JPH0459818A - Production of epoxy resin and epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin useful as semiconductor sealing material, etc., providing a cured material having excellent heat resistance, water resistance and toughness, etc., by reacting a specific phenol compound with epichlorohydrin. CONSTITUTION:(A) A di[bis(hydroxy-alkyl-phenyl)alkyllethane as a phenol compound is made to react with (B) epichlorohydrin to give the objective resin. A compound shown by the formula (R1 to R16 are H or 1-3C alkyl and at least one of R1 to R3 is 1-3C alkyl; R17 and R18 are 1-5C alkyl) is preferably used as the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an epoxy resin and an epoxy resin composition.

[Conventional technology]

As an epoxy resin that provides a cured product with heat resistance,
Japanese Unexamined Patent Publication No. 64-70524 has 1. 1. 5゜5
-tetrakis(glycidyloxyphenyl)pentane is described.

[Problem to be solved by the invention]

However, the above-mentioned 1, 1. 5. The cured product of 5-tetrakis(glycidyloxyphenyl)pentane had insufficient heat resistance.

[Means to solve the problem]

In view of the current situation, the present inventors conducted intensive research and found that monovalent alkylphenol compounds and 1. 2-
Epoxy made from di[bis(hydroxy-alkyl-phenyl)alkyl]ethane, which has four aromatic rings and four phenolic hydroxyl groups in one molecule, obtained by dehydration condensation reaction with sialic acid. The cured resin material is 1°1, 5. The present inventors have discovered that 5-tetrakis(glycidyloxyphenyl)pentane has even better heat resistance than that of pentane, and have completed the present invention.

That is, the present invention relates to a method for producing an epoxy resin in which a phenol compound is reacted with epichlorohydrin, which is characterized in that di[bis(hydroxy-alkyl-phenyl)alkyl]ethane is used as the phenol compound; An epoxy resin composition comprising an epoxy resin and a curing agent, characterized in that di[bis(glycidyloxy-alkyl-phenyl)alkyl]ethane is used as the epoxy resin. It is.

Examples of the di[bis(glycidyloxy-alkyl-phenyl)alkyl]ethane used in the present invention include epoxy resins represented by the following general formula (f).

(However, in the formula, RI"' Rl@ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and at least one of R, "-R,
In the alkyl group of ~3, RI and ~R0 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, which may be the same or different. ) The compound represented by the above general formula (ri) is, for example, a compound represented by the general formula (
I) (However, in the formula, R3 to R0 are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, which may be the same or different, and R
+% R, at least one of which has 1 to 3 carbon atoms
In the alkyl group, R3, to RIM are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be the same or different. ) It can be obtained by reacting di[bis(hydroxyalkylphenyl)alkyl]ethane represented by as one raw material with epichlorohydrin.

The di[bis(hydroxyalkylphenyl)alkyl]ethane represented by the general formula (I) is not particularly limited, and for example, 1°2-di[2,2-bis(3-methyl-4- hydroxyphenyl)ethyl]ethane, 1,2-di[2°2-bis(3-ethyl-4-hydroxyphenyl)ethyl]ethane, 1. 2-di[2,
2-bis(3-phthyl-4-hydroxyphenyl)ethyl]ethane, 1. Examples include 2-di[2,2-bis(3,5-dimethyl-4-hydroxyphenyl)ethyl]ethane. These can be used alone or in combination of two or more.

The method for producing the di[bis(hydroxy-alkyl-phenyl)alkyl]ethane is not particularly limited, but for example, 1. in the presence of an acidic catalyst. 2-Sialkaic ethane 1
4 to 1 monovalent alkylphenol compound per mole
00 moles, preferably 5 to 20 moles, 20 to 7
It is carried out by stirring at a temperature of 0°C for 5 hours to 1 week, and after the reaction is completed, the catalyst is removed or the reaction is neutralized with a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and calcium hydroxide. After the addition, water and excess monohydric alkylphenol compound are removed under reduced pressure to obtain the crude product. Any conventionally known general method can be used to remove water and excess m phenol compounds, such as washing with a solvent, distillation by residence, etc. The solid di[bis(hydroxy-alkyl-phenyl)alkyl]ethane crude product thus obtained is pulverized, the compound is recrystallized using a solvent, and purified by heating and drying to obtain a highly pure di[bis(hydroxy-alkyl-phenyl)alkyl]ethane. Monohydric phenol compounds that can be used to produce O di[bis(hydroxy-alkyl-phenyl)alkyl]ethane from which bis(hydroxyalkyl-phenyl)alkyl]ethane can be obtained are particularly limited. Rather than, for example,
Examples include orthocresol, metacresol, bovine sirenol, and propylphenol. These can be used alone or in combination of two or more, and phenol can also be used in combination.

1.2-sialic ethane is not particularly limited, and examples include acetonyl acetone, 1,
4-butanedione, 3,6-octanedione, 4,7-
Examples include dozocandione. These can be used alone or in combination of two or more.

As the catalyst used in the reaction, acid catalysts such as formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid, salicylic acid, benzoic acid, oxalic acid, p-toluenesulfonic acid, hydrogen chloride, hydrogen bromide, etc. can be used. . The amount of these catalysts used is the same number of moles as the number of moles of acetonyl acetone, preferably 8 times or more. Although the catalyst may be used in large excess, it may require time for post-processes such as purification, so it may be determined at the appropriate time.

Furthermore, 1. In order to selectively react the two carbonyl groups of 2-sialkaic ethane with the para-position of the hydroxyl group of the monohydric phenol compound, β-mercaptopropionic acid, 3-pyridinemethanethiol, thio Organic thiol compounds such as ethanolamine are 1.2-
0.05 to 0 per mole of sialic ethane
．． It is preferable to use them together in a ratio of 2 moles.

Note that this dehydration condensation reaction does not require a particular solvent; inert solvents such as benzene, toluene, xylene, chloroform, and tetrahydrofuran can also be used.

The epoxy resin used in the present invention is easily obtained by reacting the above di[bis(hydroxy-alkyl-phenyl)alkyl]ethane with epichlorohydrin.

The reaction conditions in this case are the same as those for conventional production of epoxy resins, and are not particularly limited.

Example □Eva, 1.4 to 20 mol of epichlorohydrin is added to 1 mol of the hydroxyl group of the above Si[bis(hydroxy-alkyl-phenyl)alkyl]ethane, and 2 to 7 mol of epichlorohydrin is added at 20 to 120°C in the presence of a base. It can be easily produced by performing a time epoxidation reaction.

The base used in epoxidation is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, etc. Among them, potassium hydroxide or sodium hydroxide is preferred.

By adjusting the excess ratio of the number of moles of epichlorohydrin to the number of moles of hydroxyl groups in the above-mentioned cy[bis(hydroxy-alkyl-phenyl)alkyl]ethane, the production ratio of monomers and multimers can be changed. The molecular weight, epoxy equivalent, and softening point of the epoxy resin can be adjusted.

Reducing the molar excess of epichlorohydrin will increase the molecular weight of the epoxy resin; conversely, increasing it will result in a lower molecular weight (
Become. As the molecular weight increases, the epoxy equivalent and softening point also increase (
However, for boat fishing, if the molar excess of epichlorohydrin exceeds 10 times, the molecular weight, epoxy equivalent, and softening point will not change much. Therefore, it is not preferable from an economic point of view to use more epichlorohydrin than necessary.

In preparing the epoxy resin composition of the present invention,
First, the above di[bis(hydroxy-alkyl-phenyl)
Using an epoxy resin prepared by reacting epichlorohydrin with [alkyl]ethane, a curing agent, and, if necessary, a curing accelerator, these components may be blended and mixed according to a conventional method.

The epoxy resin (π) according to the present invention can be used alone or in combination with known and commonly used epoxy resins, if necessary.

As the curing agent that can be used in the present invention, any compound that is normally used as a curing agent for this type of epoxy resin can be used, but for example, various novolak resins, diethylene triamine, triamine Various aliphatic amines such as ethylenetetramine; Alicyclic amines such as bis(3-methyl-4-aminocyclohexyl)methane; Various aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; polyamide resins or various modified products thereof; various acids such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, benzophenonetetracarboxylic dianhydride, pyromelli nodoic anhydride Examples include anhydrides and various latent curing agents such as dicyandiamide, imidazole, BF2-amine complexes, and various guanidine derivatives.

The amount of curing agent used depends on the number of epoxy groups contained in one molecule of the epoxy resin, the number of amino groups, imino groups, active hydrogen groups such as phenolic hydroxyl groups, or the number of acid anhydride groups in the curing agent. The amount is generally close to equivalent.

Furthermore, when using the various compounds listed above as a curing agent, a curing accelerator may also be used in combination, if necessary. Examples of curing accelerators include various tertiary amines such as dimethylbenzylamine; various imidazoles such as 2-methylimidazole; or various organometallic compounds such as amine metal salts: 1,3,5-trihydroxy. Examples include polyhydric phenols such as benzene, and any known and commonly used curing accelerator can be used.

The epoxy resin composition of the present invention thus obtained further contains fillers, colorants, flame retardants, mold release agents,
Alternatively, various well-known and commonly used additive components such as coupling agents can also be blended as appropriate.

Among them, such fillers include silicas, zircon silicate, alum, mina, calcium carbonate, quartz powder, zircon oxide, talc, barium clay sulfate, asbestos powder, and milled glass, and colorants include Examples of mold release agents include stearic acid, stearic acid metal salts, natural waxes or synthetic waxes, and flame retardants include antimony dioxide or
Examples of the coupling agent include hexabromobenzene, and examples of the coupling agent include acrylic silanes, aminosilanes, and epoxysilanes.

The epoxy resin composition of the present invention provides a cured product with excellent heat resistance, water resistance, toughness, etc., and therefore is used in electrical insulating materials such as semiconductor encapsulation materials, paint insulation panels, laminates, and insulating powder coatings that require these properties. , laminates and prepregs for printed wiring boards, conductive adhesives and adhesives for structural materials such as honeycomb panels, molding materials for electrical parts other than semiconductors, GFRP 5CFRP and its prepregs, resist inks, etc. Available.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 Preparation of di[bis(hydroxy-alkyl-phenyl)alkyl]ethane 114 g (1 mol) of acetonyl acetone was dissolved in 2160 g (20 mol) of 0-cresol, and 15 ml of β-mercaptopropionic acid was dissolved at room temperature. added. After that, about 20 mol of hydrogen chloride gas was bubbled over 2 hours, and 25
The reaction was carried out by stirring at ℃ for 7 days. After the reaction was completed, the reaction solution was distilled under reduced pressure to remove phenol, and the reaction product was washed with hot water and filtered to obtain 1,2-di[2,2,-bis(3-methyl-4-hydroxyphenyl). ) Ethyl]ethane 434 g of crude product (a) was obtained.

Reference Example 2: 481 g of product (b) was obtained by carrying out the same operation as in Reference Example 1, except that 2,440 g of 2,6-xylenol was used instead of 2,160 g of 0-cresol.

Example 1 [Production of epoxy resin] 510 g of 1,2-di[2,2-bis(3-methyl-4-hydroxyphenyl)ethyl]ethane obtained in Reference Example 1 was dissolved in 1110 g of epichlorohydrin and stirred. 880 g of 20% aqueous sodium hydroxide solution at 80°C
was added dropwise over a period of 5 hours, and the reaction was continued by maintaining the same temperature for 1 hour. After discarding the aqueous layer, methyl isobutyl Add 1470 g of ketone (hereinafter referred to as MIBK) and dissolve it uniformly, then
Add 370 g of water to perform water washing, perform oil-water separation, remove water from the oil layer by azeotropic distillation, filter, and further MIB.
By distilling off K, a solid 1 with an epoxy equivalent of 193 is produced.
．． 695 g of 2-di[2,2-bis(3-methyl-4-glycidyloxyphenyl)ethyl]ethane was obtained.

Example 2 (same as above) 1,2-di[2,2-di[2,2-bis(3-methyl-4-hydroxyphenyl)ethyl]ethane obtained in Reference Example 2 was used instead of 1,2-di[2,2-bis(3-methyl-4-hydroxyphenyl)ethyl]ethane. Bis(3゜5-dimethyl-4
A solid 1,2-di[2,2-bis(3,5
-dimethyl-4-glycidyloxyphenyl)ethyl]
750 g of ethane was obtained.

Example 3 (same as above) In place of 1110 g of epichlorohydrin in Example 1, 5
670 g of a solid epoxy resin with an epoxy equivalent of 212 was prepared in the same manner except that 55 g was used.
I got it.

Example 4 The epoxy equivalent was 181 in the same manner as in Example 1, except that 454 g of 1,2-di[2,2-bis(3-methyl-4-hydroxyphenyl)ethyl]ethane was used. 640 g of solid target resin was obtained.

Comparative Example 1 1, 1. 5. 440 g of 5-tetrakis(4-hydroxyphenyl)pentane was dissolved in 1665 g of epichlorohydrin, and 880 g of a 20% aqueous sodium hydroxide solution was added dropwise at 80° C. over 5 hours with stirring, and then kept at the same temperature for 1 hour. After holding and allowing the reaction to continue and discarding the aqueous layer, 1500 g of methyl isobutyl ketone (hereinafter referred to as MIBK) was added to the reaction product obtained by distilling and recovering excess epichlorohydrin and uniformly dissolved. Thereafter, 800 g of water was added to wash with water, oil and water were separated, water was removed from the oil layer by azeotropic distillation, filtered, and MIBK was distilled off to obtain a solid 1. 1. 5゜62 of 5-tetrakis(4-glycidyloxyphenyl)pentane
5g was obtained.

Examples 5 to 7 and Comparative Example 2 The epoxy resins obtained in Examples 1 to 4 and the epoxy resins of Comparative Example 1 were used as epoxy resins, and as a curing agent, Epiclon B-570 (Dainippon Ink Co., Ltd.) was used. Methyltetrahydrophthalic anhydride (manufactured by Kagaku Kogyo Co., Ltd.), dimethylbenzylamine was used as a curing accelerator, and one of the epoxy groups in the epoxy resin was
Each component was blended at the composition ratio shown in Table 1 in such a ratio that the curing agent contained one acid anhydride group per epoxy resin of the present invention and the control. A resin composition was obtained.

Each epoxy resin composition was heated at 100°C for 2 hours, then at 160°C for 2 hours, and then at 180°C.
Test specimens were prepared by curing them separately for 2 hours at ) Bending strength, tensile strength, and tensile elongation were evaluated and measured. The results are shown in Table 1.

Examples 8 to 1O and Comparative Example 3 The epoxy resins obtained in Examples 1 to 4 and the epoxy resins obtained in Comparative Example 1 were used as the epoxy resins, and Barcum TD-213 was used as the curing agent.
1 (phenol/novolac resin manufactured by Dainippon Ink and Chemicals Co., Ltd.; softening point = 80°C)], dimethylbenzylamine was used as a curing accelerator, and the curing agent was added to each epoxy group in the epoxy resin. Each of these components is separately blended in the proportions shown in Table 2 so that there is one phenolic hydroxyl group in the mixture.
Epoxy resin compositions for the present invention and a control were obtained.

Each epoxy resin composition was cured at 80° C. for 5 hours and then at 160° C. for 4 hours to prepare test pieces.

Thereafter, various performances were evaluated and measured in the same manner as in the above Examples and Comparative Examples, and the results shown in Table 2 were obtained.

As is clear from each table, it is known that the cured product of the epoxy resin composition of the present invention has excellent heat resistance.

〔Effect of the invention〕

A cured product of an epoxy resin composition using an epoxy resin obtained by the production method of the present invention has an advantage of superior heat resistance compared to conventional products.

Therefore, the epoxy composition of the present invention is particularly useful for molding materials, casting materials, jigs and tools, laminated materials, electrical insulating materials, paints, civil engineering materials, etc., including sealing materials for various electric circuits such as semiconductor integrated circuits. It can be used in a wide range of fields such as building materials, adhesives or composites.

Claims (1)

[Claims] 1. A method for producing an epoxy resin by reacting a phenol compound with epichlorohydrin, characterized in that di[bis(hydroxy-alkyl-phenyl)alkyl]ethane is used as the phenol compound. Production method. 2. In the method for producing epoxy resin by reacting epichlorohydrin with a phenol compound, the above phenol compound has the general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (However, R_1 to R_1_6 in the formula may be the same) Hydrogen atoms or alkyl groups having 1 to 3 carbon atoms which may be different, and at least one of R_1 to R_1_6 is an alkyl group having 1 to 3 carbon atoms, and R_1_7 to R_1_8 are hydrogen atoms which may be the same or different. Atom or number of carbon atoms 1~
5 is an alkyl group. ) A method for producing an epoxy resin, characterized by using a phenol compound represented by: 3. In an epoxy resin composition composed of an epoxy resin and a curing agent, the epoxy resin is di[bis(glycidyloxy-alkyl-phenyl)alkyl]
An epoxy resin composition characterized by using ethane. 4. Di[bis(glycidyloxy-alkyl-phenyl)alkyl]ethane has the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, in the formula, R_1 to R_1_6 may be the same or different. a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and at least one of R_1 to R_1_6 is an alkyl group having 1 to 3 carbon atoms, and R_1_7 to R_1_8 may be the same or different; or an alkyl group having 1 to 5 carbon atoms.) The composition according to claim 3, which is a compound represented by the following formula. 5. The composition according to claim 3, wherein the di[bis(glycidyloxy-alkyl-phenyl)alkyl]ethane is an epoxy resin prepared by reacting di[bis(hydroxy-alkyl-phenyl)alkyl]ethane with epichlorohydrin. 6. Di[bis(glycidyloxy-alkyl-phenyl)alkyl]ethane is 1,2-di[2,2-bis(3
-Methyl-4-glycidyloxyphenyl)ethyl]ethane. 7. Di[bis(hydroxyalkylphenyl)alkyl]ethane has the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R_1 to R_1_6 are hydrogen atoms that may be the same or different. or an alkyl group having 1 to 3 carbon atoms, and at least one of R_1 to R_1_6 is an alkyl group having 1 to 3 carbon atoms, and R_1_7 to R_1_8 may be the same or different, or a hydrogen atom having 1 carbon atom 5. The composition according to claim 4, which is a compound represented by the following formula. 8. Di[bis(hydroxyalkylphenyl)alkyl]ethane is 1,2-di[2,2-bis(3-methyl-4
-Hydroxyphenyl)ethyl]ethane Claim 5
Compositions as described.