JPH0653784B2 - New epoxy resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel epoxy resin. For more details,
The present invention relates to a new epoxy resin having excellent heat resistance and mechanical properties.

[Prior Art] and [Problems to be Solved by the Invention] Epoxy resin containing an aromatic polyamine, an aliphatic polyamine,
Polyamine amine, amine adduct, dicyandiamide, acid anhydride, phenol novolac resin-based compounding various curing agents are used as adhesives, paints, molding materials, casting materials, etc. Varnish with, and impregnate and apply this to the reinforcing base material,
It is also well known in the past to be used for forming laminated plates.

By the way, in recent years, especially with miniaturization and refinement in the electric and electronic fields, adhesives for electronic parts, insulating paints, sealing materials,
In applications such as laminates, there is a strong demand for improved heat resistance in order to increase reliability during high temperature use. That is, adhesives, paints, encapsulants, laminates, etc. prepared using bisphenol A type epoxy resins that have been commercially available in the past cause a decrease in heat distortion temperature or electrical insulation, resulting in reliability. There was a problem of chipping.

On the other hand, for the purpose of improving heat resistance, polyfunctional epoxy resins such as phenol novolac epoxy resin and o-cresol novolac epoxy resin are used. However, although these cured products are excellent in heat resistance, Due to its high elasticity, it is hard and brittle, cracks easily occur due to heat shots, and it is prevented from increasing internal stress due to curing shrinkage of resin, etc., to satisfy the requirements for miniaturization and precision of electronic parts. I haven't arrived.

Therefore, an epoxy resin excellent in heat resistance and mechanical properties is strongly desired, but it has been found that the following new epoxy resins can sufficiently satisfy such requirements.

[Means for solving problems]

Therefore, the present invention relates to a novel epoxy resin, which is represented by the following general formula.

here, R: hydrogen atom or methyl group R ′, R ″: hydrogen atom, halogen atom, lower alkyl group or lower alkoxy group, each R ′ of R _{1 to} R ₃ ,
R ″ may be the same or different from each other. The novel epoxy resin represented by the above general formula [I] is a trisphenol compound represented by the following general formula. here, R ′, R ″: The same as above.

Is reacted with epihalohydrin or β-methylepihalohydrin, preferably with about 3 to 30 times the molar amount of epichlorohydrin.

This reaction can be carried out in various ways following the conventionally known reaction of this type. One method is to use alkaline compounds such as sodium hydroxide, potassium hydroxide,
An alkali metal hydroxide such as lithium hydroxide, preferably sodium hydroxide, is used in a molar amount 1 time or more, preferably 1.
02 to 1.05 times the molar amount of the etherification step and the dehydrohalogenation step at the same time in the presence of water to about 60 to 90
The reaction is carried out at a temperature of ℃, after the reaction is completed, the unreacted halohydrins, water and salts formed are removed, and the epoxy resin as the reaction product is dried and obtained.

However, if a method in which the etherification step and the dehydrohalogenation step are sequentially performed is adopted, an epoxy resin of stable quality can be obtained, and therefore, it is a more preferable method.

In the etherification step, about 0.005 to 5 mol% of an etherification catalyst, for example, a tertiary amine such as trimethylamine or triethylamine, a tertiary phosphine such as triphenylphosphine, or tributylphosphine, is used with respect to 1 equivalent of the phenolic hydroxyl group of trisphenol. Tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, fourth ammonium salt such as choline chloride, tetramethylphosphonium bromide, tetramethylphosphonium iodide, fourth phosphonium salt such as triphenylpropylphosphonium bromide, Tertiary sulfonium salts such as benzyldibutylsulfonium chloride and benzyldimethylsulfonium chloride are preferred. The reaction is carried out in the presence of a quaternary ammonium salt.

In this etherification step, the reaction is carried out until at least about 50% or more, preferably about 80% or more of the hydroxyl groups of trisphenol are etherified. This reaction is generally about 60
It is carried out at a temperature of ~ 110 ° C for about 1 to 12 hours, in which water is preferably absent, and the presence of water is controlled to 3.0% by weight or less.

In the subsequent dehydrohalogenation step, the reaction product of the etherification step is subjected to the reaction as it is, that is, while containing unreacted epihalohydrin. As the catalyst for this reaction, the same alkali compound as used in the above-mentioned first method, for example, an alkali metal hydroxide, preferably sodium hydroxide, is used in an amount of 0.5 times mol per 1 equivalent of phenolic hydroxyl group of trisphenol. It is used in the above proportion, preferably 0.8 times or more. However, it is desirable that the usage ratio is 1 times or less mol in order to avoid inconvenience such as gelation.

This reaction is generally carried out at a temperature of about 60 to 100 ° C. for about 1 to 3 hours, and when sodium hydroxide is used as a catalyst, it is preferably carried out while removing by-produced water from the reaction system. After completion of the reaction, unreacted epihalohydrin is removed by vacuum distillation, by-product salts are removed by washing with water, and if necessary, neutralization is carried out with weak acids such as phosphoric acid and sodium dihydrogen phosphate, and dried. The target epoxy resin is obtained.

The novel epoxy resin thus obtained is a known curing agent for epoxy resin, for example, folinamines, modified polyamines, polyamidoamines, polycarboxylic acids, acid anhydrides, boron trifluoride-amine complex, imidazole. It can be cured by blending a compound, dicyandiamide, phenol novolac resin and the like. The amount used varies depending on the type of the curing agent, and when polyamines are used, the ratio of the epoxy equivalent to the active hydrogen equivalent is a standard. Also, the curing accelerator,
Used as needed.

The epoxy resin according to the present invention is another epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, within a range that does not impair the purpose.
Use in combination with 1,1-bis (glycidoxyphenyl) ethane, phenol novolac type epoxy resin, o-cresol-novolac type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, etc. You can Further, in the case of imparting flame retardancy, diglycidyl ether of tetrabromobisphenol A and the like are used together.

In addition to the above components, the epoxy resin composition may include phthalic acid esters, ethers or esters of glycols, non-reactive diluents such as phenol, long-chain alkylene oxides, butyl glycidyl ether, phenyl glycidyl ether, p- Reactive diluent such as butylphenyl glycidyl ether, calcium carbonate, clay, asbestos, silica, mica, quartz powder, aluminum powder,
Fillers such as graphite, titanium oxide, alumina, iron oxide, glass powder, glass battlefield, carbon black, toluidine red, Hansa yellow, phthalocyanine blue,
A colorant such as phthalocyanine green is appropriately mixed.

When this epoxy resin is used as a molding material for a laminated plate or the like, it is liquefied using a solvent such as toluene, aromatic hydrocarbons such as xylene, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, and a curing agent and If necessary, add a curing accelerator to form a varnish, and impregnate this into a reinforcing base cloth such as glass cloth, glass fiber, carbon fiber, paper, asbestos, polyester fiber, aromatic polyamide fiber, and prepreg it. After that, the laminate can be formed by heating under pressure. It is also possible to employ a method of heating and melting an epoxy resin and a curing agent and impregnating the reinforcing base material.

〔The invention's effect〕

The novel epoxy resin according to the present invention, when cured, gives a cured product having higher flexural strength and lower elastic modulus than the conventional cured epoxy resin and a heat distortion temperature of 230 ° C. or higher. .

Accordingly, the present invention provides an epoxy resin that gives a cured product that is reliable even at high temperatures when used as a molding material such as an adhesive, a coating material, a sealing material, a molding material, a varnish and a laminated board molding. .

〔Example〕

 Next, the present invention will be described with reference to examples.

Example 1 Epichlorohydrin 462.5 g, 1- [α-methyl-α
(4'-Hydroxyphenyl) ethyl] -4- [α ',
141.3 g of α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene and 2.73 g of tetramethylammonium chloride were placed in a glass four-necked flask having a capacity of 1 equipped with a stirrer and a reflux device, and stirred at 70 ° C. Three
Reacted for hours.

Then, while maintaining this temperature, 79 g of 48% aqueous sodium hydroxide solution (molar ratio to the above trisphenol of 2.8
5) was continuously added dropwise over 2 hours. At this time,
The pressure in the system was reduced to 150 to 250 mmHg, the generated water was removed to the outside of the system, and the azeotropic epichlorohydrin was returned to the system. After the dropping was completed, water was removed to the outside of the system until the generation of water was no longer observed, and then unreacted epichlorohydrin was distilled out of the system. 230 g of methyl isobutyketone and 230 g of water were added to the residue and stirred, the generated salt was transferred to the aqueous phase and then allowed to stand, and the separated aqueous phase was removed.

Next, 20 g of a 24% aqueous sodium hydroxide solution was added to the oil phase, and the mixture was stirred at 90 ° C. for 2 hours to carry out a second dehydrochlorination reaction. Then the oil phase is separated from the water phase and
A 76% aqueous solution of sodium dihydrogen phosphate was added for neutralization, followed by removal of water by azeotropic distillation and filtration of salt by a G glass filter.

Methyl inbutyl ketone was completely removed from the oil phase under reduced pressure of 5 mmHg and 150 ° C., and 1- [α-methyl-α- (4′-glycidoxyphenyl) ethyl] having an epoxy equivalent of 219 and a softening point of 63 ° C. 180 g of -4- [α ', α'-bis (4 "-glycidoxyphenyl) ethyl] benzene was obtained. The infrared absorption spectrum of the obtained epoxy resin was 1st.
As shown in the figure. ¹ H-NMR (proton nuclear magnetic resonance; CDCl ₃ solution) δ = 1.62,6H, s δ = 3.17-3.44,3H, m 2.07,3H, s 3.77-4.24,6H, m 2.64-2.94,6H, m 6.69 ~ 7.20,16H, m Example 2 In Example 1, as trisphenol, 1- [α
-Methyl-α- (3 ', 5'-dimethyl-4'-hydroxyphenyl) ethyl] -4- [α', α'-bis (3 ", 5" -dimethyl-4 "-hydroxyphenyl)
Ethyl] benzene 155.0 g, epoxy equivalent 240,
1- [α-methyl-α- (3 ′, 5′-dimethyl-4′-glycidoxyphenyl) ethyl] -4- having a softening point of 87 ° C.
196 g of [α ', α'-bis (3 ", 5" -dimethyl-4 "-glycidoxyphenyl) ethyl] benzene were obtained.
The infrared absorption spectrum of the obtained epoxy resin is
It is shown in FIG. ¹ H-NMR (proton nuclear magnetic resonance; CDCl ₃ solution) δ = 1.62,6H, s δ = 3.18-3.44,3H, m 2.06,3H, s 3.60-4.15,6H, m 2.17,12H, s 6.65,4H , s 2.21,6H, s 6.82,2H, s 2.61 to 2.95,6H, m 6.95 to 7.03,4H, D Application Example 1 100 parts (weight, the same below) of the epoxy resin obtained in Example 1, methyl nadic acid Anhydrous (Nippon Kayaku product Kayahard MCD) (78 parts) and -ethyl-4-methylimidazole (Shikoku Kasei product 2E4MZ) (1 part) were added at 100 ° C for 3 hours.
At 230 ℃, mixed by heating for 2 hours, the cured product obtained,
The following items were measured.

Heat distortion temperature: According to ASTM D-648 Bending strength: According to JIS K-6911 Bending elastic modulus: According to IJS K-6911 Application example 2 50 parts of the epoxy resin obtained in Example 1, bisphenol A type epoxy resin (Mitsui Petrochemical Product EPOMIK R
-140) 50 parts, 84 parts of methyl nadic acid anhydride and 2-
Application Example 1 using 1 part of ethyl-4-methylimidazole
Curing and measurement of the cured product were performed in the same manner as in.

Application Example 3 Using 100 parts of the epoxy resin obtained in Example 2, 71 parts of methyl nadic acid anhydride and 1 part of 2-ethyl-4-methylimidazole, curing and measurement of the cured product were carried out in the same manner as in Application Example 1. It was conducted.

Comparative Application Example 1 Bisphenol A type epoxy resin (EPOMIK R-
140) 100 parts, 90 parts of methyl nadic acid anhydride and 2-
Application Example 1 using 1 part of ethyl-4-methylimidazole
Curing and measurement of the cured product were performed in the same manner as in.

Comparative Application Example 2 Using 100 parts of o-cresol novolac type epoxy resin (EOCN102 manufactured by Nippon Kayaku Co., Ltd.), 81 parts of methyl nadic acid anhydride and 1 part of 2-ethyl-4-methylimidazole, curing and curing were carried out in the same manner as in Application Example 1. Measurements were performed on the cured product.

The measurement results of the above-described application examples and comparative application examples are shown in the following table.

[Brief description of drawings]

1 and 2 are infrared absorption spectra of the novel epoxy resins obtained in Examples 1 and 2, respectively.

Claims (1)

[Claims] 1. A novel epoxy resin represented by the following general formula. here, R: hydrogen atom or methyl group R ′, R ″: hydrogen atom, halogen atom, lower alkyl group or lower alkoxy group, each R ′ of R _{1 to} R ₃ ,
R ″ may be the same or different from each other