JPH0730235B2 - Haku modified epoxy resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy resin composition used for, for example, paints, adhesives, sealing agents, and the like, and more specifically, thixotropic epoxy resin. The present invention relates to improvements in resin compositions.

[Conventional technology]

In the epoxy resin composition used for the above applications, an inorganic filler is usually added in order to improve the workability and reduce the cost, but thixotropic is used to prevent the sedimentation of the inorganic filler. Need to be granted.

Conventionally, a thixotropic material such as finely powdered silica, finely powdered aluminum silicate, organic bentonite, or castor oil hardened oil has been used to impart thixotropic properties to a liquid epoxy resin.

[Problems to be Solved by the Invention]

If an inorganic substance such as finely powdered silica or finely powdered calcium silicate is used as the thixotropic material for epoxy resin, the viscosity of the composition increases at the same time that thixotropy appears, resulting in a decrease in workability. Therefore, the complicated work of thoroughly mixing with three paint rolls is required. Moreover, when this composition is cured, the hardness of the cured product becomes high, and the internal stress generated during curing is less likely to be relaxed, resulting in a so-called brittle cured product.

On the other hand, when a thixotropic material composed of an organic substance such as castor oil hydrogenated oil or fatty acid bisamide is used, expression of thixotropy is caused by recrystallization or swelling. It is difficult to control the temperature, time, stirring method, etc. Further, there is a drawback that the adhesiveness is deteriorated when a large amount of these is used.

An object of the present invention is to provide a thixotropic epoxy resin composition which is small in changes in adhesiveness and physical properties of a cured product and can be easily obtained.

[Means and Actions for Solving Technical Problems]

The present inventor, as a result of extensive studies to solve the above problems, a formulation containing a specific liquid epoxy resin and a specific alkaline inorganic powder, if containing a dialkyltin laurate compound, adhesiveness and The inventors have found that changes in the physical properties of a cured product can be reduced, and have completed the present invention.

That is, the present invention comprises calcium carbonate, magnesium carbonate, cement, talc, and sodium hydrogen carbonate based on 100 parts by weight of at least one liquid epoxy resin selected from the group consisting of bisphenol A type and bisphenol F type. A thixotropic epoxy resin composition comprising 10 to 200 parts by weight of at least one alkaline inorganic powder selected from the group and 0.1 to 10 parts by weight of a dialkyltin laurate compound.

Epoxy resins other than the above liquid epoxy resin cannot exhibit excellent thixotropy as in the present invention in the uncured state in the combination of the alkaline inorganic powder and the dialkyltin laurate compound.

Further, when the amount of the alkaline inorganic powder added is less than 10 parts by weight, it becomes difficult to impart an appropriate viscosity to the composition in an uncured state, and further, the shear strength and T-type peel strength of the cured product after curing. It becomes difficult to obtain sufficient physical properties such as. On the other hand, if the amount exceeds 200 parts by weight, the clay of the composition becomes too high and the workability is deteriorated and sufficient thixotropy cannot be obtained.

If necessary, butyl glycidyl ether (BGE)
And a non-reactive diluent such as toluene, methyl ethyl ketone (MEK), benzyl alcohol or acetylacetone can be added.

Examples of the dialkyltin laurate compound include dibutyltin dilaurate and a reaction product of dibutyltin dilaurate and dibutyltin oxide. The amount of the dialkyltin laurate compound added is determined according to the amount, type and application of the inorganic powder. If it is less than 0.1 part by weight, the thixotropic effect is small, and if it exceeds 10 parts by weight, the cured product is cured. It affects durability and is not preferable in terms of cost.

If necessary, other thixotropic materials such as fine powder silica
It is also possible to add castor oil and hydrogenated oil together.

In the present invention, thixotropy is imparted because the dialkyltin laurate compound is polarized and the tin atom has an affinity for the alkaline inorganic powder, while the alkyl group and the laurate group have an affinity for the epoxy resin. It is considered that this is due to the presence of a weak interaction between the particles due to such a state, thereby exhibiting thixotropic properties.

[Explanation of Examples]

Hereinafter, representative examples of the present invention will be described in comparison with comparative examples.

Comparative Examples 1 to 9 50 parts by weight of the inorganic powder shown in Table 1 was weighed with respect to 100 parts by weight of the liquid epoxy resin, stirred with a three-one motor for 15 minutes, and uniformly dispersed, then, in an atmosphere of 23 ° C. Let stand for one day. Next, the rotational speed dependence of the viscosity was measured with a B8U type viscometer (manufactured by Tokyo Keiki Co., Ltd.), and the ratio between the viscosity at 10 rpm and the viscosity at 100 rpm was calculated using rotor No. 6.

Further, the obtained composition was allowed to stand in a constant temperature layer at 50 ° C. for 1 month, and the state of sedimentation of the inorganic powder was observed.

Examples 1 to 9 After uniformly dispersing the inorganic powder as in Comparative Examples 1 to 9,
The dialkyl tin laurate compounds were weighed and mixed in the proportions shown in Table 2, and the rotational speed dependence of viscosity was measured and calculated in the same manner as in Comparative Examples 1-9. Further, similarly to Comparative Examples 1 to 9, the sedimentation of the inorganic powder was also observed.

However, in Tables 1 and 2 above, heavy calcium carbonate: Whiten SB (manufactured by Shiraishi Calcium Co., Ltd.).

Light calcium carbonate: Silver W (manufactured by Shiraishi Calcium Co.).

Cement: Alofix-DU (manufactured by Onoda Cement Co.).

Epicoat 828: Bisphenol A type diglycidyl ether (produced by Yuka Shell Epoxy Co., Ltd.).

Epicoat 807: Bisphenol F-type diglycidyl ether (Id.).

Epikote 815: Epikote 828 / BGE = 90/10 mixture (Id.).

EROSIL 200: Ultrafine particulate anhydrous silica (manufactured by Nippon Aerosil).

Disbaron 305: Castor oil hydrogenated oil (Kusumoto Kasei Co., Ltd.).

Stann BL: Dibutyltin dilaurate (manufactured by Sansha Kisei Co., Ltd.).

SB65: Reaction product of dibutyltin dioxide and Stann BL.

Caking: The state in which the precipitated inorganic filler was solidified and was not uniform with light agitation was defined as "present".

From Table 2, it is understood that caking does not occur in any of Examples 1 to 9. Further, in Comparative Example 9, the viscosity ratio is high although no caking occurs, whereas in Examples 1 to 9, the viscosity ratio is not high.

Example 10 To 153 g of the same epoxy resin composition as in Example 1, 100 g of polyaminoamide (Tomeide 2151: manufactured by Fuji Kasei Kogyo Co., Ltd.) was mixed and stirred, whereby soft steel plates were fixed to each other with a bonding clip, and at 23 ° C After curing for 7 days, the tensile shear strength and T-type peel strength were measured. The results are shown in Table 3.

Comparative Examples 10 and 11 To 150 g of the same epoxy resin composition as in Comparative Examples 1 and 9, 100 g of Tomeide 2151 was mixed and stirred, and bonded and cured under the same conditions as in Example 10 to obtain tensile shear strength and T-type peeling. The strength was measured. The results are also shown in Table 3.

(However, the measurement ratio in Table 3 is an average value of three test numbers) [Effect of the invention] As is clear from the above-mentioned examples, in the thixotropic epoxy resin composition according to the present invention, mixing and stirring were not performed. It's easy. Therefore, it is possible to omit the use of three paint rolls and heating. Further, in the conventional thixotropic epoxy resin composition, since the stirring and mixing are not easy, the properties tend to vary depending on the manufacturing conditions.However, in the present invention, the mixing and stirring are easy, so that the composition having a uniform property is obtained. Things can be obtained stably and easily. Moreover, the thixotropic material used in the present invention has almost no influence on the adhesiveness.

Claims (1)

[Claims] 1. At least one liquid epoxy resin selected from the group consisting of bisphenol A type and bisphenol F type 100 parts by weight selected from the group consisting of calcium carbonate, magnesium carbonate, cement, talc and sodium hydrogen carbonate. A thixotropic epoxy resin composition comprising 10 to 200 parts by weight of at least one kind of alkaline inorganic powder and 0.1 to 10 parts by weight of a dialkyltin laurate compound.