WO1997011981A1 - Epoxy resin composition - Google Patents

Abstract

An epoxy resin composition comprising (A) an epoxy resin having at least two epoxy groups in its molecule, (B) an ether compound having a β-methylglycidyl group represented by formula (1), and (C) a curing agent.

Description

 Specification

 Epoxy resin composition

 Technical field

 The present invention relates to an epoxy resin composition suitable for embedding, casting, bonding, painting, laminating, and the like of electric and electronic components.

 Jujutsu

 If the epoxy resin composition is used by bonding, casting, impregnating, etc., lower the viscosity of the epoxy resin composition to remove bubbles (easily remove bubbles contained in uncured epoxy resin) Various diluents are used to improve the impregnation (easiness of flowing into the gap) and to improve the workability, and in a composition containing a large amount of inorganic filler. There are two types of diluents: non-reactive diluents and reactive diluents.Non-reactive diluents do not react with the base resin (epoxy resin), so the performance of the resulting cured product is greatly reduced. Therefore, reactive diluents are generally widely used.

 Reactive diluents include, for example, ethers containing a glycidyl group such as butyldaricidyl ether, arylglycidyl ether, ethylene glycol diglycidyl ether, phenyldaricidyl ether, octylene oxide, dodecenoxide, and the like. And the like, daricidylamines such as diglycidylaniline, carboxylic acid daricidyl esters such as diglycidyl dimer, etc., and these reactive diluents are used depending on the purpose. It is necessary to select a reactive diluent that has the same level of reactivity as the epoxy resin of the base resin.If the reactivity is significantly lower than that of the epoxy resin of the base resin, the reactive diluent remains one after curing. Part is not preferable in terms of residual properties.

Among the above reactive diluents, those having the highest dilution effect (effect of lowering the viscosity of the epoxy resin composition and improving impregnation) are aliphatic glycidyl ethers, for example, butyl alcohol and ebichlor. Butyldaricidyl ether obtained by reaction with hydrin; In addition, aromatic glycidyl ethers are used as reactive diluents to give cured products with excellent water resistance, heat resistance, and hardness. Examples include phenylglycidyl ether obtained by reaction with piclorhydrin.

 JP-A-59-159819 discloses a reaction of an epoxy resin with butyldaricidyl ether, arylglycidyl ether, phenyldaricidyl ether, glycidyl oleate, tertiary carboxylic acid dalicidyl ester, and the like. Epoxy resin compositions containing an acidic diluent are exemplified.

 Butyldaricidyl ether described in JP-A-59-159819 has an effect of lowering the viscosity of the epoxy resin composition without changing the physical properties of the epoxy resin composition by adding a small amount because of its small molecular weight. However, low molecular weight daricidyl ethers, such as butyl glycidyl ether, are highly volatile and this ether compound comes into contact with the skin as vapor when defoaming. There are many opportunities to do so. Generally, when an ether compound having a glycidyl group is used as a reactive diluent, it has a strong irritating property to the skin, which poses a serious problem in handling these epoxy resin compositions. I have. This is considered to be due not only to the molecular weight and the volatility of the ether compound having a daricidyl group, but also to the degree of irritation to the skin inherent to the daricidyl group.

 We searched for a reactive diluent that has a high effect of lowering the viscosity of the epoxy resin composition and does not have a significant skin irritation, without lowering the original curing performance of the epoxy resin as the main ingredient. As a result, reactive diluents using β-methyldaricidyl group-containing ether compounds obtained by reacting phenols or alcohols with β-methylepalipha genohydrin are similar to phenols or alcohols and ephi-ha-genohydrin. Glycidyl group-containing ether compound obtained by reacting with a diluent, less irritating to the skin than the diluent, and has the same viscosity-lowering effect and similar reactivity or physical properties of the cured product I found something.

The present invention uses the ether compound having a β-methyldaricidyl group as a reactive diluent, thereby lowering the viscosity without lowering the inherent performance of the epoxy resin as a base resin when the epoxy resin is cured, thereby improving handling properties. To improve and to the skin An object of the present invention is to provide an epoxy resin composition which is less irritating to the work environment and is good in working environment.

 Disclosure of the invention

 The present invention relates to the following component (A), component (B) and component (C);

 (A) an epoxy resin having at least two epoxy groups in the molecule,

 Equation (B) (1):

CH ₃

C—CH ₂ -Formula (1)

An ether compound having a β-methyldaricidyl group represented by

(C) An epoxy resin material comprising: a curing agent.

 The component (II) used in the present invention is an epoxy resin having at least two epoxy groups in a molecule. This epoxy resin is, for example, a bisphenol A epoxy resin or a bisphenol F epoxy resin obtained by a polymerization reaction of bisphenol and ephalogenohydrin such as bisphenol II, bisphenol F, and bisphenol S. Epoxy resins, bisphenol S-type epoxy resins, and epoxy resins obtained by polymerizing evihalogenohydrin with 4,4'-dihydroxybiphenyl, dihydroxynaphthalene, etc., and ephalogenohydrides on novolak resin polymers Novolak epoxy resin obtained by reacting phosphorus, and the like. These epoxy resins can be used alone or as a mixture of two or more.

 The component (B) used in the present invention is an ether compound having a β-methyldaricidyl group represented by the formula (1). This ether compound has the following formula (2), formula (3), formula (4) or formula (5);

Formula (2): Ar-OH (where Ar represents an aryl group),

^ Οί ^ -ΟΗ (however, R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms), Formula (4): HO-R ² -OH (where R ² represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms), or

Formula (5): HO- 〖CH (R ³ ) -CH ₂₀ ] _n -H (where R ³ represents a hydrogen atom, a methyl group or an ethyl group, and n represents a natural number of 1 or Ii2) A hydroxyl group-containing organic compound, formula (6):

CH ₃

CH ₂ — C— CH ₂ X formula (6)

 It is preferable that the compound be at least one selected from the group consisting of ether compounds obtained by reacting β-methylepiha mouth genohydrin represented by c with X (wherein X represents a halogen atom).

 The aryl group of the hydroxyl-containing organic compound of the formula (2) used for the synthesis of the component (II) includes a phenyl group, a naphthyl group, a biphenyl group and a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. It is preferably one kind of organic group selected from the group consisting of a phenyl group, a naphthyl group, and a biphenyl group. Then, by reacting these hydroxyl group-containing organic compounds with β-methyl methine genohydrin, aryl methyldaricidyl ether is obtained. Particularly, the hydroxyl group-containing organic compound of the formula (2) used for the synthesis of the component (II) is preferably phenol, cresol or butylphenol. Then, phenol, cresol, or butylphenol is reacted with β-methylepihalogenohydrin to obtain phenyl-β-methyldaricidyl ether, cresol-β-methyldaricidyl ether, or butylphenyl-β-methyldaricidyl ether.

Formula (7) obtained by reacting a hydroxyl group-containing organic compound represented by the above formula (2) with β-methylephalogenohydrin represented by the above formula (6) (where X represents a halogen atom) The aryl β-methyldaricidyl ether is shown below.

 OH

-HX I

Ar— O— CH ₂ -CH ₂ formula (7)

The above reaction is achieved by adding an alkaline aqueous solution such as an aqueous sodium hydroxide solution to Ar-OH and β-methylebihalogenohydrin. First, an adduct of Ar-OH and β-methylebihalogenohydrin is produced, followed by dehydrohalogenation to produce aryl 硫 -methyldaricidyl ether of the formula (7). The obtained product is washed with water and isolated by distillation or the like. In the above reaction, it is preferable that excess β-methylepihalogenohydrin is present relative to Ar—OH. For example, it is preferable to add 2 to 10 mol of p-methylepihalogenohydrin to 1 mol of (OH group) of Ar-OH. If the excess of β-methylebihalogenohydrin relative to Ar-OH is low, that is, if the above molar ratio is close to 1, the reaction rate and the reaction selectivity are low, which is not preferable. The above reaction is carried out at a temperature of 100 to 150 ° C. for 5 to 20 hours.

Reaction of the hydroxyl-containing organic compound of formula (3) used in the synthesis of component (B) with β-methylephalogenohydrin of formula (6) gives alkyl β-methyldaricidyl ether . In particular, the hydroxyl group-containing organic compound of the formula (3) used for the synthesis of the component (II) is preferably butanol or aryl alcohol. And butanol, and Is obtained by reacting β-methylephalogenohydrin with aryl alcohol to obtain butyl-β-methyldaricidyl ether or aryl-β-methyldaricidyl ether.

 The alkyl of the formula (8) obtained by reacting the hydroxyl group-containing organic compound represented by the above formula (3) with the dimethylhydrazine genohydrin represented by the above formula (6) (wherein X represents a halogen atom) β-methyldaricidyl ether is shown below.

CH ₃

^R '— ^OH + Who? ^C H ^H ₃ ^2X

R ¹ — 0— CH ₂ — C— CH ₂ X

 OH

-HX?

 R '-O— CH2-½ formula (8)

The above reaction is performed by adding boron trifluoride etherate (for example, boron trifluoride acetyl ether; BF ₃ ′ (C ₂ H ₅ ) 20) to Ri-OH and β-methylepihalogenohydrin. , R OH and an adduct of β-methylepihalogenohydrin are formed, and subsequently an aqueous solution of sodium hydroxide or the like is added to cause dehydrohalogenation, and the alkyl of formula (8) β-methyldaricidyl ether is produced. The obtained product is washed with water and isolated by distillation or the like. In the above reaction, it is preferable that excess ROH is present relative to β-methylepiha genohydrin. For example, add 4 to 20 moles of Ι ^ -ΟΗ (0Η group) to 1 mole of β-methylephalogenohydrin. Is preferred. If the excess of ROH (ΟΗ group) relative to β-methylepihalogenohydrin is low, that is, if the above molar ratio is close to 1, the reaction proceeds further and a polymer (resin) is obtained, which is not preferable. . The above reaction is carried out at a temperature of 10 to 50 ° C. for 6 to 20 hours.

 By reacting the hydroxyl group-containing organic compound of the formula (4) used for the synthesis of the component (B) with the β-methylepiha mouth genohydrin of the formula (6), an alkylenedaricolic di (β-methyldaricidyl) ether is obtained. In particular, the hydroxyl group-containing organic compound of the formula (4) used for the synthesis of the component (II) is preferably ethylene glycol, tetramethylene glycol, or hexamethylene glycol. Then, by reacting ethylene glycol, tetramethylendalicol, or hexamethylene glycol with β-methylepihalogenohydrin, ethylene glycol-diβ-methyldaricidyl ether, tetramethylenedaricol-diβ-methyldaricidyl ether Or hexamethylene dalicol-di β-methyldaricidyl ether is obtained.

 Formula (9) obtained by reacting a hydroxyl group-containing organic compound represented by the above formula (4) with β-methylepihalogenohydrin represented by the above formula (6) (where X represents a halogen atom) The alkylenedaricol di (β-methyldaricidyl) ether of ()) is shown below.

C Les H Π _{2 2} H ₂ Equation (9)

The ether compound of the formula (9) can be obtained in the same manner as the ether compound of the formula (8).

(II) The etheric compound of the formula (10) is obtained by reacting the hydroxyl-containing organic compound of the formula (5) used in the synthesis of the component with the β-methylepihalogenohydrin of the formula (6). can get. In particular, the hydroxyl group-containing organic compound of the formula (5) used for the synthesis of the component (II) is preferably ethylene glycol or propylene glycol. And diethylene glycol By recall or reaction of propylene glycol with β-methylepihalogenohydrin, diethylene glycol-diβ-methyldaricidyl ether or brovirendaricol-diβ-methyldaricidyl ether is obtained.

 Formula (10) obtained by reacting a hydroxyl group-containing organic compound represented by the above formula (5) with β-methylbihalogenohydrin represented by the above formula (6), wherein X represents a halogen atom. The ether compounds are shown below.

 Formula (10) The ether compound of the formula (10) is obtained in the same manner as the ether compound of the formula (8).

 The component (C) used in the present invention is a curing agent, and any substance can be used as long as it reacts with the epoxy group of the component (A) and the component (B). Alternatively, it is preferable to use amine.

 Examples of the above acid anhydride include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and tricarboxylic acid anhydride. Menlitic anhydride and the like can be mentioned, and these can be used alone or as a mixture of two or more.

 As the amine, primary and secondary amines can be used, and they can have a linear or cyclic structure.

Examples of these amines include isophorone diamine, ethylene diamine, diethylene triamine, triethylene tetramine, metaphenylenediamine, metaxylylenediamine, dicyandiamide and the like. The present invention has good impregnating properties by lowering the viscosity of the epoxy resin composition and improving the flowability without lowering the curability of the epoxy resin as the main agent or the physical properties of the cured product, An epoxy resin composition containing a reactive diluent having low skin irritation during handling can be obtained.

 The epoxy resin composition of the present invention is excellent in defoaming property, impregnation property, and skin irritation resistance, and its cured product has heat resistance, high bending strength value, water resistance, chemical resistance, and high hardness value. For this purpose, it can be used for embedding, casting, bonding, painting, laminating, etc. of electric and electronic components.

 BEST MODE FOR CARRYING OUT THE INVENTION

 In the eboxy resin composition of the present invention, the component (A) and the component (B) are in a weight ratio,

(A) :( B) force, preferably in a mixing ratio of '60: 40 to 95: 5.

 When the amount of the component (A) is higher than the above ratio, the viscosity does not sufficiently decrease, and when the amount of the component (A) is lower than the above ratio, the cross-linking density decreases and the heat resistance and mechanical properties of the cured product are reduced. It is not good because it drops.

 In the ethoxylated resin composition of the present invention, the component (C) may be mixed at a mixing ratio of 0.5 to 1.2 equivalents relative to 1 equivalent of the ethoxy group obtained by adding the components (A) and (B). It is good. In the above component (C), the primary amino group acts as 2 equivalents, the secondary amino group as 1 equivalent, the acid anhydride group as 1 equivalent, and the carboxyl group as 1 equivalent.

In the epoxy resin composition of the present invention, the viscosity of the composition extremely increases even when the inorganic filler is added as a filler because the component (C) acts as a reactive diluent. It maintains good workability and does not adversely affect the physical properties of the resulting cured product. By adding these inorganic fillers, the hardness and water resistance of the cured product can be increased, and the coefficient of linear expansion and the internal stress can be reduced. Examples of the filler include silica, titanium oxide, calcium carbonate, and the like. This filler can be added in an amount of 10 to 90% by weight, preferably 30 to 80% by weight in the above composition. The epoxy resin composition of the present invention comprises an imidazole, an imidazole derivative (for example, 2-ethyl-4-methylimidazole), tris (dimethylaminomethyl) phenol. By adding a curing accelerator such as benzyl or benzyl dimethylamine, curing can be performed efficiently. Further, a coloring agent or the like can be contained.

 In the epoxy resin composition of the present invention, the component (A), the component (B), and the component (C) can be mixed and adjusted in any order. Mixing of these components can be carried out using a device such as a mixing tank with stirring blades. The resulting composition can be stored stably at a temperature of 23'C for more than one month.

 The epoxy resin composition obtained by the present invention is degassed, coated on a substrate or filled in a mold, and then cured, for example, by heating at 100 ° C. for 2 hours and further at 150 ° C. for 3 hours. Can be obtained. This heating can be performed using a heating device such as an oven furnace.

Example

 (Synthesis of phenyl-β-methyldaricidyl ether)

 Heat 94 g (l mol) of phenol, 583.5 g (5 mol) of β-methyl-evic luchydrin and 5 g of tetramethylammonium chloride at 125-130 ° C for 10 hours, cool to 60 ° C, and reduce the pressure to 70 torr under reduced pressure. While maintaining the temperature at 60 ° C, a 50% aqueous solution of caustic soda

89 g (l.l mol) were added continuously over 2 hours. After washing with water, distillation was performed to obtain phenyl-β-methyldaricidyl ether. The epoxy equivalent was 164, which was in agreement with the theoretical value.

(Synthesis of cresol-β-methyldaricidyl ether)

 Cresol 108 g (1 mol), β-methylepic hydrhydrin 583.5 g (5 mol) and tetramethylammonium chloride 5 g were heated at 125 to 130 ° C for 10 hours, cooled to 60 ° C, and then reduced to 70 torr. While maintaining the temperature at 60 ° C., 89 g (ll mol) of a 50% strength aqueous sodium hydroxide solution was continuously added thereto over 2 hours. After washing with water, distillation was performed to obtain cresol-β-methyl glycidyl ether. The epoxy equivalent was 178, which was in agreement with the theoretical value.

(Synthesis of η-butyl-β-methylglycidyl ether)

296 g (4 mol) of η-butanol, 53.3 g (0.5 mol) of β-methylebichlorohydrin and 1.6 g of boron trifluoride ethyl ether [BF ₃ '(C2H ₅ ) 20] are stirred at 25 to 30'C for 10 hours. After stirring, the mixture was cooled to 50 ° C., and 120 g (1.5 mol) of a 50% aqueous solution of caustic soda was continuously added over 2 hours while maintaining the pressure at 50 under a reduced pressure of 70 torr. After washing, distill n Thus, -β-methyldaricidyl ether was obtained. The epoxy equivalent was 144, which matched the theoretical value.

 (Synthesis of aryl- リ ル methyldaricidyl ether)

232.4 g (4 mol) of allylic alcohol, 53.3 g (0.5 mol) of β-methylebichlorohydrin and 1.6 g of boron trifluoride ethyl ether [BF _3- (C2H ₅ ) ₂₀ ] at 25-30 ° C After stirring for 10 hours, cool to 50 ° C, and maintain the temperature at 50 ° C under a reduced pressure of 70 torr, continuously add 120 g (1.5 mol) of 50% caustic soda aqueous solution over 2 hours. I did it. After washing with water, distillation was performed to obtain aryl-β-methyldaricidyl ether. The epoxy equivalent was 128, which was in agreement with the theoretical value.

 (Synthesis of Ethylene Glycol-Di β-Methyldaricidyl Ether)

Ethylene glycol 31 g (0.5 mol),卩methyl E Pi chlorohydrin 106.5 g (1.0 molar) and boron trifluoride Echirueteru _{[BF3 '(C 2 H 5)} 20 ] was 0.4g in 65'C 4 h攙拌Thereafter, after cooling to 50 ° C., 120 g (1.5 mol) of a 50% aqueous solution of caustic soda was continuously added over 2 hours while maintaining the temperature at 50 ° C. under a reduced pressure of 70 torr. After dilution with 50 g of toluene and washing with water, toluene was distilled off to obtain ethylenedaricol-di-β-methyldaricidyl ether. The epoxy equivalent was 126.

(Synthesis of hexamethylene glycol-di β-methyldaricidyl ether)

 Hexamethylene glycol 59 g (0.5 mol), β-methylepiclorhydrin

106.5 g (1.0 mol) and boron trifluoride ethyl ether (BF ₃ '(C2H ₅ ) ₂₀ ) 0.4 g were stirred at 65 ° C for 4 hours, cooled to 50'C, and then reduced to 50 ° C under a reduced pressure of 70 torr. While maintaining C, 120 g (1.5 mol) of a 50% aqueous solution of caustic soda was continuously added over 2 hours. After diluting with 50 g of toluene and washing with water, toluene was distilled off to obtain hexamethylenedalicol-diβ-methylglycidyl ether. The epoxy equivalent was 164.

 The following raw materials were prepared.

A1: Bisphenol II type epoxy resin (manufactured by Yuka Seal Epoxy Co., Ltd., trade name: Epikote 828, molecular weight: about 355, epoxy equivalent: 189, viscosity at 25 ° C: 13000 mPa's) B1: phenyl-β-methyldaricidyl ether (epoxy (Equivalent is 164)

Β2: Cresol-β-methyldaricidyl ether (epoxy equivalent is 178) B3: n-butyl-β-methyldaricidyl ether (epoxy equivalent is 144)

 Β4: Aryl-β-methyldaricidyl ether (epoxy equivalent is 128)

 Β5: Ethylene glycol-di β-methyldaricidyl ether (epoxy equivalent is 126)

Β6: Hexamethylenedaricol-diβ-methyldaricidyl ether (epoxy equivalent is

164)

 Β7: phenyl-daricidyl ether (reagent, epoxy equivalent is 150)

 Β8: η-butyl-glycidyl ether (reagent, epoxy equivalent is 130)

 C1: Hexahydrophthalic anhydride (Shin Nippon Rika Co., Ltd., equivalent 154)

 C2: methylhexahydrophthalic anhydride (Shin Nippon Rika Co., Ltd., equivalent 168)

 C3: isophorone diamine (manufactured by Huls, active hydrogen equivalent 42.5)

 D1: Fused silica GR-90 (manufactured by Toshiba Chemical Corporation, average particle size is about ΙΟμπι)

 El: 2-ethyl-4-methylimidazole (reagent)

Example 1

 Bisphenol Α-type epoxy resin and phenyl-β-methyldaricidyl ether were mixed by visual mixing at room temperature at the weight ratio shown in Table 1 and dissolved to obtain an epoxy resin mixed solution. Table 3 shows the results of the evaluation of the viscosity and skin irritation of the obtained epoxy resin mixture. In Table 1, (-) means that the component is not contained.

Examples 2 to 6

 The components and weight ratios shown in Table 1 were adjusted in the same manner as in Example 1, and the obtained epoxy resin mixture was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 1

 Bisphenol Α type epoxy resin and phenyl-dalicidyl ether were stirred and mixed at room temperature at the weight ratio shown in Table 2 and dissolved to obtain an epoxy resin mixed solution. Table 4 shows the results of evaluation of the viscosity and skin irritation of the obtained epoxy resin mixture. In Table 2, (-) means that the component is not contained.

 Comparative Examples 2-3

The components and weight ratios shown in Table 2 were adjusted in the same manner as in Comparative Example 1, and the obtained epoxy resin solution was evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4. Table 1 (parts by weight) Example 1 2 3 4 5 6 Component \

 A 1 85 85 85 85 85 85

B 1 15 — one one one one

B 2 one 15 — one one one

B 3 1 1 15 — 1

B 4 — one one 15 — one

B 5 1 1 1 1 1 15 —

B 6 1 1 1 1 1 15

B 7 1 1 1 1 1 1 1

B 8 1 1 1 1 1 1 1

Table 2 (parts by weight)

 Comparative Example 2 3

 Ingredient \

 A 1 85 100 85

 B 1

 B 2

 B 3

 B 4

 B 5

 B 6

B 7 15 (Test 1: Viscosity measurement)

 It was measured using a Brookfield viscometer at a temperature of 25 ° C. The obtained viscosity value was expressed in mPa.s (millipascal second).

(Test 2: Evaluation of primary skin irritation)

 The evaluation was performed by the Draize method. 0.5 0.5 g of the epoxy resin mixture of Examples 1 to 6 and Comparative Examples 1 to 3 is applied to the shaved part of a heron, and the cloth is closed and adhered. Observation of skin changes immediately after removal of the patch pieces and at 24 hours and 72 hours after removal, judging the degree of redness and scab formation and the degree of edema, mild (redness and scabs hardly formed) Safety was classified into three groups: moderate (redness and scab formation) and severe (redness and scab formation).

(Test 3: Evaluation of skin irritation cumulative irritation)

 The test substance solution of the epoxy resin mixture of Examples 1 to 6 and Comparative Examples 1 to 3 was injected intradermally into the shaved part of a pig (guiea pigs) three times a week every other day for a total of eight times. . In addition, three weeks later, intradermal injections were similarly performed three times a week every other day for a total of eight times. The number of injections was 16 in total. In the ninth and subsequent injections, observe the changes in the skin at 24 and 48 hours after the injection to determine the degree of erythema and crusting, edema, and damage. The results of the judgment were digitized to 1-3. 1 is the one that has little change from the initial state, 2 is the one that has changed from the initial state, and 3 is the one that has a high change from the initial state.

Table 3

 Example 1 2 3 4 5 6

 Ι ^ Νο \

 Release 1 1500 1550 410 450 1800 2300

 Fiber 2 mi Id mi Id mi Id mi id mi ld mi Id

3 1 1 1 1 1 1 Table 4

 Comparative Example 1 2 3

1300 13000 360

 2 moderate mi Id moderate

 3 3 1 3

Example 7

 An epoxy resin mixture consisting of bisphenol A-type epoxy resin and phenyl-β-methyldaricidyl ether is listed in Table 5 with hexahydrophthalic anhydride as a curing agent and GR-90 as a filler. The mixture was added in a weight ratio and stirred vigorously at room temperature for 1 hour to obtain an epoxy resin composition. Using the obtained epoxy resin, viscosity measurement and impregnation test were performed. Further, 2-ethyl-4-methylimidazole as a curing accelerator was added at the weight ratio shown in Table 5, and after degassing, casting was performed at 100 ° C for 2 hours, and then at 150 ° C for 3 hours. And cured. Furthermore, the cured product obtained by curing the epoxy resin composition was subjected to a heat resistance test, a bending strength test, a water absorption measurement, a pencil hardness, and a chemical resistance test. The epoxy groups and the acid anhydride in the cured product of the epoxy resin composition were quantified in order to examine the reactivity between the epoxy group in the epoxy resin composition and the hardener. In Table 5, (-) means that the component is not contained.

Examples 8 to 21

 An epoxy resin composition was prepared in the same manner as in Example 7 using the components and weight ratios shown in Table 5, and after the obtained epoxy resin composition was degassed, it was cast at 100 ° C for 2 hours. Thereafter, it was further cured by heating at 150 ° C for 3 hours. The same evaluation test as that of Example 7 was performed on the obtained epoxy resin composition and the cured product thereof.

Comparative Example 4 An epoxy resin mixture consisting of bisphenol A-type epoxy resin and phenyl-daricidyl ether, hexahydrophthalic anhydride as a curing agent, and molten silica GR-90 as a filler are listed in Table 6. The mixture was added by weight and vigorously stirred at room temperature for 1 hour to obtain an epoxy resin material. Using the obtained epoxy resin composition, viscosity measurement and impregnation test were performed. Furthermore, 2-ethyl-4-methylimidazole was added as a curing accelerator at the weight ratio shown in Table 6, and after degassing, casting was performed at 100'C for 2 hours, and then at 150 ° C for 3 hours. It was cured by heating. Furthermore, the cured product obtained by curing the epoxy resin composition was subjected to a heat resistance test, a bending strength test, a water absorption measurement, a pencil hardness, and a chemical resistance test. Then, in order to examine the reactivity between the epoxy group in the epoxy resin composition and the curing agent, the epoxy group and the acid anhydride in the cured product of the epoxy resin composition were quantified. In Table 6, (-) means that the component is not contained.

Comparative Example 5: 12

An epoxy resin composition was prepared in the same manner as in Comparative Example 4 using the components and weight ratios shown in Table 6 and the obtained epoxy resin ffi ^ was degassed, cast, and then cast at 100 ° C for 2 hours. Thereafter, heating was further performed at 150'C for 3 hours to cure. An evaluation test similar to that of Comparative Example 4 was performed on the obtained epoxy resin product and its cured product.

Table 5 (parts by weight) Example 7 8 9 10 11 12 13 14 Component \

 A 1 85 85 85 85 85 85 85 85 B 1 15-15-15---B 2-15-15-15--B 3------15 15 B 4

B 5

B 6

B 7

B 8

C 1 83 83 — one — one 85 — C 2 — one 93 91 — — — 91 C 3 one one — one 23 23 — one D 1 183 182 193 191 53 53 185 191 E 1 2 2 2 2--2 2

Continuation of Table 5 (parts by weight) Example 15 16】 7 18 19 20 21 Component \

 A 1 85 85 85 85 85 85 85 B 1

B 2

B 3 15

B 4 1 15 15 — — B 5 15 1 1 15 — B 6 1 15 1 1 15 B 7

B 8

C 1

C 2 1 96% 91 — 1 C 3 23 1 25 25 24 D 1 53 196 196 191 53 53 53 E 1 1 2 2 2

Table 6 (parts by weight)

 Comparative Example 4 5 6 7 8 9 10 11 12 Component \

 A 1 85 100 85 100 85 100 85 85 85 B 1

B 2

B 3

B 4

B 5

B 6

B 7 15-15-15---B 8------15 15 15 C 1 85 82----87 — one C 2 — — 95 89 — — one 92-C 3 — one one 23 23 — — 23 D 1 185 182 195 189 53 53 187 192 53 E 1 2 2 2 2 — 1 2 2 —

(Test 4: Impregnation test 1)

 In the above epoxy resin composition using an acid anhydride as a curing agent, the above epoxy resin composition is drop-coated on a substrate on which the chip is mounted, and heated at 100 ° C for 1 hour and further heated at 150'C for 2 hours. And cured. The coating surface and the cured product were cut, and the internal voids (voids) were visually observed to evaluate the impregnation property and the coating smoothness. If there is no void on the surface or inside (〇), if there is even a small amount of void (△), if there is a void, it is indicated by (X).

(Test 5: Impregnation test 2)

 In the above epoxy resin composition using an amine as a curing agent, apply the epoxy resin composition between two degreased and polished steel plates, and while pressing, cure at 100 ° C for 1 hour and then at 150 ° C for 2 hours. did. The cured product was cut and the internal voids and adhesion were observed, and the impregnation and wettability were visually observed. If there is no void inside and it is in close contact with the substrate (〇), void voids inside are slightly voids and the area of adhesion to the substrate is reduced by the void (か な り). (X) indicates the presence of a void and insufficient bonding to the substrate due to the void.

(Test 6: Heat resistance test)

 The heat resistance was evaluated by measuring the glass transition temperature (Tg).

 The above epoxy resin composition was cast, heated at 100 ° C for 2 hours, and further heated at 150 ° C for 3 hours, and a 50 mm X 4 mm X 3 mm sample was cut from the cured product with a diamond cutter. The viscoelastic spectrum from room temperature to 200 ° C was measured in a bending mode with a viscoelastic spectrometer manufactured by Seiko Electronic Industry Co., Ltd., and the glass transition temperature of the cured product of each epoxy resin composition ( Tg) ° C was determined.

(Test 7: Flexural strength measurement)

The bending strength was measured based on JIS-K6911. The epoxy resin composition was cast and heated at 100 ° C. for 2 hours, and then further heated at 150 ° C. for 3 hours, and cured to obtain a test piece from the cured product. The height and width of the test piece were measured with a micrometer, both ends of the test piece were supported by fulcrums, a load was applied to the center, the load when the test piece was broken was measured, and the bending strength was measured. Bending strength a _ffi (kgfymm ² ) is given by o _ffl = 3PL _V / 2Wh ² Can be calculated. However, P is a load when broken test piece (kgf), L _V is distance between fulcrums (mm), the width of the W test piece (mm), the height of h the test piece (mm).

(Test 8: Flexural modulus measurement)

Flexural modulus was measured based on JIS ^ K6911. The epoxy resin composition was cast and heated at 100 ° C. for 2 hours and then at 150 ° C. for 3 hours to prepare a test piece from the cured product obtained by curing. The height and width of the test piece were measured with a micrometer, both ends of the test piece were supported by fulcrums, a load was applied to the center, the load and deflection were read, and the re-bending modulus was measured. Flexural modulus E kgf / mm ²⁾ _{is, E f = L V "/} 4Wh 3 -F / Y by it you to calculate. However, L _V is distance between fulcrums (mm), W is the width of the test piece (mm), h is the height (mm) of the test piece, and F / Y is the slope (kgf / mm) of the linear part of the load-deflection curve (Test 9: Water absorption measurement)

Water absorption was measured based on JIS-K6911. The above epoxy resin material was cast and heated at 100 ° C for 2 hours and then at 150 ° C for 3 hours, and a test piece was prepared from the cured product obtained by stiffening. The 50 mm square test piece was dried in a thermostat kept at 50 ° C. for 24 hours. The test piece after the drying treatment was cooled to 20'C in a desiccator, and the weight was accurately measured. Next, it was immersed for 24 hours in a water container filled with distilled water at 23 ° C, taken out, wiped with dry gauze, and weighed after absorbing water within 1 minute. The water absorption A (%) can be calculated by A = (W ₂ -Wi) Wrl00. However, the weight of the intake water before the test piece (g), the weight of W ₂ are after water absorption test piece (g).

(Test 10: Determination of epoxy group)

The above epoxy resin composition was cast and heated at 100 ° C. for 2 hours, and then further heated at 150 ° C. for 3 hours to form a test piece from the cured product obtained by curing. After pulverizing the obtained cured product to about ΙΟμπι, take it into a titration solution with a weight ratio of (tetraethylammonium bromide): (acetone): (acetic acid) = 7:50:50, and ultrasonic for 20 minutes. The test piece was swollen into the titration solution by a washing device. Thereafter, potentiometric titration was performed with a 0.1N-HClO ₄ / CH ₃ COOH solution, and the reaction rate (%) of the epoxy group in the epoxy resin composition at the time of curing was measured. The amount of the amine catalyst used was corrected.

(Test 11: Determination of acid anhydride) With respect to the epoxy resin composition using an acid anhydride as a hardener, the reaction rate of the curing agent was quantified. A test piece was prepared from the cured product obtained by casting the epoxy resin composition and heating it for 10 hours (TC for 2 hours, and then further at 150'C for 3 hours.) After crushing to about ΙΟμπι, take it into a titration solution of (acetone) :( pure water) = 1: 1 and perform potentiometric titration with O.lN-NaOH aqueous solution to obtain acid anhydride in the epoxy resin composition at the time of curing. The reaction rate (%) of the product (curing agent) was measured, and the analytical value was quantified as an acid.

In Tables 7 and 8 below, (-) means that measurement was not performed.

Table 7

 Example 7 8 9 10 11 12 13 14 Trial. ,

Test 1 3170 3190 2100 2130 700 760 1950 1310 Test 4 〇 〇 〇 〇 〇 〇 Test 5 〇 〇

Test 6 126 134 128 130 128 131 128 129 Test 7 15 15 15 14 15 15 15 14 Test 8 280 290 270 270 290 295 260 250 Test 9 0.13 0.18 0.14 0.12 0.13 0.11 0.15 0.15 Exam 10 99 99 99 99

Exam 11 99 99 99 99

Table 7 continued

 Example 15 16 17 18 19 20 21

Trial translation. ,

Exam 1 560 1500 2300 2800 570 800 850

 4 1 〇 〇 〇

 5 o---〇 〇 〇

Exam 6 121 130 135 134 122 127 130

Exam 7 15 15 14 15 14 14 15

 8 280 260 255 245 280 285 275

Difficult 9 L 15 0.16 0.15

1 * ^ 10

Exam 11

Table 8

 Comparative Example 4 10 11 12 No \

Test 1 3230 7600 2180 6100 600 7200 1890 1150 560 Test 4 〇 X 〇 X 〇 〇 Test 5 〇 X 〇 Fiber 6) 33 156 134 134 155 130 164 133 133 126 126 7 15 15 15 14 15 14 15 14 14 8 250 250 260 250 230 295 260 250 290 .9 0.15 0.18 0.16 0.19 0.13 0.17 0.16 0.17 0.14 Test 10 99 98 99 98--Test 11 99 98 99 98 — one As can be seen from the above results, the bisphenol A-type epoxy resin as the base material has a high viscosity and impregnation is not sufficient, but by using a reactive diluent, the impregnation without impairing the physical properties of the cured product is improved. Can be improved.

 By adding a small amount of a low molecular weight reactive diluent, the viscosity is reduced and the impregnation is improved without impairing the physical properties of the cured product. However, since these low-molecular-weight reactive diluents have high volatility, when handling epoxy resin compositions containing them, the low-molecular-weight reactive diluent is generated as vapor. Among these low-molecular-weight reactive diluents, ether compounds having a daricidyl group are not preferred because they have strong irritation to the skin, while ether compounds having a β-methyldaricidyl group are irritating to the skin. Sex was found to be low.

Claims

The scope of the claims 1. The following components (A), (B) and (C);  (A) an epoxy resin having at least two epoxy groups in the molecule,  Equation (B) (1): CH ₃ CH ₂ — C— CH ₂ ~ formula. )  O An ether compound having a β-methyldaricidyl group represented by (C) an epoxy resin composition comprising: a curing agent.  2. The ether compound having a β-methyldaricidyl group of the component (Β) is represented by the following formula (2), (3), (4) or (5); Formula (2): Ar-OH (where Ar represents an aryl group), Formula (^ Ι ^ -ΟΗ (R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms), Formula (4): HO-R ² -OH (where R ² is 1-20 saturated or unsaturated hydrocarbon groups), or Formula (5): HO- (CH (R ³ ) -CH ₂₀ ) _n -H (where R ³ is a hydrogen atom, a methyl group or an ethyl group, n is 1 or (indicating a natural number of i2)) A hydroxyl group-containing organic compound represented by the formula (6): CH ₃ CH ₂ — C—— CH ₂ X formula (6)  ゝ 2. The epoxy according to claim 1, which is at least one member selected from the group consisting of ether compounds obtained by reacting with β-methyl phenol genohydrin represented by the formula (where X represents a halogen atom). Resin composition. 3. The aryl group of the hydroxyl-containing organic compound of the formula (2) used for the synthesis of the component (B) is a phenyl group, a naphthyl group, a biphenyl group, or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. 3. The epoxy resin composition according to claim 2, wherein the epoxy resin composition is one kind of organic group selected from the group consisting of a phenyl group, a naphthyl group, and a biphenyl group.  4. The epoxy resin composition according to claim 2, wherein the hydroxyl-containing organic compound of the formula (2) used for the synthesis of the component (B) is phenol, cresol, or butylphenol.  5. The epoxy resin composition according to claim 2, wherein the hydroxyl-containing organic compound of the formula (3) used in the synthesis of the component (B) is butanol or aryl alcohol. object.  6. The method according to claim 2, wherein the hydroxyl-containing organic compound of the formula (4) used for the synthesis of the component (B) is ethylene glycol, tetramethylene glycol, or hexamethylene glycol. Item 14. The epoxy resin composition according to Item.  7. The epoxy resin according to any one of claims 2 to 6, wherein the hydroxyl-containing organic compound of the formula (5) used in the synthesis of the component (B) is diethylene daricol or propylene daricol. Composition.