JPS6239616A - Epoxy resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an epoxy resin composition that has excellent heat resistance, flexibility, etc., and excellent water resistance.

[Conventional technology]

Epoxy resins have excellent heat resistance, electrical insulation, chemical resistance, and mechanical properties, and are therefore widely used in fields such as paint adhesives, sealants, and structural materials. In particular, in recent years, composite materials with carbon fiber (CFRP) have been used as structural materials for aerospace equipment, railways, Base materials for the transportation industry such as automobiles, golf shafts,
It is used as a leisure component for fishing rods, skis, etc., and great development is expected in the future.

[Problems to be solved by the invention]

CFRP using epoxy resin as matrix resin
elongation (flexibility) required for aircraft structures, etc.
At present, there is no composition that fully satisfies functions such as heat resistance, water resistance, and elastic modulus. Epoxy resins having spiroacecool rings are known as resins that provide resin compositions with excellent flexibility. The resins described in U.S.P. 3347871 and U.S.P. 338098 Mig.
It has excellent heat resistance and impact resistance, but has the disadvantage of low flexibility.

In addition, epoxy resin (bisphenol type epoxy resin,
It has the disadvantage of low compatibility with other materials such as novolak type resins.

[Means for Solving the Problems] In order to develop a resin with excellent flexibility and heat resistance, the present inventors conducted intensive studies and found the following formula: Indicates an integer of 15. ]1~
The inventors have discovered that an epoxy resin having a lycyclo(5,2,1,02, et al.)decane ring is suitable for the intended purpose, leading to the present invention.

The resin (L) represented by the above general formula is a ketone solvent,
It dissolves in precipitated solvents such as tetrahydrofuran and chloroform, and is compatible with various epoxy resins. That is, the gist of the present invention is that 10 to 90% of an epoxy resin (component A) having a dicyclopentadiene ring represented by the general formula (1), a bisphenol type epoxy resin, a novolac type epoxy resin, or more. This relates to an epoxy resin composition formed by blending a curing agent into a mixture with a selected epoxy resin (component B) of 10 to 40 weight percent, and as the curing agent, diaminoxylene is advantageously used. .

[Effect]

The epoxy compound having a dicyclopentadiene derivative as component (A) represented by the general formula (I) of the present invention is produced by the method shown in Japanese Patent Application No. 59-245795.

That is, it is obtained by reacting epichlorohydrin with a resin polymerized with cresols and dicyclopentadiene.

The epoxy resin of component (B) has a viscosity of 9%,
It is blended for the purpose of improving the heat resistance of the cured product (phenol novolac type epoxy resin, etc.).

Containing the dicyclopentadiene derivative in component (A) means that the molding material contains i? 4i! It is possible to obtain a composition with improved ductility and flexibility.

In addition, moisture resistance can be further improved by containing alkylphenols.

Component (A) is 10 to 90% by weight of the epoxy resin component.
It is preferably used in a proportion of 40 to 10% by weight. If the amount is less than 10% by weight, the flexibility of the cured product will be poor.

As the curing agent for curing these epoxy resins, various curing agents similar to those used in known epoxy resins can be used. For example, aliphatic amines, aromatic amines,
Examples include heterocyclic amines, Lewis acids such as boron trifluoride and their salts, organic acids, and organic acid anhydrides.

Specific examples thereof include aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, 2-4-diaminotoxylene, 2-methylimidazole, 2,4.5-triphenylimidazole, 1-cyanoethyl-2- Imidazole such as methyl-imidazole, substituted imidazole products, or salts of these with organic acids: organic carboxylic acids such as trimellitic acid, hexahydrophthalic acid; tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Organic acid anhydrides such as hexahydrophthalic anhydride and pyromellitic anhydride; urea derivatives such as dicyandiamide, melamine, and guanamine; nitriethylenetetramine, xylylene diamine, isophorone diamine, 1°8-diazobicyclo(5,4,0 ) Fatty acid polyamines such as undecene-7, phenol type novolac resins, etc. can be used. The curing agents can be used alone or in combination. The amount used is in the range of 0.01 to 1.0% by weight based on the total amount of the base agent and curing agent.

Furthermore, this epoxy resin composition contains four curing agents, carbon fiber, glass fiber, plasticizer, organic solvent, reactive diluent, extender, filler, reinforcing agent, pigment, flame retardant, etc. Various additives such as thickeners, thickeners, accelerators, and flexibilizing agents can be included. As curing accelerators for epoxy resins, commonly used polycyclic amines, Lewis acids such as boron trifluoride and their salts, organic acids, organic acid anhydrides, urea or their derivatives are used. Can be used singly or in combination.

[Example] Production example of Δ component 1,000 parts of para-cresol was charged into a reactor equipped with a thermometer, a refrigerator, a stirring device, and a dropping tube.
After adding 15 parts of 47% BF3 ether comb L/x while maintaining the temperature at °C, 416.9 parts of dicyclopentadiene was added dropwise over 4 hours. 100±5 for 1 hour after dripping
After the temperature was maintained at 150° C. and 4 mm Hg, unreacted bala-cresol and BF3 were distilled off to remove 950 parts of the polymer.

Next, 100 parts of the polymer obtained by 1FI, 1 part of TeI-ramethylammonium bromide, and 250 parts of epichlorohydrin were added.
80 parts were reacted at 5°C for 10 hours. After the completion of the addition reaction, a water separator was installed, and 36 parts of a 50% by weight aqueous sodium hydroxide solution was added dropwise, successively so that the water content in the reaction system fell within the range of 0.1 to 2.0% by weight during the addition. Water was separated from the reaction system.

After dropping the entire amount, the mixture was reacted for 4 hours, and then epichlorohydrin was distilled under reduced pressure. After dissolving the remaining reactant in methyl isobutyl ketone, helium chloride in the reaction system was filtered off, the filtrate was further washed with pure water, and the organic solvent was distilled off from the organic layer to obtain the epoxy resin of component A. I got it.

Examples 1 to 4 Component A dicyclopentane phenolic polymer epoxy resin (D CE-400) Component B listed in Table 1 A curing agent xylene diamine curing accelerator 2-methylimidazole was blended to prepare an epoxy resin composition.

The curing agent xylene diamine is added in stoichiometric proportions. 0.5 part of 2-methylimidazole was added.

This resin composition was thoroughly kneaded with a twin-screw roll, and
Cured at 0°C for 4 hours, further cured at 200°C for 2 hours,
A cured product was obtained.

The physical properties of this cured product are shown in Table-1.

Comparative Examples 1 to 3 Epoxy resin compositions having the compositions shown in Table 1 were prepared and cured in the same manner as in Examples 1 to 4 to obtain cured products.

The results are shown in Table-1.

Hand Uc Neho True Tone (Jiko) November 19, 1985 1, Matter (Indication of 'I' 1985 Patent Application No. 178087 2, Name of Invention Epoxy Resin Composition 3, Person Who Makes Corrections) Relationship with '-1
1-4-5 Marunouchi, Chiyo E [] Ward, Tokyo Name (
234) Sanyo Kokusaku Pulp Co., Ltd. 4, Agent Address: 16-16 Kanda Kita Jomono-cho, Chiyo B1-ku, Kyoto 101 Ei Building, 3rd Floor 5, Detailed Description of the Invention Detailed Description of the Specification Subject to Amendment ＼Co), - Contents of fan correction 1. On the 5th line of page 4 of the detailed output, the word "having a ring" should be replaced with "ring (abbreviated as dicyclopentadiene derivative under D)" and 8
1 correct.

2. Line 1 of page 5 for specification "Having a ring" is required. Corrected to "contains derivatives."

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, n represents an integer from 0 to 15. ] Tricyclo[5,2,1,0^2^,^6]
10 to 90% by weight of an epoxy resin having a decane ring (component A) and 10% by weight of an epoxy resin selected from bisphenol-type epoxy resins and novolak-type epoxy resins (component B)
An epoxy resin composition characterized by comprising a curing agent in a mixture of ~40% by weight. (2) The epoxy resin composition according to claim 1, wherein the curing agent is diaminoxylene.