JPH0959499A - Corrosion preventive lining composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a corrosion preventive lining composition excellent in defoamability and stability in viscosity even in a high viscosity state by combining a corrosion preventive lining composition with an organic bentonite and a small amount of a defoamer. SOLUTION: This composition is a corrosion preventive lining composition comprising (A) 100 pts.wt. unsaturated polyester or vinyl ester resin, (B) 10 to 100 pts.wt. glass flakes, (C) 0.5 to 20 pts.wt. thixotropic agent of an organic bentonite, and (D) 0.01 to 2 pts.wt. defoamer whose major components are an alkyl vinyl ether copolymer and mineral spirits.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a combination of an anticorrosion lining composition, an organic bentonite, and a small amount of an antifoaming agent, which is excellent in defoaming property even in a high viscosity state and improves defects caused by bubbles in a coating film. It is an object of the present invention to provide an anticorrosion lining composition which can be produced and has little change in viscosity with time and excellent storage stability.

[0002]

2. Description of the Related Art Originally, resin linings for the purpose of anticorrosion of metals have been applied to tanks, ship bottoms, exhaust ducts, etc., mainly in various chemical devices and environmental devices. As the resins used for these linings, unsaturated polyester resins, vinyl ester resins, and the like are used from the viewpoint of room temperature curability, price, and workability. As the lining method, FRP lining using glass fiber,
Flaking using glass flakes is often used. Glass flaking has excellent corrosion resistance by orienting the blended scale-like glass flakes in the coating film and significantly delaying the permeation of corrosive substances, so it is applied by spray coating or trowel coating. It

Since the glass flake lining material used as the lining material is applied to a vertical surface or troweled, it is necessary to increase the viscosity of the compound to be applied with fine silica to ensure workability. The defoaming property remarkably decreases due to the increase in viscosity. Further, since the glass flakes are oriented in the coating film, bubbles are more likely to remain, and the bubbles become defects in the coating film. Further, a resin whose viscosity has been increased by fine silica has a large change in viscosity over time due to the addition of a curing accelerator such as cobalt octenoate and is inferior in storage stability, which causes dripping during work. Conventionally, in order to solve this problem, the defoaming property was improved by adding a defoaming agent or an antifoaming agent, but the effect was not sufficient. Further, it was known that the addition of asbestos powder was effective for the change in viscosity with time, but it could not be used due to the carcinogenicity of asbestos.

[0004]

DISCLOSURE OF THE INVENTION The present invention uses an anticorrosion lining composition in combination with an organic bentonite and a small amount of an antifoaming agent to provide excellent defoaming properties even in a high viscosity state and excellent viscosity stability. Another object of the present invention is to provide an anticorrosion lining composition.

[0005]

[Means for Solving the Problems]

(A) 100 parts by weight of unsaturated polyester resin or vinyl ester resin, (B) 10 to 100 glass flakes
Parts by weight, (C) 0.5 to 20 parts by weight of a thixotropic agent consisting of organic bentonite, and (D) 0.01 to 2 parts by weight of an antifoaming agent whose main component is an alkyl vinyl ether copolymer and mineral spirits. The present invention relates to an anticorrosion lining composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester resin and vinyl ester resin (A) used in the present invention are described below. An unsaturated polyester resin and a vinyl ester resin are mixed with a polymerizable monomer. The unsaturated polyester is obtained by reacting an acid component, an alcohol component, and optionally a modifying component, but usually α, β-
Obtained by reacting an unsaturated dibasic acid and / or its acid anhydride and a polyhydric alcohol, and a saturated polybasic acid can be further reacted, if necessary.

Examples of the α, β-unsaturated dibasic acid and / or its acid anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid and maleic anhydride. These may be used in combination of two or more.

As the polyhydric alcohol, ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, 1,3-butanediol,
1,6-hexanediol, neopentyl glycol,
Dihydric alcohols such as 1,4-cyclohexanediol and hydrogenated bisphenol A, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol can be used. These may be used in combination of two or more.

Examples of the saturated polybasic acid used as necessary include phthalic acid, phthalic anhydride, trimellitic anhydride, succinic acid, azelaic acid, adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride and hexahydrophthalic acid. Acid, hexahydrophthalic anhydride, rosin-maleic anhydride adduct and the like. These may be used in combination of two or more.

The method for producing the unsaturated polyester is not particularly limited, and for example, it is carried out by subjecting the acid component and the alcohol component to a condensation reaction to release water generated when the two components react to the outside of the system. As the reaction device at this time, glass, stainless steel or the like is selected, and a stirring device, a diversion device for preventing the distillation of the alcohol component due to the azeotropic distillation of water and the alcohol component, and a heating device for increasing the temperature of the reaction system. It is preferable to use a reaction device equipped with a temperature control device for this heating device, a blowing device for nitrogen and the like. The reaction temperature is preferably 150 ° C. or higher, and it is preferable to carry out the reaction while aerating an inert gas such as nitrogen or carbon dioxide to prevent a side reaction due to oxidation.

The reaction proceeds while heating a system in which an acid component and an alcohol component are mixed, and removing low molecular weight compounds such as condensed water produced outside the system. This is preferably done by natural or vacuum distillation by passing an inert gas. A solvent such as toluene or xylene can be added to the system as an azeotropic component in order to accelerate the distillation of the condensed water. The progress of the reaction can be generally known by measuring the amount of distillate generated by the reaction, quantifying the functional group at the end, measuring the viscosity of the reaction system, and the like.

The vinyl ester is not particularly limited, and an epoxy resin, an unsaturated monobasic acid, and if necessary a polybasic acid reacted may be used. 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 AE manufactured by Asahi Kasei Kogyo Co., Ltd.
R-664H, AER-331, AER-337, trade name DER330, DER660, D.C.
There are ER664 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]. The commercially available product is DEN4 under the trade name of Dow Chemical Co., Ltd.
31, DEN438, trade name Epicoat 152, Epicoat 154 manufactured by Shell Chemical Co., Ltd., trade name EPN1 manufactured by Ciba
138 and the like.

The unsaturated monobasic acid which is reacted with the epoxy resin includes acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, tricyclo [5.2.1.0 ^2,6 ] -4-decene-8 or 9 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 and citraconic acid are heated at 70 to 150 ° C. under an inert gas stream. There is an unsaturated dibasic acid monoester obtained. Examples of the polybasic acid that is reacted as necessary include 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 the unsaturated monobasic acid and optionally the polybasic acid at a temperature of 60 to 150 ° C., preferably 70 to 130 ° C. to form a vinyl ester.

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.

Glass flakes (B) used in the present invention
Has an average thickness of 0.5 to 10 μm, preferably 3 to 5 μm.
It is a flat glass substance having a size of m and an average size of 100 to 4000 μm, preferably 150 to 300 μm. Since the glass flakes are laminated in parallel within the coating film, the glass flakes have the effects of improving the strength of the coating film and delaying the permeation of vapor, moisture and other corrosive substances from the outside. When the thickness of the glass flakes is less than 0.5 μm, the strength of the flakes is weak and breakage occurs when mixed with the resin.
On the other hand, when it exceeds 10 μm, the number of layers of parallel orientation in the coating film decreases, and the effect of preventing permeation of vapor, moisture and other corrosive substances from the outside decreases. If the size of the glass flakes is less than 100 μm, it becomes difficult to orient parallel to the material, and if it exceeds 4000 μm, the mixing with the resin becomes poor and the wettability of the glass flakes with the resin becomes poor. Glass flake is RCF from Nippon Glass Fiber Co., Ltd.
-600, RCF-140, RCF-015, REF-
It is commercially available under the trade name of GF-C150 from Asahi Fiber Co., Ltd. under the trade names of 600, REF-140 and REF-015. The amount of the glass flakes (B) used is the unsaturated polyester resin or vinyl ester resin (A) 10
The amount is 10 to 100 parts by weight with respect to 0 parts by weight. If the amount used is less than 10 parts by weight, it is not possible to prevent the permeation of steam, moisture and other corrosive substances from the outside, and if it exceeds 100 parts by weight, the flexibility of the coating film decreases and the adhesion to the material May worsen and cause blisters.

As the organic bentonite (C) used in the present invention, bentonite clay whose surface is organically treated is used. This commercially available product is B manufactured by RHEOX.
ENTON SD-2, BENTON SD-1, BE
NTON 27, BENTON 34, BENATHI
X, BENATHIX1-4-1, TIXOGEL VP, TIXOEL MP, T manufactured by Nissan Gardler Catalyst Co., Ltd.
IXOGEL MPZ, TIXOEL MP-250
and so on. The defoaming agent (D) used in the present invention contains an alkyl vinyl ether copolymer and mineral spirit as main components, and as a commercially available product, Byk
For example, Bymi-A515 manufactured by Chemi.

In the composition of the present invention, it is preferable to use cobalt octenoate or cobalt naphthenate as a curing accelerator. From the standpoint of effect, the amount used is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin or vinyl ester resin (A). Further, as a co-promoter, dimethylaniline, diethylaniline,
It is preferable to use 0.01 to 1.0 part by weight of N, N-dimethylparatoluidine or the like with respect to 100 parts by weight of the vinyl ester resin. Furthermore, it is preferable to add hydroquinone, methylhydroquinone, tertiary butyl catechol, p-benzoquinone or the like as a polymerization inhibitor to the anticorrosion lining composition of the present invention. Fillers such as calcium carbonate, barium hydroxide, aluminum hydroxide, talc, and glass powder, and pigments can be added to the composition of the present invention. Further, a silane coupling agent or the like can be added to improve the coupling between the glass flakes and the vinyl ester resin.

[0018]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight”. Example 1 60 parts of Polyset 6120S (vinyl ester resin, trade name of Hitachi Chemical Co., Ltd.), 0.5 parts of 6% cobalt octenoate solution, 0.1 parts of N, N-dimethylparatoluidine, 0.04 parts of methyl hydroquinone, BEN
ATHIXI-4-1 (organic bentonite, RHEOX
5 parts by product name), Byk-A515 (an antifoaming agent whose main component is an alkyl vinyl ether copolymer and mineral spirits, Byk chemi product name) by 0.1 part, RC
35 parts of F-140 (glass flakes, trade name of Nippon Glass Fiber Co., Ltd.) was added, and well stirred and dispersed by a stirrer to prepare compound A.

Comparative Example 1 Compound B was prepared in the same manner as in Example 1 except that the defoaming agent Byk-A515 was not added.

Comparative Example 2 A compound C was prepared in the same manner as in Example 1 except that the defoaming agent Byk-A515 was not added.

Comparative Example 3 In Example 1, the antifoaming agent Byk-A515 was replaced with the antifoaming agent B.
Compound D was prepared in the same manner as in Example 1 by substituting yk-A501 (butadiene polymer system).

Comparative Example 4 In Example 1, the antifoaming agent Byk-A515 was replaced with the antifoaming agent B.
Compound E was prepared in the same manner as in Example 1 by substituting yk-A506 (silicon type).

Comparative Example 5 To 60 parts of Polyset 6120S, 0.5 part of 6% cobalt octenoate solution, 0.5 part of N, N-dimethylparatoluidine, 0.05 part of methylhydroquinone, and Aerosil 200 (fine silica) , Thixotropic agent, trade name of Nippon Aerosil Co., Ltd., 3 parts, 0.06 part of Tween 20 (polymer nonionic surfactant, thixotropic agent, trade name of Kao Atlas Co., Ltd.), Byk-A515 (an antifoaming agent containing alkyl vinyl ether copolymer and mineral spirit as a main component, trade name by Byk chemi) 0.1 part, RC
35 parts of F-140 (glass flake, trade name of Nippon Glass Fiber Co., Ltd.) was added, and well stirred and dispersed by a stirrer to prepare compound F.

Comparative Example 6 Compound G was prepared in the same manner as in Comparative Example 5 except that the defoaming agent Byk-A515 was not added in Comparative Example 5.

Comparative Example 7 Compound H was prepared in the same manner as in Comparative Example 5, except that the defoaming agent Byk-A515 was not added.

Comparative Example 8 In Comparative Example 5, the antifoaming agent Byk-A515 was replaced with the antifoaming agent B.
Compound I was prepared in the same manner as in Comparative Example 5 by substituting yk-A501 (butadiene polymer system).

Comparative Example 9 In Comparative Example 5, the antifoaming agent Byk-A515 was replaced with the antifoaming agent B.
Compound J was prepared in the same manner as in Comparative Example 5 by replacing yk-A506 (silicon type).

(Test Example) Specific densities of the cured products of the compounds (A to J) obtained in Example 1 and Comparative Examples 1 to 9 and the compounds (A and F) obtained in Example 1 and Comparative Example 5 The change in viscosity with time was examined under the following conditions, and the results are shown in Tables 1 and 2.

[0029]

[Table 1]

[0030]

[Table 2]

(1) Specific gravity of cured compound After defoaming the compound under reduced pressure, 2.0 parts of 55% by weight methyl ethyl ketone peroxide was added, dispersed with a stirrer, and poured onto a metal Petri dish of φ60 (mm). Molded, about 6
After being left at room temperature for 80 hours, post-curing was performed at 80 ° C. for 2 hours, and the test piece was removed from the petri dish. This test piece is JIS
The specific gravity was measured by K6911, and the larger the specific gravity, the better the defoaming property. Comparative example 1 and comparative example 6
For, in order to create a completely defoamed condition, defoaming was further performed under reduced pressure before casting in a petri dish.

(2) Change in viscosity with time A change in viscosity was measured under the following conditions by heating the compound at 50 ° C. for an acceleration test. (A) Viscosity The viscosity was measured according to JIS K6901. A BH type viscometer was used as the viscometer.

From Table 1, it can be seen that Example 1 has the closest specific gravity to Comparative Example 1 degassed under reduced pressure and is excellent in defoaming property. Further, it can be seen from Table 2 that Example 1 has a small decrease in viscosity and is excellent in storage stability.

[0034]

EFFECTS OF THE INVENTION By using the anticorrosion lining composition obtained by the method of the present invention, even in a high viscosity state, the defoaming property is excellent, defects due to bubbles in the coating film can be improved, and the viscosity changes with time. It is possible to obtain an anticorrosion lining composition having a low storage stability and excellent storage stability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C09D 167/06 PEC C09D 167/06 PEC

Claims (1)

[Claims] 1. An unsaturated polyester resin or vinyl ester resin (A) 100 parts by weight, (B) glass flakes 10 to 100 parts by weight, and (C) an organic bentonite thixotropic agent 0.5 to 20 parts by weight. , (D) an anticorrosion lining composition containing 0.01 to 2 parts by weight of an antifoaming agent containing (D) an alkyl vinyl ether copolymer and mineral spirit as main components.