JPH02255667A - New epoxy resin and new epoxy resin composition - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R1 to R8 are H, 1-3C alkyl or halogen; Y is a group of formula II (R9 to R16 are H, 1-3C alkyl or halogen); n is 0-3]. USE:Useful for an adhesive, coating, laminating material, molding material, casting material, etc. Cured products have both good toughness and heat resistance. PREPARATION:4,4'-Diaminobenzophenone compound of formula III is epoxidized with epichlorohydrin in the presence of a base at 20-120 deg.C, followed by removing the water layer and by distilling off the excess epichlorohydrin. The reaction product is dissolved in an organic solvent and washed with water and the oil layer is taken out. The oil layer is dehydrated by an azeotropic distillation method, filtered and subjected to the distillation of the solvent to provide the compound of formula I.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to epoxy resins and epoxy resin compositions.

(Prior art) Epoxy resins are generally cured with various curing agents to improve mechanical properties, water resistance, chemical resistance, heat resistance,
It becomes a cured product with excellent electrical properties, and can be used as adhesives, paints,
It is used in a wide range of fields, including laminates, molding materials, and casting materials.

As an epoxy resin that provides a cured product with excellent heat resistance,
Glycidylamine type and glycidylamine ether type epoxy resins based on diaminodiphenylmethane, aminophenol, etc. are known.

On the other hand, Nogelac-type epoxy resin, which is based on Nogelac resin, is known as an epoxy resin that provides a cured product with superior toughness, although its heat resistance is inferior to the above-mentioned glycidylamine type and glycidylamine ether type epoxy resins. ing.

(Problem to be Solved by the Invention) However, there is no epoxy resin that has both the toughness of the cured product of novolak deaf epoxy resin and the heat resistance of the cured product of glycidylamine type and glycizolamine ether type epoxy resins. The development of resin is expected.

Moreover, since sealing materials for electrical and electronic parts are required to have extremely high heat resistance, even the heat resistance of cured products of glycidylamine type and glycidylamine ether type epoxy resins is insufficient.

(Means for Solving the Problems) As a result of intensive research in view of the above circumstances, the present inventors have discovered a specific glycidylamine deafening compound obtained by reacting a 4,4'-diaminobenzophenone compound with epichlorohydrin. The present inventors have discovered that the resin provides a cured product that has both heat resistance superior to cured products of conventional glycidylamine type epoxy resins and toughness of cured products of Norac type epoxy resins.

That is, the present invention provides an epoxy resin composition comprising an epoxy resin represented by the general formula (1), a nixy resin, a curing agent, and, if necessary, a curing accelerator. The present invention provides an epoxy resin composition characterized by containing an epoxy resin obtained by reacting epoxyaminobenzophenone shown in ) with chlorohydrintra.

The epoxy resin (1) of the present invention has the general formula [■] with respect to epichlorohydrin (However, R1 to R8 may be the same or different,
A hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halodane atom. ) It can be produced by reacting the compounds shown below.

The compound represented by the above general formula (III) is one in which the aromatic nucleus represented by the general formula CIV) (R, to R8 are as defined above) is an alkyl group having 1 to 3 carbon atoms and/or a halodane atom. Optionally substituted 4,4'-
Cyaminobenzophenone is preferred because of its easy availability.

4,4'-diaminobenzophenone (hereinafter simply 4,
It is abbreviated as 4'-diaminobenzophenone compound. )
As, 4.4'-diaminobenzophenone, 4
．． 4'-diamino-2-methylbenzophenone, 4.4
'-Diamino-3-propylbenzophenone, 4,4'
-diamino-z * z'= s ta'-tetramethylbenzophenone, 4.4'-diamino-2,2'
-dichlorobenzophenone, 4,4'-diamino-2
,2'.

6, tertetrabromobenzophenone, 4.4'-diamino-2-methyl-3'-famobenzophenone, 4.4'-diamino-3,3',5,5'-tetramethyl-2,2' .

Examples include 6.6'-tetrabromobenzophenone.

The method for producing the epoxy resin (1) of the present invention using the above-mentioned raw materials is not particularly limited, and is similar to conventional methods such as a method in which an addition reaction and a dehydrochlorination reaction are carried out at once using the above-mentioned raw materials using a base. You can do it using this method.

For example, when dichlorohydrin is added to a 4,4'-diaminobenzophenone compound, 20 to 1
After carrying out the doxylation at 20° C., the aqueous layer is removed and excess epichlorohydrin is distilled off.

Next, an organic solvent is added to the reaction product to dissolve it, water is added, the product is washed with water, and the oil layer is taken out.

Furthermore, water is removed from this oil layer by azeotropic distillation, followed by filtration and the solvent is distilled off to produce the desired epoxy resin [! ] can be obtained.

4. Nyxy resins (I) with different epoxy equivalents and softening points can be obtained by appropriately adjusting the charging ratio of epichlorohydrin to the 4'-diaminobenzophenone compound during the reaction.
can be manufactured.

The charging ratio of epichlorohydrin during the production of epoxy resin [■] is not particularly limited, but is 4.4
The charging ratio is usually 2.5 mol or more, preferably 5 to 15 mol, per 1 mol of the '-diaminobenzophenone compound.

Epoxy resin obtained by reacting at a charging ratio of [!
] can provide a cured product that has both heat resistance superior to cured products of conventional glycidylamine-reduced epoxy resins and toughness of cured products of Norilac type epoxy resins.

As is clear from its structural formula, the epoxy resin (1) of the present invention produced in this manner has 4, which was used as a raw material,
It is a tetraglycidyl etherified product of a 4'-diaminobenzophenone compound or a derivative thereof.

This epoxy resin (13) is rarely separated alone, and becomes a mixture of a tetrafunctional epoxy resin and its dimer, trimer, and tetramer.

The epoxy resin (1) of the present invention can be used alone or, if necessary, in combination with a known and commonly used epoxy resin, mixed with a curing agent, and cured by heating to obtain a cured product.

As the curing agent used in the present invention, all compounds commonly used as curing agents for 21-oxy resins can be used, including aliphatic amines such as diethylenetriamine and triethylenetetramine, metaphenylenediamine, diamino Aromatic amines such as diphenylmethane and diaminodiphenylsulfone, polyamide resins and modified products thereof, acid anhydride curing agents such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride, dicyanamide, imidazole, BF, -
Examples include latent curing agents such as amine complexes and guanidine derivatives.

These curing agents may be used alone or in combination of two or more.

The amount of these curing agents used is generally such that the number of epoxy groups contained in one molecule of the epoxy compound used and the number of active hydrogens in the curing agent are approximately equivalent.

When using each of the compounds listed above as a curing agent, a curing accelerator can be used as appropriate.

Any known and commonly used curing accelerator can be used, and examples thereof include tertiary amines, imidazole, organic acid metal salts, Lewis acids, amine complex salts, etc. These can be used alone or in combination of two or more. Combination use is also possible.

The epoxy resin composition of the present invention may further contain various well-known and commonly used additives such as fillers and colorants as required, including tar, pitch, amino resin, alkyd resin, and phenol. Resin etc. can also be used together.

Next, the present invention will be specifically explained using production examples, examples, and comparative examples. In the examples, all parts are by weight unless otherwise specified.

Production Example 1 After dissolving 212 parts of 4'-diaminobenzophenone in 740 parts of t-epichlorohydrin, 5.
800 parts of a 20% sodium hydroxide aqueous solution was added dropwise over 5 hours at 0 to 60°C, and the mixture was allowed to react for an additional 1 hour.
After discarding @, excess epichlorohydrin was distilled and recovered to obtain a reaction composition.

650 parts of toluene was added to this reaction composition to dissolve it uniformly, 220 parts of water was added and washed, the oil and water were separated, the oil layer was taken out, water was removed from the oil layer by azeotropic distillation, and then filtered. By distilling off toluene, an epoxy resin with an epoxy equivalent of 121 (theoretical 109) is produced (
a) 414 parts were obtained.

The infrared absorption spectrum of this epoxy resin (&) showed specific absorption gold at the positions shown below.

-N (1340 to 1330 Tan-1 e-< 1215 cps-' (To815 cmg-' (b) 408 parts were obtained.

Production Example 3 An epoxy resin (+414 parts) having an epoxy equivalent of 119 was obtained in the same manner as Production Example 1 except that the amount of epichlorohydrin used was 1110 parts.

Examples 1 to 3 and Comparative Examples 1 to 2 Epoxy resins (a) to (C) obtained in Production Examples 1 to 3 as Nixy resin, phenol tumerac epoxy resin Ebicuron N-738 (Dainippon Ink & Chemicals Co., Ltd. #8
manufactured by Ebicuron 430 (epoxy equivalent: 180) or diaminodiphenylmethane glycidylamine epoxy resin Evicron 430 (
The epoxy resin (manufactured by the same company, epoxy equivalent: 120) was used as a curing agent, Evicron B-570 (manufactured by the same company, methyltetrahydrophthalic anhydride) was used as a curing agent, and 2-ethyl-4-methylimidazole was used as a curing accelerator. The compositions shown in Table 1 were blended so that the number of acid anhydride groups in the curing agent was 1 per 11, to obtain one Nyxi resin composition for the present invention and a comparative control.

Corella's epoxy resin composition was cured at 100°C for 2 hours, then at 160°C for 2 hours, and then at 180°C for 2 hours to form a test piece. ), bending strength, flexural modulus, tensile strength, tensile elongation (a measure of toughness), and boiling water absorption. The results are shown in Table-1.

Examples 4 to 6 and Comparative Examples 3 to 4 Epoxy resin (,) as the epoxy resin as above
~(,), Epicron N-738 or Epicron 430
and DDM (diaminodiphenylmethane) as a curing agent, and were blended in the composition shown in Table 1 so that the number of active hydrogen groups in the curing agent was one per epoxy group in the epoxy resin as shown in Table 1. And an epoxy resin composition for comparison was obtained.

These epoxy resin compositions were cured at t-5oc for 5 hours and then at 160°C for 4 hours to form test pieces.
The same items as in the above example were measured in accordance with JISK-6911. The results are shown in Table-1.

(Effects of the present invention) The epoxy resin composition using the epoxy resin of the present invention provides a cured product having both the toughness of a cured product of a nogelac type epoxy resin and the heat resistance superior to a cured product of a glycidylamine type epoxy resin. It can be used for electrical insulating materials such as insulating panels, casting, laminates, tipping, and insulating powder coatings, laminates and prepregs for printed wiring boards, conductive adhesives, and structural materials such as honeycombs and tunnels. glue,
Molding materials for IC encapsulation, electrical parts, etc., GFRP, CF
R.P.

It is extremely useful for applications such as FRP and prepreg, composite materials such as ships, aircraft, automobiles, sporting goods, molds, tanks, etc., molds, brake linings, clutch facings, abrasives, etc., and resist inks.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1 to R_8 are hydrogen atoms, which may be the same or different, and have 1 to 3 carbon atoms. (However, R_9 to R_1_6 may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. ), n is 0-3. ] Epoxy resin shown by. 2. In an epoxy resin composition composed of an epoxy resin, a curing agent, and, if necessary, a curing accelerator, the epoxy resin components include the general formula [I] ▲mathematical formula, chemical formula, table, etc.▼[I] [Formula where R_1 to R_8 may be the same or different; hydrogen atom, alkyl group having 1 to 3 carbon atoms, or halogen atom; or a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom, which may be different from each other. An epoxy resin composition characterized by containing an epoxy resin represented by: 3. In an epoxy resin composition composed of an epoxy resin, a curing agent, and, if necessary, a curing accelerator, the epoxy resin component has an aromatic nucleus substituted with an alkyl group having 1 to 3 carbon atoms and/or a halogen atom. 1. An epoxy resin composition comprising an epoxy resin obtained by reacting 4,4'-diaminobenzophenone, which may be an optional compound, with epichlorohydrin.