly improved. The use of the organic phosphorus compound (b2) , It is necessary to adjust the usage amount according to the intended characteristics. When the flame retardancy is required within the range of the weight ratio of (b1) / (b2) = 50/50 to 100/0, the use ratio of the organic phosphorus compound (b2) is increased, The use ratio of the organic phosphorus compound (b1) may be increased.

The organophosphorus compound may be used by mixing a previously synthesized organophosphorus compound (b1) represented by the general formula (5) and the organophosphorus compound (b2) represented by the general formula (6) May be reacted with an organic phosphorus compound (b2) represented by the general formula In this case, the quinone is preferably reacted at less than 1 mole with respect to 1 mole of the organic phosphorus compound (b2) represented by the formula (6). When 1 mole or more of quinones is used relative to 1 mole of the compound (b2) represented by the general formula (6), the quinones of the raw material remain in the resulting phosphorus-containing epoxy resin, and the moisture resistance of the cured product deteriorates.

The reaction of the epoxy resin (A) and the organic phosphorus compound (B) used in the present invention can be carried out by a known method. The reaction may be carried out at a temperature of 100 to 200 ° C, more preferably 120 to 180 ° C. The reaction time can be determined by measuring the epoxy equivalent. The measurement can be performed by the method of JIS K-7236. The epoxy equivalent is increased by the reaction between the epoxy resin (A) and the organic phosphorus compound, and the reaction end point can be determined by comparison with the theoretical epoxy equivalent.

In addition, when the reaction rate is low, productivity can be improved by using a catalyst as needed. Specific examples thereof include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, Phosphonium salts such as phosphonium bromide, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole. These catalysts may be used alone or in combination of two or more.

The epoxy equivalent of the phosphorus-containing epoxy resin obtained by the production method of the present invention is preferably 200 g / eq to 600 g / eq. When the epoxy equivalent is less than 200 g / eq, the adhesiveness is poor. When the epoxy equivalent is more than 600 g / eq, the viscosity is increased, and the heat resistance of the resulting cured product is greatly impaired. Therefore, the epoxy equivalent is preferably 200 g / eq to 600 g / eq, more preferably 230 g / eq to 550 g / eq, and still more preferably 250 g / eq to 500 g / eq.

The phosphorus content of the phosphorus-containing epoxy resin obtained by the production method of the present invention is preferably 1 wt% to 6 wt%. From the viewpoint of flame retardancy, it is preferable that the phosphorus content is high, but as the phosphorus content increases, the viscosity of the phosphorus-containing epoxy resin increases and the epoxy equivalent increases, and the heat resistance of the resulting cured product is greatly impaired. Therefore, the phosphorus content is preferably 1 wt% to 6 wt%, more preferably 1.5 wt% to 4 wt%, and still more preferably 2 wt% to 3 wt%.

The total chlorine content of the phosphorus-containing epoxy resin obtained by the production method of the present invention is correlated with the lowering of the electrical reliability of the resulting cured product, and the electrical reliability of the cured product is lowered when the amount is increased. Considering the electrical reliability of the allowable hardened product, the total chlorine content is preferably 0.2% by weight or less, more preferably 0.09% by weight or less, still more preferably 0.05% by weight or less, as in general epoxy resin for encapsulating material .

The melting point of the phosphorus-containing epoxy resin obtained by the production method of the present invention at 100 캜 is preferably 1,000 mPa s or less, more preferably 600 mPa s or less, and furthermore preferably 300 mPa s or less. If the melt viscosity at 100 ° C is more than 1,000 mPa · s, the viscosity of the epoxy resin composition increases even when a curing agent having a relatively low viscosity is used, which makes it difficult to perform actual work, and it is difficult to obtain a normal molded article.

An epoxy resin other than the phosphorus-containing epoxy resin obtained by the production method of the present invention may be added to the composition of the present invention to such an extent that the properties are not impaired.

The phosphorus content of the entire epoxy resin component in the epoxy resin composition of the present invention does not need to be specially specified. However, from the viewpoint of flame retardancy, the phosphorus content is preferably high and the phosphorus content is preferably low from the viewpoint of low viscosity. Therefore, it is preferably 0.5% by weight to 5% by weight, more preferably 1% by weight to 4% by weight, and still more preferably 2% by weight to 3% by weight in order to satisfy both requirements.

Examples of the curing agent of the present invention include various polyhydric phenol resins and acid anhydrides typified by phenol novolac resins, amines such as dicyandiamine and diethyldiaminodiphenylmethane, hydrazides, acidic polyesters, etc. May be used. These curing agents may be used either singly or in combinations of two or more.

In the epoxy resin composition of the present invention, a curing accelerator may be used if necessary. Examples of the curing accelerator include phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3- (3,4-dichlorodiphenyl) Urea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea and the like, but are not limited thereto.

These curing accelerators are preferably in the range of 0.01 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts of the epoxy resin, depending on the kind of the epoxy resin to be used, the kind of the epoxy resin curing agent used, the molding method, the curing temperature, 10 parts by weight is preferable.

The epoxy resin composition of the present invention may optionally contain an inorganic filler and / or an organic filler. Examples of the filler include inorganic fillers such as fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, Fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, and aramid fiber. These fillers are preferably 1 to 95% by weight in the epoxy resin composition.

The epoxy resin composition of the present invention may further contain various additives such as a silane coupling agent, an antioxidant, a releasing agent, a defoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant and a pigment. These additives are preferably in the range of 0.01 to 20% by weight in the total amount of the epoxy resin composition.

The epoxy resin composition of the present invention can be formed into a cured product by molding and curing in the same manner as the known epoxy resin composition. The molding method and the curing method can be carried out in the same manner as the known epoxy resin composition, and a method inherent to the epoxy resin composition of the present invention is unnecessary.

The epoxy resin cured product of the present invention may take the form of a coating film, an adhesive layer, a molded product, a laminate, a film and the like.

As a result of evaluating a molded article obtained using the epoxy resin composition of the present invention, it is possible to obtain a cured product having flame retardancy and a relatively low water absorption rate as compared with the conventional low viscosity resin composition. The epoxy resin composition and the cured product thereof are used for a resin composition for producing a copper-clad laminate used for an electronic circuit board or a sealing material, a molding material, a mold material, an adhesive, a film material, Materials and the like.

Example

Hereinafter, the present invention will be specifically described based on Synthesis Examples, Examples and Comparative Examples, but the technical scope of the present invention is not limited to Examples. Incidentally, the mixing ratio of each component in the examples and comparative examples indicates parts by weight unless otherwise specified.

In the present invention, the following analysis method was used.

Epoxy equivalent: the method described in JIS K-7236. Specifically, 20 mL of anhydrous acetic acid and 10 mL of a 20% aqueous solution of tetraethylammonium bromide acetic acid were added to each sample, and the solution was titrated with a 0.1 mol / L perchloric acid acetic acid standard solution using a potentiometric titration apparatus, The epoxy equivalents contained in the epoxy resin were measured from the concentrations, addition amounts and appropriate amounts of each reagent.

Total chlorine amount: The method described in JIS K-7243-3. That is, the sample is dissolved in 25 mL of diethylene glycol monobutyl ether, 25 mL of a 1,2-propanediol solution of 1 mol / L potassium hydroxide is added, and the mixture is reacted on a hot plate under heating and refluxing for 10 minutes. After cooling to room temperature, 50 mL of anhydrous acetic acid was added, and the solution was titrated with a 0.01 mol / L silver nitrate solution using a potentiometric titrator. The total amount of chlorine contained in the epoxy resin was measured from the concentration of each reagent, Respectively.

Viscosity: The method described in JIS K-7233. That is, 400 g of a resin was weighed out in a 500-mL cylindrical can, and the rotor was allowed to stand in a constant temperature water bath at 25 ± 0.2 ° C for 5 hours and immersed in the resin.

Softening point: the method described in JIS K-7234. In other words, the sample was filled in a prescribed ring by a ring method, supported horizontally in a glycerin bath, and heated at a rate of 5 ° C / min with a specified sphere placed at the center of the sample.

Concentration of hydroxyl group: To the amount of hydroxyl groups contained in the epoxy resin, an equivalent amount of phenyl isocyanate and a dibutyl tin maleate as a catalyst were added to sufficiently react the hydroxyl group and the isocyanate, and then dibutyl Amine was added to consume excess phenyl isocyanate, and finally titration was carried out with perchloric acid. The concentration of hydroxyl groups contained in the epoxy resin was measured from the concentrations, addition amounts and appropriate amounts of the respective reagents.

Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample, and the mixture was heated and wet-mixed to make orthophosphoric acid. Metabanadate and molybdate were reacted in an acidic sulfuric acid solution to measure the absorbance at 420 nm of the resulting phosphorus molybdate complex and the content of phosphorus atoms determined by a previously prepared calibration curve in weight% And the content of phosphorus contained in the epoxy resin was measured.

? -diol content: the method described in JIS K-7146.

That is, chloroform is added to the sample and dissolved. Then, ortho-iodic acid solution is added and reacted for 2 hours. Thereafter, potassium iodide solution was added, and iodine generated was titrated with sodium thiosulfate. The amount of alpha -diol contained in the epoxy resin was measured from the concentration of each reagent, the amount of addition, and the appropriate amount.

Melt viscosity: Using a cone plate type viscometer (MODEL CV-1S, manufactured by Toa Corporation), the rotor was measured at a measurement temperature of 100 占 폚 using 5 poise cone (?: 24 mm,?: Respectively.

Flammability: The measurement was carried out in accordance with UL (Underwriters Laboratories Inc.) standard and UL94 vertical test method, and it was judged to be four levels of V-0, V-1, V-2 and NG (no flammability) (The flame retardancy is worse as it goes back).

Adhesion: The method according to JIS C-6481 5.7. That is, peeling was performed at a rate of 50 mm / min in a perpendicular direction between one prepreg and the other three sheets, and the measurement was carried out.

Moisture absorptivity: The method according to JIS C-6481 5.13. That is, after drying for 24 hours in an oven at 50 占 폚 using a test piece cut into 50 mm 占 50 mm, the dry weight was measured, and then the weight after 72 hours of storage in a treatment tank adjusted to 85 占 폚 / 85% RH And the moisture absorption rate was measured based on the increment from the dry weight.

Heat resistance: Method according to IPC-TM-650, 2.4.24.1. That is, when the peeling time by the TMA apparatus was measured, the sample was held at a constant temperature of 260 占 폚 in the TMA apparatus, and when the time elapsed until the displacement of the test piece occurred in all directions was 10 minutes or longer, Was evaluated as " x ". The TMA apparatus used was TMA / SS120U manufactured by SII Co., Ltd., Nanotechnology.

Chloride ion: The cured product was pulverized and subjected to a pressure cooker test at 150 캜 for 20 hours at a sample having a particle size of 2 mm pass and 1 mm temperature. Chloride ion of extracted water was measured by ion chromatography, And converted into the concentration in the cargo.

Example 1.

In a four-glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, Epototo TX-0929 (manufactured by Dainippon Ink and Chemicals, Inc.) was used as the bifunctional aromatic epoxy resin Epoxy equivalent: 144 g / eq, total chlorine: 0.11 wt%, viscosity: 50 mPa 揃 s, hydroxyl group concentration: 39 meq / 100 g, α-diol content: 2.3 and 252.6 g of DOPO-HQ (trade name: HCA-HQ, hydroxyl group equivalent: 162 g / eq, phosphorus content: 9.5 wt%) was added as an organophosphorous compound to the mantle After heating to 130 ° C with a mantle heater, the mixture was heated to 130 ° C, and 0.25 g of triphenylphosphine (product name: TPP, manufactured by Hokko Chemical Co., Ltd.) was added as a catalyst and the reaction temperature was adjusted to 160 And the reaction was carried out for 4 hours while maintaining the temperature at < RTI ID = 0.0 > 165 C < / RTI > to obtain 795 g of the phosphorus-containing epoxy resin (E-1) . Table 1 shows properties of the obtained phosphorus-containing epoxy resin (E-1).

Example 2.

In a four-glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device and a cooling tube, 602.5 g of Eptotor TX-0929 (described above) as the bifunctional aromatic epoxy resin (a1) As the organic phosphorus compound, DOPO-NQ (1,4-naphthoquinone adduct of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hydroxyl equivalent of 187 g / 197.5 g) was added and heated to 130 캜 with stirring in a mantle heater. When the temperature reached 130 캜, 2 ethyl 4 methylimidazole (product name: 2E4MZ (trade name, manufactured by Shikoku Kasei Kabushiki Kaisha) ) Was added and reacted for 4 hours while maintaining the reaction temperature at 160 ° C to 165 ° C to obtain 795 g of phosphorus-containing epoxy resin (E-2). Table 1 shows properties of the obtained phosphorus-containing epoxy resin (E-2).

Example 3.

To a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a condenser tube was charged 80 parts by mass of Epototo TX-0934 (trade name: Epoxy equivalent: 184 g / eq, total chlorine: 0.11 wt%, viscosity: 200 mPa 揃 s, hydroxyl group concentration: 63 meq / 100 g, α-diol content: 2.5 meq / 100 g) and 116.3 g of DOPO-NQ (tactic) as an organic phosphorus compound and 75.0 g of DOPO (trade name: HCA, phosphorus content: 14.2% by weight) , 0.19 g of triphenylphosphine (as a catalyst) was added as a catalyst at the time when the temperature reached 130 占 폚, and the reaction was carried out for 4 hours while maintaining the reaction temperature at 160 占 폚 to 165 占 폚 to obtain a phosphorus-containing epoxy resin (E -3). Table 1 shows properties of the obtained phosphorus-containing epoxy resin (E-3).

Example 4.

182.0 g of DOPO (as described above) as an organic phosphorus compound and 420 g of toluene were added to four separable glass separable flasks equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas introducing device and heated under stirring in nitrogen atmosphere to completely dissolve Respectively. Thereafter, 56.7 g of 1,4-naphthoquinone (3% functional product, manufactured by Kawasaki Kasei K.K.) as a quinone was added in portions while paying attention to the temperature rise by the reaction heat. The molar ratio of 1,4-naphthoquinone to DOPO was 1,4-naphthoquinone / DOPO = 0.41. After the heating reaction, Epototo TX-0917 (manufactured by Tokto Chemical Co., Ltd., R ₁ of formula ( ₁ ) is a compound of formula (7-12), epoxy equivalent: 563.0 g) was added to the solution while introducing nitrogen gas, and the solution was agitated while introducing nitrogen gas, and the solution was stirred And heating was performed to 130 DEG C to remove toluene from the system. Thereafter, 0.24 g of triphenylphosphine (the foregoing) was added as a catalyst, and the reaction was carried out for 4 hours while maintaining the reaction temperature at 160 ° C to 165 ° C to obtain 790 g of phosphorus-containing epoxy resin (E-4). Table 1 shows properties of the obtained phosphorus-containing epoxy resin (E-4).

Example 5.

165 g (manufactured by Dainippon Ink and Chemicals, Inc.) was added as a bifunctional aliphatic epoxy resin (a2) of formula (3) to four separable glass flasks equipped with a stirrer, a thermometer, A cyclohexanedimethanol diglycidyl ether resin, an epoxy equivalent of 140 g / eq, a total chlorine of 0.075 wt%, a viscosity of 45 mPa s, a hydroxyl group concentration of 19 meq / 100 g, an alpha -diol content of 2.8 meq / 100 g) and 252.6 g of DOPO-HQ (described above) as an organophosphorus compound were added and heated with stirring to 130 DEG C with a mantle heater. After the temperature was maintained at 130 DEG C for 1 hour, , 0.25 g of triphenylphosphine (tactical) was added, and the reaction was carried out for 4 hours while maintaining the reaction temperature at 160 ° C to 165 ° C to obtain 795 g of phosphorus-containing epoxy resin (E-5). Table 1 shows properties of the obtained phosphorus-containing epoxy resin (E-5).

Example 6.

In a four-glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device and a condenser tube, HBPADGE (manufactured by Maruzen Sekiyu Kagaku Kogyo Co., Ltd.) was used as the bifunctional aliphatic epoxy resin (a2) , Hydrogenated bisphenol A diglycidyl ether resin, epoxy equivalent: 210 g / eq, total chlorine: 0.14 wt%, viscosity: 780 mPa 揃 s, hydroxyl group concentration: 66 meq / 100 g, 100 g) and 168.0 g of DOPO-HQ (described above) as an organophosphorus compound were added and heated with stirring to 130 캜 with a mantle heater. After the temperature was maintained at 130 캜 for one hour, 0.17 g of triphenylphosphine (tactic) was added and reacted for 4 hours while maintaining the reaction temperature at 160 to 165 ° C to obtain 795 g of phosphorus-containing epoxy resin (E-6). Table 1 shows properties of the obtained phosphorus-containing epoxy resin (E-6).

Example 7.

A four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube was charged with 80 parts by weight of Epototo ZX-1542 (manufactured by Dainippon Ink and Chemicals, Inc.) as the polyfunctional aliphatic epoxy resin (a3) Trimethylolpropane polyglycidyl ether resin, epoxy equivalent: 118 g / eq, total chlorine: 0.072 weight%, viscosity: 80 mPa.s, hydroxyl group concentration: 195 meq / 100 g, , 50.0 g of DOPO (as described above) and 180.0 g of DOPO-HQ (tactic) as an organophosphorous compound were added and heated with stirring to 130 캜 with a mantle heater. After reaching 130 캜, And 0.23 g of phenylphosphine (described above) were added and reacted for 4 hours while maintaining the reaction temperature at 160 캜 to 165 캜 to obtain 795 g of phosphorus-containing epoxy resin (E-7). Table 1 shows properties of the obtained phosphorus-containing epoxy resin (E-7).

Comparative Example 1

A four-glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device and a cooling tube was charged with Epototo PG-207GS (polypropylene glycol diglycidyl ether resin, manufactured by Tokto Kasei Kabushiki Kaisha, , Epoxy equivalent: 319 g / eq, total chlorine: 0.10 wt%, viscosity: 45 mPa 揃 s, hydroxyl group concentration: 88 meq / 100 g, α-diol content: 2.0 meq / 100 g) -HQ (tactical) was added, and the mixture was heated with stirring to 130 캜 with a mantle heater. After reaching 130 캜, 0.17 g of triphenylphosphine (the foregoing) was added as a catalyst, The reaction was conducted for 4 hours while maintaining the temperature at 165 캜 to obtain 795 g of phosphorus-containing epoxy resin (E-8). Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-8).

Comparative Example 2

757.9 g of Eptotor TX-0917 (described above) as an epoxy resin, and DOPO-HQ (described above) 42.1 (as a organophosphorous compound) were added to four separable glass separable flasks equipped with a stirrer, a thermometer, g, and heated with stirring to 130 캜 with a mantle heater. When the temperature reached 130 캜, 0.05 g of triphenylphosphine (tactic) was added as a catalyst, and while maintaining the reaction temperature at 160 캜 to 165 캜, 4 The reaction was conducted for a period of time to obtain 795 g of a phosphorus-containing epoxy resin (E-9). Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-9).

Comparative Example 3

480.0 g of Eptotor TX-0917 (as described above) as an epoxy resin, 220.0 g of DOPO (as a tackifying agent) as an organic phosphorus compound, and 200.0 g of an organic phosphorus compound were added to four glass spherical separable flasks equipped with a stirrer, a thermometer, 100.0 g of DOPO-HQ (tactical) was added and heated with stirring to 130 캜 with a mantle heater. When the temperature reached 130 캜, 0.32 g of triphenylphosphine (the foregoing) was added as a catalyst, And reacted for 4 hours while maintaining the temperature at -165 占 폚 to obtain 795 g of a phosphorus-containing epoxy resin (E-10). Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-10).

Comparative Example 4

505.0 g of Eptoto TX-0934 (described above) as an epoxy resin, and DOPO-HQ (a tactic) of 295.0 g as an organic phosphorus compound were placed in four glass separable flasks equipped with a stirrer, a thermometer, g, and the mixture was heated with stirring to 130 캜 with a mantle heater. When the temperature reached 130 캜, 0.30 g of triphenylphosphine (the foregoing) was added as a catalyst, and while maintaining the reaction temperature at 160 캜 to 165 캜, And reacted for a time to obtain 795 g of a phosphorus-containing epoxy resin (E-11). Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-11).

Comparative Example 5

137.6 g of DOPO (as described above) as an organic phosphorus compound and 330 g of toluene were added to four spherical glass separable flasks equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device and heated under stirring in nitrogen atmosphere to completely dissolve Respectively. Thereafter, 31.3 g of 1,4-naphthoquinone (described above) as a quinone was added in portions while paying attention to the temperature rise by the reaction heat. At this time, the molar ratio of 1,4-naphthoquinone to DOPO was 1,4-naphthoquinone / DOPO = 0.13. After the heating reaction, Epototo ZX-1659 (hydrogenated bisphenol A diglycidyl ether resin, epoxy equivalent: 215 g / eq, total chlorine: 0.45% by weight, manufactured by Dainippon Ink and Chemicals, 632.0 g) was added to the flask, and nitrogen gas was introduced into the flask. While the flask was heated to 130 ° C, the toluene was removed to the outside of the system Respectively. Thereafter, 0.17 g of triphenylphosphine (described above) was added as a catalyst, and the reaction was carried out for 4 hours while maintaining the reaction temperature at 160 ° C to 165 ° C to obtain 790 g of phosphorus-containing epoxy resin (E-13). Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-12).

Comparative Example 6

A four-glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube was charged with 1600 g of Epototo ZX-1542 (manufactured by Dotor Kasei K.K., trimethylolpropane polyglycidyl ether resin , Epoxy equivalent: 122 g / eq, total chlorine: 0.065 wt%, viscosity: 80 mPa 揃 s, hydroxyl group concentration: 262 meq / 100 g, α-diol content: 1.5 meq / 100 g) (Tactical) and 180.0 g of DOPO-HQ (tactical) were added and heated with stirring to 130 캜 with a mantle heater. Upon reaching 130 캜, 0.23 g of triphenylphosphine , And reacted for 4 hours while maintaining the reaction temperature at 160 ° C to 165 ° C to obtain 795 g of phosphorus-containing epoxy resin (E-13). Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-13).

Comparative Example 7

A four-glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube was charged with 80 parts by weight of Epototo YDF-170 (bisphenol F diglycidyl ether resin, manufactured by Dotagosei Co., , 547.4 g of epoxy equivalent weight: 168 g / eq, total chlorine: 0.15 wt%, viscosity: 3,000 mPa.s), and 252.6 g of DOPO-HQ (the foregoing) as an organic phosphorus compound were added and stirred with a mantle heater (E-14) was obtained by reacting with 0.25 g of triphenylphosphine (described above) as a catalyst at the time of reaching 130 캜 and maintaining the reaction temperature at 160 캜 to 165 캜 for 4 hours, 795 g was obtained. Table 2 shows properties of the obtained phosphorus-containing epoxy resin (E-14).

Examples 8 to 10 and Comparative Examples 8 to 11

Phosphorus-containing epoxy resin, curing agent, curing accelerator and the like were compounded according to the formulation shown in Table 3. The phosphorus-containing epoxy resin was dissolved in methyl ethyl ketone. Dicyandiamide (DICY, active hydrogen equivalent: 21.0 g / eq) was used as a curing agent previously dissolved in methyl cellosolve and dimethylformamide and 2 ethyl 4 Methylimidazole (described above) was added to prepare a resin composition varnish so that the non-volatile content was 50% by weight. Thereafter, the obtained resin varnish was used to impregnate the glass fiber (WEA 116E 106S 136, thickness: 100 占 퐉, manufactured by Nitto Boseki Co., Ltd.) as a base material, and the impregnated glass fiber was heated in a hot air circulating oven at 150 占 폚 Minute drying to obtain a prepreg. Subsequently, the obtained four prepregs were superimposed and heated and pressed under conditions of 130 占 폚 for 15 minutes and 170 占 폚 for 2.0 MPa 占 70 minutes to obtain a 0.5 mm thick laminated plate. Each of the obtained laminated plates was tested for various physical properties such as flame retardancy, adhesiveness, and moisture absorption rate. The results are shown in Table 4.

In Comparative Example 8, since an aliphatic phosphorus-containing epoxy resin is used, the adhesive property is good but the flame retardancy is poor and the moisture absorption resistance is poor. Comparative Example 9 is a phosphorus-containing epoxy resin of the formula (1). Since the phosphorus content is as low as 0.5% by weight, the flame retardancy is poor and the epoxy equivalent is also small at 196 g / eq. Comparative Example 10 is a phosphorus-containing epoxy resin represented by the following formula (1), and its epoxy equivalent weight is 705 g / eq, which means that the heat resistance is poor and the weight ratio of phosphorus compound (b1) / phosphorus compound The adhesiveness is poor and the moisture absorption resistance is poor. Comparative Example 11 is a phosphorus-containing epoxy resin of Formula 1, which has a large epoxy equivalent weight of 880 g / eq and a high melt viscosity of 1,300 mPa · s, so that the adhesive property is good but the heat resistance is poor. On the other hand, all of the examples are good in adhesiveness while ensuring sufficient flame retardancy, and have good moisture absorption resistance and heat resistance.

Examples 11 to 14 and Comparative Examples 12 to 14

A phosphorus-containing epoxy resin, a curing agent, a curing accelerator and the like were compounded according to the formulation shown in Table 5. As the curing agent, diethyldiaminodiphenylmethane (trade name: Kaya Hard AA, active hydrogen equivalent: 63 g / eq, viscosity: 2,500 mPa.s) (manufactured by Nippon Kayaku Co., Ltd.) , And the mixture was stirred and homogenized to obtain an epoxy resin composition. The resulting epoxy resin composition was defoamed, molded into a mold, and cured at a temperature of 150 DEG C for 120 minutes to obtain a 2-mm-thick cured product specimen. The obtained cured product test piece was tested for various physical properties such as chloride ion, flame retardance and moisture absorption rate. The results are shown in Table 6. In Comparative Example 12, a mixture of Epototo ZX-1059 (a mixture of bisphenol F diglycidyl ether resin and bisphenol A diglycidyl ether resin, manufactured by Tokto Kasei Co., Ltd., epoxy equivalent: 165 g / eq, total chlorine: 0.08% by weight, viscosity: 2,300 mPa.s) was used as the additive type flame retardant, and 1,3-phenylenebis-di-2,6-xylenyl phosphate (Daihachi Kagaku Kogyo Co., Trade name: PX-200, phosphorus content: 9.0% by weight) was added so that the phosphorus content in the epoxy resin composition became 2.0% by weight.

Comparative Example 12 is the phosphorus-containing epoxy resin of Chemical Formula 3, and since the total chlorine content of the raw material epoxy resin is as large as 0.45% by weight, the chloride ion of the cured product is 5 to 10 times as many as that in the Examples. This indicates that reliability is deteriorating. Further, since the hydroxyl group concentration is as high as 230 meq / 100 g and the? -Diol content is as high as 11 meq / 100 g, the hygroscopicity is also poor. Further, since the weight ratio of the phosphorus compound (b1) / phosphorus compound (b2) as a raw material is lower than 50/50 by weight as 43/57, the cured state of the cured product deteriorates and the flame retardancy is also slightly worse. Comparative Example 13 is a phosphorus-containing epoxy resin of Chemical Formula 4, in which the moisture absorption of the starting epoxy resin is as high as 262 meq / 100 g and the moisture absorption is poor and the weight ratio of the phosphorus compound (b1) / phosphorus compound (b2) / 61, which is lower than 50/50, the cured state of the cured product deteriorates and the flame retardancy is also slightly worse. Comparative Example 14 is an epoxy resin composition in which a flame retardant is blended with a commonly used low chlorine liquid resin. Even when the content of phosphorus is combined with that in Examples, flame retardancy is poor and moisture absorption resistance is poor. On the other hand, all of the examples are low in chlorine ion and good in hygroscopicity while ensuring sufficient flame retardancy. This indicates that the reliability is good.

Examples 15 to 17 and Comparative Examples 15 to 17

A phosphorus-containing epoxy resin, a curing agent, a curing accelerator and the like were compounded according to the formulation shown in Table 7. As a curing agent, a triphenylmethane type phenol resin (trade name: TMP-100, a hydroxyl group equivalent: 97.5 g / eq, softening point: 107 ° C, manufactured by Gunega Kagaku Kogyo Co., Ltd.) And homogenized to obtain an epoxy resin composition. The resulting epoxy resin composition was defoamed, molded into a mold, and cured at a temperature of 150 DEG C x 120 minutes + 180 DEG C x 60 minutes to obtain a 2 mm thick cured test piece. The obtained cured product test piece was tested for various properties such as moldability, flame retardance and moisture absorption rate. The results are shown in Table 8. In Example 14, Epototo ZX-1059 (described above) was used in combination as an epoxy resin other than the phosphorus-containing epoxy resin, and Epototo ZX-1542 Trimethylolpropane polyglycidyl ether resin, epoxy equivalent: 122 g / eq, total chlorine: 0.065 wt%, viscosity: 80 mPa s) manufactured by TOTO KASEI KOGYO CO., LTD.

In Comparative Example 15, since an epoxy resin containing an aliphatic phosphorus is used, the flame retardancy is poor and the moisture absorption resistance is poor. Comparative Example 16 is a phosphorus-containing epoxy resin obtained by the production method disclosed in Patent Document 4. Since the phosphorus-containing epoxy resin of Chemical Formula 1 is not used, the viscosity of the epoxy resin composition is too high and mold formation is difficult, I could not. In Comparative Example 17, an epoxy resin composition obtained by using a diluent in combination with a phosphorus-containing epoxy resin obtained by the production method disclosed in Patent Document 4 was lowered in viscosity, but the moldability was improved, but the flame retardancy was deteriorated and the moisture resistance was also deteriorated. On the other hand, all of the examples are good in moldability and hygroscopicity while ensuring sufficient flame retardancy.

Since the epoxy resin composition of the present invention is a low viscosity composition and its cured product is excellent in flame retardancy and moisture resistance, it can be used as a mold material, a laminate material, a sealing material, a composite material and the like.

Claims (6)

An epoxy resin (A) comprising at least one of an epoxy resin (a1) represented by the general formula (1) or the epoxy resin (a2) represented by the general formula (3) or the epoxy resin (a3) represented by the general formula (4) (B) composed of at least one compound selected from the group consisting of the compound (b1) and the organic phosphorus compound (b2) represented by the general formula (6) to give an epoxy equivalent of 200 to 600 g / eq and a phosphorus content of 1 to 6 Wherein the epoxy resin (A) has a hydroxyl group concentration of 200 meq / 100 g or less, a total chlorine content of 0.4 weight% or less, an alpha -diol content of 10 meq / 100 g or less, Wherein the weight ratio of the organic phosphorus compound (b1) to the organic phosphorus compound (b2) in the organophosphorus compound (B) is 50/50 to 100/0.
[Chemical Formula 1]

Wherein R ₁ is a hydrocarbon group having 6 to 31 carbon atoms, which may contain an oxygen atom, a nitrogen atom or a sulfur atom, which has at least one aromatic ring, and G represents any one of the formula 2 or hydrogen, 2.
(2)

(3)

In the formula, R ₂ is an aliphatic hydrocarbon group having 6 to 17 carbon atoms, which may be an oxygen atom, a nitrogen atom or a sulfur atom, having at least one cyclohexane ring which may be monocyclic or heterocyclic, G is a group represented by the formula One or more of which is represented by the formula (2).
[Chemical Formula 4]

R ₃ represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom, and R ₄ represents -R ₃ -OG, -R ₃ -H, or hydrogen , G represents any one of the formula (2) or hydrogen, at least one of them is represented by the formula (2), and k represents an integer of 0 or 1.
[Chemical Formula 5]

In the formula, R ₅ and R ₆ represent hydrogen or a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic. R ₅ and R ₆ may combine to form a cyclic structure. n represents an integer of 0 or 1; Ar represents any one of benzene, biphenyl, naphthalene, anthracene, phenanthrene, and hydrocarbon substituents thereof.
[Chemical Formula 6]

In the formula, R ₇ and R ₈ represent hydrogen or a hydrocarbon group, and each may be the same or different, and may be linear, branched or cyclic. R ₇ and R ₈ may combine to form a cyclic structure. and m represents an integer of 0 or 1. The method according to claim 1,
A process for producing a phosphorus-containing epoxy resin characterized in that the epoxy resin (A) according to claim 1 is at least one of an epoxy resin represented by the following general formula (8), (9) or (11)
[Chemical Formula 8]

[Chemical Formula 9]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

The method according to claim 1,
A process for producing a phosphorus-containing epoxy resin characterized in that the organic phosphorus compound (b1) according to claim 1 is at least one organic phosphorus compound represented by the formula (15) or (16).
[Chemical Formula 15]

[Chemical Formula 16]

The method according to claim 1,
A process for producing a phosphorus-containing epoxy resin characterized in that the organic phosphorus compound (b2) according to claim 1 is an organic phosphorus compound represented by the general formula (14).
[Chemical Formula 14]

An epoxy resin composition comprising a phosphorus-containing epoxy resin obtained by the process for producing a phosphorus-containing epoxy resin according to any one of claims 1 to 4 and a curing agent as essential components. A cured product obtained by curing the epoxy resin composition according to claim 5.