JPH08134155A - Thixotropic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition suitable for providing a fiber- reinforced plastic with excellent appearance and corrosion resistance due to excellent allowance of viscosity and degree of thixotropy and no sagging, comprising a vinyl ester resin, a specific thixotropy imparting agent and a urethane prepolymer. CONSTITUTION: This composition comprises (A) a vinyl ester resin [e.g. one obtained by reacting an epoxy resin of the formula ((k) is 0-15) with an unsaturated monobasic acid such as (meth)acrylic acid and optionally a polybasic acid such as phthalic anhydride and dissolving the reaction product in a polymerizable monomer after the reaction], (B) a thixotropy imparting agent prepared by treating a quaternary ammonium salt of an organic compound with bentonite clay and (C) a urethane prepolymer. The contents of the components are 0.5-20 pts.wt. of the component Band 0.01-2 pts.wt. of the component C based on 100 pts.wt. of the component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thixotropic resin composition having excellent viscosity and thixotropic property.

[0002]

2. Description of the Related Art Conventionally, thixotropic resin compositions are (1) coated with a synthetic resin paint, particularly when thickly applied,
(2) When a surface resin layer called a gel coat or a top coat layer is applied in order to improve the aesthetic appearance and the corrosion resistance of the surface of a reinforced plastic molded product such as a bath or a corrosion resistant tank, (3) a reinforced plastic. It is used for molding by hand lay-up method or spray-up method in the molding process of molded products, but there are problems such as so-called “dripping” and “sliding off” of the resin during or after the work. Likely to happen. For example, in the case of thick coating at the time of coating, or when the viscosity and thixotropy of the liquid resin used for the gel coat and the top coat layer are small, so-called "dripping" occurs and the thickness of the top coat layer becomes non-uniform. Corrosion resistance and appearance cannot be obtained.
Also, when performing reinforced plastic molding work by the hand lay-up method and spray-up method, an appropriate viscosity,
If the degree of thixotropy is not maintained, resin sagging and vertical laminated surface “sliding” occur, and excellent molded products cannot be made. This is particularly noticeable in spray-up molding operations.

Therefore, conventionally, various kinds of inorganic or organic substances have been added to such resins to increase the viscosity of the liquid resin and to impart thixotropy. In particular, vinyl ester resins are difficult to impart thixotropy with ordinary fine silica used in unsaturated polyester resins (for example, Nippon Aerosil Co., Ltd., trade name: Aerosil, Aerosil).

Therefore, a clay surface such as bentonite clay which has been subjected to an organic treatment and a fine silica surface treated to have been used. However, if the addition amount of the thixotropic agent is increased in order to impart thixotropy, the corrosion resistance and appearance of the resin may be deteriorated. Further, the addition of a polar solvent such as methanol or ethylene glycol as an auxiliary agent increases thixotropy, but its effect is not sufficient.

[0005]

SUMMARY OF THE INVENTION The present invention uses a urethane prepolymer when using a thixotropic agent obtained by treating bentonite clay with a quaternary ammonium salt of an organic compound in order to impart thixotropy to a vinyl ester resin. By doing so, a thixotropic resin composition excellent in imparting thixotropy is provided.

[0006]

The present invention contains (A) a vinyl ester resin, (B) a bentonite clay treated with a quaternary ammonium salt of an organic compound, and (C) a urethane prepolymer. The present invention relates to a thixotropic resin composition.

The vinyl ester resin used in the present invention is not particularly limited, and is obtained by reacting an epoxy resin, an unsaturated monobasic acid and, if necessary, a polybasic acid, and dissolving the resulting mixture in a polymerizable monomer. To be

There is no particular limitation on the epoxy resin, for example, the general formula

Embedded image [In the formula, x means an integer in the range of 0 to 15]. The commercially available products are Epicoat 828 and Epicoat 100 manufactured by Shell Chemical Co., Ltd.
1. Epicoat 1004, product name AER manufactured by Asahi Kasei Corporation
-664H, AER-331, AER-337, trade name D.C. manufactured by Dow Chemical Company. E. FIG. R. 330, D.I. E. FIG. R. 6
60, D.I. E. FIG. R. 664 etc. Also, the general formula is

Embedded image [Wherein, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group, and x represents an integer in the range of 0 to 15]. As this commercially available product, trade name D. E. FIG.
N. 431, D.I. E. FIG. N. 438, Epichemical 152 and Epicoat 154 manufactured by Shell Chemical Co., and EPN1138 manufactured by Ciba.

[0009] The unsaturated monobasic acid to be reacted with epoxy resin, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, tricyclo [5.2.1.0 ^{2 '6]} -4-decene -8 or 6 A residue and a partially esterified carboxylic acid containing an unsaturated dibasic acid residue as a constituent can be used. Examples of partially esterified carboxylic acids are 8- or 9-hydroxytricyclodecene-4- [5.2.
1.0 ² ' ⁶ ] 1.00 to 1.20 mol and 1 mol of an unsaturated dibasic acid such as maleic anhydride, itaconic acid, citraconic acid, etc. are heated at 70 to 150 ° C under an inert gas stream. There is an unsaturated dibasic acid monoester obtained.

The polybasic acid which is reacted as required includes phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, glutaric acid, adipic acid. , Sebacic acid, trimellitic acid, pyromellitic acid, dimer acid and the like.

The epoxy resin is reacted with an unsaturated monobasic acid and optionally a polybasic acid at a temperature of 60 to 150 ° C, preferably 70 to 130 ° C. The unsaturated monobasic acid and the polybasic acid used as necessary are preferably used in such a ratio that the carboxyl groups of these acid components and the epoxy groups in the epoxy resin are almost equivalent. In the reaction, hydroquinone, parabenzoquinone, p-tertiary butyl catechol, in order to prevent gelation due to polymerization,
It is preferable to use a polymerization inhibitor such as hydroquinone monomethyl ether. In the esterification reaction, quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride and stannic chloride. The reaction time can be shortened by using an esterification catalyst such as.

The polymerizable monomer is used alone or in combination with other polymerizable monomers. Other polymerizable monomers include, for example, styrene, chlorostyrene, divinylbenzene, tertiary butyl styrene, styrene bromide,
Diallyl phthalate, methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, β-
Ethyl hydroxymethacrylate, ethyl β-hydroxyacrylate, acrylamide, phenylmaleimide and the like are used. Further, polyfunctional (meth) acrylic acid esters such as ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimetatyl propane trimethacrylate can also be used.

The thixotropic agent obtained by treating the bentonite clay used in the present invention with a quaternary ammonium salt of an organic compound is BENTON manufactured by NL Chemical.
SD-2, BENTON SD-1, BENTON 2
7, BENTON 34, TIX made by Nissan Gardler Catalyst
OGEL VP, TIXOEL MP, TIXOGE
L MPZ, TIXO GEL MP-250 and the like.

The urethane prepolymer used in the present invention is obtained by reacting an organic isocyanate with a polyester polyol.

As the organic isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and the like are used. As the polyester polyol, one obtained by reacting a linear dicarboxylic acid such as adipic acid with a linear diol such as 1,4 butanediol, 1,6 hexanediol or polyethylene glycol is used. Examples of this commercially available product include Byk-LP-W6236. As the catalyst, amine, diamine or the like is used. This commercially available product is Byk-LP-W6236.
(A mixture of 70% by weight of urethane prepolymer and 30% by weight of butyl acetate).

From the viscosity of the composition, vinyl ester resin 1
It is preferable to use 0.5 to 20 parts by weight of a thixotropic agent obtained by organically treating bentonite clay and 0.01 to 2 parts by weight of a urethane prepolymer with respect to 00 parts by weight.

In the composition of the present invention, it is preferable to use cobalt octenoate or cobalt naphthenate as a curing accelerator. From the viewpoint of effect, the amount used is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the vinyl ester resin. Further, as a co-promoter, dimethylaniline, diethylaniline, N, N-dimethylparatoluidine, etc. are added in an amount of 0.01 to 100 parts by weight based on 100 parts by weight of the vinyl ester resin.
It is preferable to use 1.0 part by weight.

Further, in the thixotropic resin composition of the present invention, hydroquinone, methylhydroquinone, tertiary butyl catechol, p-benzoquinone and the like as polymerization inhibitors are added in an amount of 0.005 with respect to 100 parts by weight of the vinyl ester resin.
It is preferable to use 0.1 to 0.1 parts by weight.

The composition of the present invention contains 10 to 300 parts by weight of fillers such as calcium carbonate, barium hydroxide, aluminum hydroxide, talc, glass flakes, glass powder, and pigments, and 100 parts by weight of vinyl ester resin. You can add parts.

[0020]

The present invention will be described below with reference to examples. In the examples, “part” means “part by weight”, and “%” means “% by weight”. Example 1 100 parts of Polyset 6120S (vinyl ester resin, trade name manufactured by Hitachi Chemical Co., Ltd.), BENTON SD-2
(Quaternary ammonium salt treated bentonite clay, NL
Chemical product name), 2 parts, Byk-LP-W
6236 (urethane prepolymer 70% butyl acetate 30
% Of the mixture (trade name, manufactured by Bykchemi) was added, and well stirred and dispersed by a stirrer. Using a Brookfield type (BL type) rotational viscometer, JI
The viscosity and the degree of thixotropy were measured according to S-K6091. The viscosity is measured by using a viscometer rotor # 3 at 60 rpm. The thixotropy was defined as the ratio of the viscosity measurement values at 6 rpm and 60 rpm. The degree of rocking was 1.7.

Comparative Example 1 In Example 1, the same evaluation as in Example 1 was performed without adding the urethane prepolymer. The degree of thixotropic change was 0.9.

Comparative Example 2 The same evaluation as in Example 1 was carried out by replacing the urethane prepolymer in Example 1 with methanol. The degree of thixotropic change was 1.0.

Comparative Example 3 In Example 1, the urethane prepolymer was replaced with ethylene glycol, and the same evaluation as in Example 1 was performed.
The degree of thixotropic change was 1.0.

Comparative Example 4 In Example 1, the urethane prepolymer was replaced with glycerin, and the same evaluation as in Example 1 was performed. The degree of thixotropic change was 1.0. Table 1 shows the above results.

[Table 1]

Example 2 100 parts of Polyset 6120S (vinyl ester resin, trade name of Hitachi Chemical Co., Ltd.) was added to TIXOGEL MP-
2 parts of 250 (Quaternary ammonium salt treated bentonite clay, trade name of Nissan Gardler Catalyst), Byk-L
Add 0.5 parts of P-W6236, stir well with a stirrer,
Dispersed. This resin was evaluated in the same manner as in Example 1. The degree of rocking was 1.7.

Comparative Example 5 In Example 1, the same evaluation as in Example 1 was performed without adding the urethane prepolymer. The degree of thixotropic change was 1.0.

Comparative Example 6 The same evaluation as in Example 1 was carried out by replacing the urethane prepolymer in Example 1 with methanol. The degree of rocking was 1.2.

Comparative Example 7 The same evaluation as in Example 1 was carried out by replacing the urethane prepolymer in Example 1 with ethylene glycol.
The degree of rocking was 1.5.

Comparative Example 8 In Example 1, the urethane prepolymer was replaced with glycerin and the same evaluation as in Example 1 was performed. The degree of rocking was 1.5. Table 2 shows the above results.

[Table 2]

[0030]

The thixotropic resin composition of the present invention is a thixotropic resin composition having an improved thixotropic effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // (C08L 63/10 75:04)

Claims (1)

[Claims] 1. A thixotropic resin composition comprising (A) a vinyl ester resin, (B) a bentonite clay treated with a quaternary ammonium salt of an organic compound, and (C) a urethane prepolymer. .