JPH0742399B2 - Epoxy resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an epoxy resin composition having excellent workability, heat resistance and curability.

[0002]

2. Description of the Related Art Conventionally, epoxy resins alone have high softening points and viscosities. Therefore, a method of adding a reactive diluent to epoxy resins has been used to improve workability. As the reactive diluent, diepoxy compounds such as 1,6-hexanediol glycidyl ether and neopentyl glycol glycidyl ether are widely known.

[0003]

However, although these reactive diluents have an excellent diluting effect, they have a problem that the heat resistance and the curability of the cured product are remarkably lowered.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention comprises an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms and a glycidyl ether compound (A) having two or more glycidyl ether groups bonded thereto and an epoxy resin (B). It is a characteristic epoxy resin composition.

Specific examples of the glycidyl ether compound (A) having an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms and two or more glycidyl ether groups bonded thereto in the present invention include butenediol glycidyl ether,
Examples thereof include butynediol glycidyl ether, octadiene diol glycidyl ether, vinylcyclohexane diol glycidyl ether, and the like, butene diol glycidyl ether and butyne diol glycidyl ether are preferred.

The glycidyl ether (A) can be produced by either of the conventionally known one-step method or two-step method. For example, in the one-step method, a glycol having an unsaturated group can be synthesized by reacting it with epichlorohydrin in the presence of caustic soda, usually at 30 to 70 ° C. In the two-step method, a glycol having an unsaturated group and epichlorohydrin are subjected to an addition reaction in the presence of a catalyst, and then caustic alkali is added to carry out a dehydrochlorination reaction to synthesize the compound. Of the two methods, the one-step method is preferable because the total chlorine content remaining in the produced (A) is small.

The epoxy equivalent of (A) is usually 70 to 200 g / e.
q, preferably 90-150 g / eq.

Examples of the epoxy resin (B) in the present invention include bisphenol type epoxy resin (for example, diglycidyl ether of bisphenol A); phenol novolac type epoxy resin (for example, polyglycidyl ether of phenol novolac, alkylbenzene-modified phenol novolac). Cresol novolac type epoxy resin (eg ortho-cresol novolac polyglycidyl ether); phenol type epoxy resin (eg resorcin diglycidyl ether, phloroglysin diglycidyl ether) or their bromides and Examples thereof include epoxidized products of conjugated diene polymers (eg, epoxy group-containing polybutadiene). These may be used alone or in combination of two or more.

The epoxy equivalent of (B) is usually 50-1500 g / e.
q, preferably 100-600 g / eq.

The amount of (A) used in the present invention is (B)
Usually from 1 to 70% by weight, preferably from 2 to 50% by weight
% By weight. If it is less than 1% by weight, the dilution effect is insufficient, and if it exceeds 70% by weight, the heat resistance decreases.

Examples of the epoxy resin curing agent (C) used in the present invention include polyamines (chain aliphatic polyamines such as diethylenetriamine: alicyclic polyamines such as N-aminoethylpiperazine: xylenediamine, xylenediamine formalin polycondensation). Aromatic polyamines such as compounds: Aromatic polyamines such as metaphenylenediamine: Dicyandiamide: Hydrazine derivatives such as adipic acid dihydrazide: Polyamide polyamines obtained by polycondensation of dimer acid and polyamine), polybasic acids (phthalic acid, triacid) Mellitic acid, etc.), polybasic acid anhydrides (phthalic anhydride, hexahydrophthalic anhydride, etc.), polyphenols (phenol novolac resin, cresol novolac resin, various novolac resins synthesized from bisphenol A and resorcin), po Mercaptans, imidazoles, BF ₃ complexes, and the like. These may be used alone or in combination of two or more.

The amount of (C) used is usually (0.2 to 1.4) in terms of the equivalent ratio of the active hydrogen equivalent of the curing agent and the total epoxy equivalent (total epoxy equivalent) of (A) and (B). : 1 and preferably (0.4 to 1.2): 1.

If desired, a known curing accelerator can be used in the resin composition of the present invention. As the curing accelerator, phosphorus compounds such as triphenylphosphine, 2-
Examples thereof include imidazoles such as methylimidazole and tertiary amines such as benzyldimethylamine.

When a curing accelerator is used, the amount added is
It is usually 0.1 to 5.0% by weight based on the total weight of (A) and (B).

In the present invention, by using a radical polymerization initiator (D) in addition to the above (A), (B) and (C), the heat resistance of the cured epoxy resin can be further improved. Examples of the (D) include organic peroxide-based polymerization initiators (lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, etc.), azo-based polymerization initiators (azobisisobutyronitrile, azobisdimethylvaleronitrile, etc.). ) Is mentioned.

The amount of (D) used is based on the weight of (A).
It is usually 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight.

There are no particular restrictions on the mixing method, etc. used in the production of the resin composition of the present invention.
It may be prepared by a method such as stirring and mixing in an arbitrary container equipped with a stirrer in a room temperature range up to about 0 ° C.

The curing conditions of the resin composition of the present invention are not particularly limited, and a cured product can be obtained at any curing temperature and curing time depending on the type of curing agent. Even when a radical polymerization initiator is used, a cured product can be obtained under arbitrary curing conditions depending on the type of the initiator.

The cured product of the present invention thus obtained has excellent heat resistance. This is because the glycidyl ether compound (A), which is one of the constituent elements of the present invention, has two or more epoxy groups in the molecule and also has a heat-polymerizable or radical-polymerizable unsaturated bond. This is because the crosslinked density of the obtained cured product is increased. Therefore, by using the radical polymerization initiator together with the epoxy curing agent, a cured product having more excellent heat resistance can be obtained.

Since the epoxy resin composition of the present invention is excellent in workability, curability and heat resistance of the cured product, it can be used in casting materials, paints, adhesives, laminated materials, matrix resins for fiber reinforced plastics and the like. Can be suitably used.

[0021]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In addition, the part in an Example and a manufacture example shows a weight part.

Production Example 1 100 parts of 2-butene-1,4-diol, 420 parts of epichlorohydrin and 182 parts of sodium hydroxide were charged into a reaction vessel equipped with a thermometer, a stirrer and a nitrogen gas introducing tube, and nitrogen was added with vigorous stirring. The reaction was performed at 50 ° C. for 5 hours in the atmosphere. After the reaction, 100 parts of water was added and the mixture was stirred for 10 minutes and washed with water.
After standing still, the upper layer was separated and filtered, and then excess epichlorohydrin was removed from the filtrate under reduced pressure to obtain 210 parts of 2-butenediol glycidyl ether (A-1) as a residue. The epoxy equivalent of this glycidyl ether is 122 g / eq, viscosity 24 cps / 2
It was 5 ° C.

Production Example 2 A reaction vessel similar to that used in Production Example 1 was charged with 100 parts of 2-butyne-1,4-diol, 420 parts of epichlorohydrin and 182 parts of sodium hydroxide, and was vigorously stirred at 50 ° C. under a nitrogen atmosphere. The reaction was carried out for 5 hours. Subsequent operations are the same as in Production Example 1, and 2-butynediol glycidyl ether (A-
2) I got 214 copies. The epoxy equivalent of this glycidyl ether was 118 g / eq, and the viscosity was 65 cps / 25 ° C.

[0024]

Comparative Production Example 1 1,6-hexanediol 10 was placed in the same reaction vessel as above.
0 parts, 319 parts of epichlorohydrin and 138 parts of sodium hydroxide were charged, and the mixture was reacted under a nitrogen atmosphere at 50 ° C. for 5 hours while vigorously stirring. Subsequent operations are Production Example 1
In the same manner as in the above, 185 parts of 1,6-hexanediol glycidyl ether (S-1) was obtained. This glycidyl ether has an epoxy equivalent of 135 g / eq and a viscosity of 23 cps /
It was 25 ° C.

Comparative Production Example 2 Neopentyl glycol 100 was placed in the same reaction vessel as above.
Parts, 355 parts of epichlorohydrin and 154 parts of sodium hydroxide were charged and reacted under a nitrogen atmosphere at 50 ° C. for 5 hours with vigorous stirring. The rest of the procedure was the same as in Production Example 1 to obtain 197 parts of neopentyl glycol glycidyl ether (S-2). The epoxy equivalent of this glycidyl ether is 141 g / eq, and the viscosity is 18 cps / 25.
It was ℃.

Examples 1 to 4 and Comparative Examples 1 to 3 Based on the respective formulations and curing conditions of Examples 1 to 4 and Comparative Examples 1 to 3 shown in Table 1 below, all the components were blended and cured to obtain an epoxy resin. A resin cured product was obtained. Table 2 shows the physical properties of the cured products. Table 3 shows the viscosities and gel times (minutes) of the epoxy resin formulations of Examples 1 and 2 and Comparative Examples 1 to 3.

[0028]

[Table 1]

[0029]

[Table 2]

Measuring Method (1) Bending Strength: According to JIS-K-6911 (2) Bending Elastic Modulus: According to JIS-K-6911 (3) Glass Transition Temperature: Measured by TMA

[0031]

[Table 3]

[0032]

EFFECT OF THE INVENTION The epoxy resin composition of the present invention has a low viscosity and excellent curability and workability without deteriorating various properties originally possessed by the epoxy resin even when a reactive diluent is added to the epoxy resin. Furthermore, since the cured product of the epoxy resin composition of the present invention has excellent heat resistance, it is particularly suitable for paints and laminated materials.

Claims (4)

[Claims] 1. A glycidyl ether compound (A) having an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms and two or more glycidyl ether groups bonded thereto, and an epoxy resin (B). And an epoxy resin composition. 2. A glycidyl ether compound (A), an epoxy resin (B) and an epoxy curing agent (C) having an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms and two or more glycidyl ether groups bonded thereto. ) And an epoxy resin composition. 3. A glycidyl ether compound (A), an epoxy resin (B), an epoxy curing agent (C) having an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms and two or more glycidyl ether groups bonded thereto. And a radical polymerization initiator (D). 4. The epoxy resin composition according to claim 1, wherein (A) is butenediol glycidyl ether or butynediol glycidyl ether.