JPH1060089A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition having low irritation and a slight odor without loss of mechanical strength and viscosity. SOLUTION: This epoxy resin composition comprises 80-90wt.% bisphenol-type epoxy resin having <=10,000mPa.S viscosity at 25 deg.C and 10-20wt.% 1,6-hexanediol diglycidyl ether. A bisphenol A-type epoxy resin, bisphenol F-type epoxy resin and a mixture thereof are preferably used as the bisphenol-type epoxy resin in the epoxy resin composition. The epoxy resin composition is useful for a use such as an adhesive for civil engineering or building, a reinforcement of concrete, a coating material, casting for flooring material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive for civil engineering and construction,
The present invention relates to an epoxy resin composition useful for applications such as concrete reinforcement, paint, and casting of flooring. More specifically, the present invention relates to an epoxy resin composition which is useful for the above applications, has low viscosity, is excellent in handleability, has low irritation, and has excellent physical properties.

[0002]

2. Description of the Related Art Epoxy resins are used for various purposes because of their excellent physical properties and chemical properties. In general,
For applications such as civil engineering / architectural adhesives, concrete reinforcement, paints, and casting of floor materials, they are used after being diluted with a reactive diluent to reduce the viscosity in consideration of handleability. Generally, butyl glycidyl ethers, higher alcohol glycidyl ethers and the like can be mentioned as reactive diluents used in such applications.

However, the above butyl glycidyl ether is highly irritating to the skin and has a strong odor. Therefore, when the epoxy resin is diluted so as to have a sufficiently low viscosity, it is not preferable in terms of environmental hygiene and occupational health. Have been shunned.

On the other hand, higher alcohol glycidyl ethers have low odor and low irritation, but have a problem in the strength of the cured epoxy resin, and are particularly required in fields where high strength is required, such as concrete reinforcement. Not suitable for the field.

[0005]

SUMMARY OF THE INVENTION As described above, there is a need for a low-viscosity epoxy resin composition which has low odor, low irritation and excellent mechanical properties of a cured epoxy resin. .

[0006]

Means for Solving the Problems The inventor of the present invention has conducted intensive studies in order to solve the above-mentioned problems of the prior art, and has found that as a reactive diluent, 1,6-, which has low irritation and low odor, is used. Using hexanediol glycidyl ether, it was found that an epoxy resin composition having sufficiently low viscosity, low irritation, low odor, and excellent mechanical properties after curing was obtained, and reached the present invention. .

That is, the present invention contains 80-90% by weight of a bisphenol type epoxy resin having a viscosity at 25 ° C. of 10,000 mPa.S or less and 10-20% by weight of 1,6-hexanediol diglycidyl ether. The present invention provides an epoxy resin composition comprising:

Hereinafter, the epoxy resin composition of the present invention will be described in detail.

The viscosity of the bisphenol type epoxy resin used in the present invention at 25 ° C. is 10,000 mPa.S or less, preferably 9000 mPa.S or less, and most preferably 80 mPa.S or less.
00 mPa.S or less. If the viscosity is higher than this, the viscosity of the epoxy resin composition after dilution with the reactive diluent becomes high, so that the handleability and flowability deteriorate, and in such a case, the amount of the diluent added to reduce the viscosity is reduced. Since the epoxy resin composition must be made high, such epoxy resin composition has poor physical properties after curing, and is not preferable in environmental hygiene and occupational health.

The bisphenol type epoxy resin of the present invention can be suitably used as long as it has a low viscosity. For example, a bisphenol type epoxy resin obtained by reacting a bisphenol with epihalohydrin under appropriate reaction conditions is subjected to molecular distillation to obtain a high-viscosity epoxy resin. It can be produced by removing the molecular components or increasing the equivalent ratio of epihalohydrin when reacting the bisphenols with epihalohydrin to reduce the content of high molecular weight components.

The bisphenols useful as raw materials for the bisphenol-type epoxy resin of the present invention include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and halides thereof. These bisphenols can be used alone or in a mixture.

The bisphenol type epoxy resin of the present invention can be produced by reacting the above bisphenols with epihalohydrin under appropriate conditions. As epihalohydrin, epichlorohydrin is particularly preferably used.

As the bisphenol type epoxy resin of the present invention, a relatively low viscosity epoxy resin as described above may be used alone or mixed with another bisphenol type epoxy resin to reduce the viscosity. Can be used. Further, the bisphenol F type epoxy resin can be used alone as a relatively low-viscosity epoxy resin or blended with another resin. The compounding ratio of the bisphenol F type epoxy resin is determined by the viscosity of the mixture.
0% or more, more preferably 20% or more, most preferably 30% or more.

In the present invention, 1,6 which is hypoallergenic and low odor
-Use hexanediol diglycidyl ether as reactive diluent. The SPI method (Soci
etyof Plastic Industry method) and PII method (primary skin irritation test method) are known, and the SPI and PII values of 1,6-hexanediol diglycidyl ether and butyl glycidyl ether as a comparison are shown in the table below. . S
The smaller the PI and PII values, the less skin irritation.

1,6-hexanediol butyl glycidyl ether diglycidyl ether SPI value 24 PII value 1.7 4.2-6.8

As is apparent from the above, 1,6-hexanediol diglycidyl ether has low skin irritation and is preferred in terms of occupational health.

1,6-hexanediol diglycidyl ether has a low vapor pressure, low odor, and little influence on working environment and natural environment. The following table shows the vapor pressures of 1,6-hexanediol diglycidyl ether and butyl glycidyl ether.

1,6-hexanediol butyl glycidyl ether Temperature diglycidyl ether 25 ° C. <1.0 mmHg 3.6 mmHg 80 ° C. 0.9 mmHg 5.0 mmHg 100 ° C. 2.0 mmHg 7.5 mmHg

In order to achieve the object of the present invention, it is essential to use 1,6-hexanediol diglycidyl ether having a low skin irritation and a low vapor pressure as described above.

The epoxy resin composition of the present invention contains 5 to 25% by weight, preferably 10 to 20% by weight of 1,6-hexanediol diglycidyl ether as a reactive diluent. When the content of the reactive diluent is larger than the above range, the physical properties after curing are poor, and when the content of the reactive diluent is smaller than the above range, the viscosity of the epoxy resin composition is high, so that the flowability and handleability are high. Is bad and not preferred.

The epoxy resin composition of the present invention can be produced by mixing a relatively low-viscosity epoxy resin as described above and 1,6-hexanediol diglycidyl ether by a known method. At the time of mixing, additives can be mixed according to the purpose. Examples of such additives include curing agents, pigments, dyes, fillers, weathering materials, antioxidants, and ultraviolet absorbers.

The epoxy resin composition of the present invention has low viscosity, low irritation, low odor, and excellent mechanical properties after curing. It is suitably used for applications such as paints, flooring materials, and casting.

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

Example 1 Bisphenol A epoxy resin obtained by reacting bisphenol A with epichlorohydrin was subjected to molecular distillation to obtain a low molecular weight component and a viscosity of 4800 mP.
aS, 14% by weight of 1,6-hexanediol diglycidyl ether was added to 86% by weight of a bisphenol A type epoxy resin (a) having an epoxy equivalent of about 173, and the viscosity was 961.
An mPa.S epoxy resin composition was obtained. To this epoxy resin composition was added 66.4 parts of Ancamine 1618 (modified alicyclic polyamine-based curing agent, manufactured by Air Products), and 2
It was cured at 3 ° C. for 7 days to obtain a cured epoxy resin. Table 1 shows the physical properties of the obtained cured epoxy resin.

Example 2 Bisphenol A was reacted with an excessive amount of epichlorohydrin to obtain a low-molecular-weight component with a viscosity of 87.
Bisphenol A with an epoxy equivalent of about 180 mPa.S.
Type epoxy resin- (b) 83.5% by weight and a viscosity of 27 obtained by reacting bisphenol F with epichlorohydrin.
16.5% by weight of a bisphenol F type epoxy resin having an epoxy equivalent of 174 and a viscosity of 7000 mP.
An epoxy resin mixture of aS was obtained. 15% by weight of 1,6-hexanediol diglycidyl ether was added to 85% by weight of this epoxy resin mixture, and the viscosity was 1200 mPa.S.
Was obtained. To this epoxy resin composition, 65 parts of Ancamine 1618 (manufactured by Air Products) was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 1 shows the physical properties of the obtained cured epoxy resin.

Example 3 Bisphenol F type epoxy resin 8 used in Example 2
12% by weight of 1,6-hexanediol diglycidyl ether was added to 8% by weight to obtain an epoxy resin composition having a viscosity of 884 mPa.S. To this epoxy resin composition, 67.6 parts of Ancamine 1618 (manufactured by Air Products) was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 1 shows the physical properties of the obtained cured epoxy resin.

Example 4 Bisphenol A type epoxy resin used in Example 2
(b) 15% by weight of 1,6-hexanediol diglycidyl ether was added to 85% by weight to obtain an epoxy resin composition having a viscosity of 1300 mPa.S. To this epoxy resin composition, 64.5 parts of Ancamine 1618 (manufactured by Air Products) was added, and the mixture was cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 1 shows the physical properties of the obtained cured epoxy resin.

Example 5 Bisphenol A type epoxy resin used in Example 1
(a) 15% by weight of 1,6-hexanediol diglycidyl ether was added to 85% by weight to obtain an epoxy resin composition having a viscosity of 881 mPa.S. To this epoxy resin composition, 66.8 parts of Ancamine 1618 (manufactured by Air Products) was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin product. Table 1 shows the physical properties of the obtained cured epoxy resin.

Example 6 Bisphenol A type epoxy resin used in Example 1
(a) and the bisphenol A type epoxy resin (b) used in Example 2 were mixed at a ratio of 1: 1 to obtain an epoxy resin mixture having a viscosity of 6500 mPa.S. The epoxy resin mixture 85
15% by weight of 1,6-hexanediol diglycidyl ether was added to 1% by weight to obtain an epoxy resin composition having a viscosity of 1100 mPa.S. To this epoxy resin composition, 65.5 parts of Ancamine 1618 (manufactured by Air Products) was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 1 shows the physical properties of the obtained cured epoxy resin.

Example 7 Bisphenol A type epoxy resin used in Example 1
(a) and the bisphenol F type epoxy resin used in Example 2 were mixed at a ratio of 1: 1 to obtain an epoxy resin mixture having a viscosity of 3700 mPa.S. The epoxy resin mixture 8
12% by weight of 1,6-hexanediol diglycidyl ether was added to 8% by weight to obtain an epoxy resin composition having a viscosity of 1000 mPa.S. To this low-viscosity epoxy resin composition was added 65 parts of Ancamine 1618 (manufactured by Air Products), and the mixture was cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 1 shows the physical properties of the obtained cured epoxy resin.

COMPARATIVE EXAMPLE 1 9% by weight of butyl glycidyl ether was added to 91% by weight of a general-purpose bisphenol A type resin (c) having a viscosity of 13400 mPa.S and an epoxy equivalent of about 187 obtained by reacting epichlorohydrin with bisphenol A. And viscosity 1100mPa.S
Was obtained. Ancamine 1618 (manufactured by Air Products) 62.7 was added to this epoxy resin composition.
Was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 2 shows the physical properties of the obtained cured epoxy resin.
Shown in

Comparative Example 2 Bisphenol A type epoxy resin used in Example 2
(b) 13% by weight of C12-C14 higher alcohol glycidyl ether was added to 87% by weight to obtain an epoxy resin composition having a viscosity of 980 mPa.S. To this epoxy resin composition, 59.6 parts of Ancamine 1618 (manufactured by Air Products) was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 2 shows the physical properties of the obtained cured epoxy resin.

Comparative Example 3 Bisphenol A type epoxy resin used in Example 2
(b) 30% by weight of 1,6-hexanediol diglycidyl ether was added to 70% by weight to obtain an epoxy resin composition having a viscosity of 385 mPa.S. To this epoxy resin composition, 66.0 parts of Ancamine 1618 (manufactured by Air Products) was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 2 shows the physical properties of the obtained cured epoxy resin.

Comparative Example 4 25% by weight of 1,6-hexanediol diglycidyl ether was added to 75% by weight of the general-purpose bisphenol A type epoxy resin (c) used in Comparative Example 1, and an epoxy resin composition having a viscosity of 636 mPa.S I got To this epoxy resin composition, 53.6 parts of Ancamine 1618 (manufactured by Air Products) was added and cured at 23 ° C. for 7 days to obtain a cured epoxy resin. Table 2 shows the physical properties of the obtained cured epoxy resin.

Table 1 Example 1 2 3 4 5 6 7 Compressive strength 7.3 7.2 6.9 6.7 6.6 6.6 6.7 Compressive elasticity 213 210 196 207 207 206 205 Bending strength 7.7 7.2 6.8 7.2 6.9 6.9 6.7 Flexural modulus 276 253 239 299 299 284 284 247 All physical units are (kg / mm ² )

Table 2 Comparative Example 1 2 3 4 Compressive strength 6.9 6.0 4.1 5.0 Compressive modulus 212 185 139 --- Flexural strength 7.1 6.2 3.5 4.6 Flexural modulus 288 223 171 --- All units of physical properties are (kg / mm ² )

As is apparent from comparison of Examples 1 to 7 with Comparative Examples 2 to 4, the epoxy resin composition of the present invention has low viscosity and excellent mechanical properties. Further, the epoxy resin composition of the present invention achieves the same or higher mechanical properties and low viscosity as compared with the conventional product using butyl glycidyl ether described in Comparative Example 1, and has low vapor. Since 1,6-hexanediol diglycidyl ether, which is pressure and has low irritation, is used, there is little adverse effect on the working environment and the natural environment.

As is clear from the examples and comparative examples,
The epoxy resin composition of the present invention has both high mechanical properties and low viscosity. In addition, the epoxy resin composition of the present invention has low irritation and low odor without sacrificing mechanical properties and viscosity.

Claims (1)

[Claims] 1. An epoxy resin composition comprising 80-90% by weight of a bisphenol type epoxy resin having a viscosity at 25 ° C. of 10,000 mPa.S or less and 10-20% by weight of 1,6-hexanediol diglycidyl ether. .