JP2643463B2 - Flake lining composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a composition for a flaking material, and more particularly to a composition for a flaking material having excellent storage stability.

[Conventional technology]

BACKGROUND ART Conventionally, resin linings for the purpose of corrosion prevention and rust prevention of metals have been used for chemical devices, pipes, various types of interference prevention devices, bridges, and the like. As the resin lining, for example, an FRP lining method using glass fiber as a reinforcing material and a frame lining method using a glass frame are known.

The FRP lining method is a method of impregnating a lining resin mixed with a curing agent in advance, defoaming and curing the glass fiber while attaching the glass fiber to the object to be coated. Alternatively, a glassy flaky glass flake is mixed and applied to an object using a trowel or a spray machine. In these methods, a room temperature curing method is adopted from the viewpoint of workability in the field, so that epoxy resins, unsaturated polyester resins, unsaturated epoxy ester resins, etc. that can be cured at room temperature are used as the lining resin. ing. Of these, the curing time can be freely adjusted, and unsaturated epoxy ester resin having excellent corrosion resistance is mainly used.In recent years, however, the corrosion resistance of the object to be coated having a complicated shape has been increased with the increase in the service life of the object to be coated. For this reason, a flare lining method using an unsaturated epoxy ester resin has attracted attention.

The flaking composition must be capable of being cured at room temperature, and in order to improve the workability, it is necessary to mix an accelerator that promotes the curing of the resin in advance. However, unsaturated epoxy ester resins have poor storage stability, and have a drawback of gelling within 30 days after resin production in an atmosphere exceeding 30 ° C. Also, when a flaking composition is manufactured by mixing an accelerator in advance with the resin,
There is a problem that the gelation period after production is further shortened.
In order to improve the storage stability of such an unsaturated epoxy ester resin, studies have been made on the addition of inhibitors, preservation methods, etc. .

However, the place where the flaking composition is used is often outdoors, and it is difficult to secure a storage place in a cool and dark place. For this reason, especially in the summer, there has been a problem that the flaking composition often gels during the start of construction and cannot be used.

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and to provide a flaking composition having excellent storage stability.

[Means for solving the problem]

The present invention relates to (A) a polyepoxide having an equivalent amount of α · β
A modified unsaturated epoxy ester obtained by reacting an unsaturated epoxy ester obtained by reacting an unsaturated basic acid with 2 to 10 mol% of an acid anhydride based on hydroxyl groups of the unsaturated epoxy ester; 100 parts by weight of a modified unsaturated epoxy ester resin composed of 90 parts by weight and 70 to 10 parts by weight of an unsaturated monomer, (B) an average thickness of 0.5 to 10 microns, and an average size of 100 to 100 parts by weight 10-60 parts by weight of glass flakes of 4000 microns and (C) N,
The present invention relates to a flaking composition containing 0.01 to 2 parts by weight of N-dimethylparatoluidine.

Α · equivalent to the polyepoxide used in the present invention.
A modified unsaturated epoxy ester obtained by reacting, for example, maleic anhydride with an unsaturated epoxy ester obtained by reacting a β-unsaturated basic acid can be obtained, for example, by the following reaction formula.

(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represent hydrogen or an alkyl group) The polyepoxide is a compound containing one or more epoxy groups per molecule. Glycidyl polyethers of polyhydric alcohols or phenols, epoxidized fatty acids or drying oils, epoxidized diolefins,
Esters of epoxidized diunsaturated acids, epoxidized saturated polyesters and the like can be used.

As the α-β-unsaturated basic acid, methacrylic acid, acrylic acid, crotonic acid and the like can be used, and these can be used in combination.

As the acid anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Trimellitic anhydride, pyromellitic anhydride, endmethylene-tetrahydrophthalic anhydride and the like can be used. The acid anhydride is used in a proportion of 2 to 10 mol% based on the hydroxyl groups of the unsaturated epoxy ester.
If the amount of the acid anhydride used is out of this range, the storage stability of the unsaturated epoxy ester resin will not be structured, and the unsaturated epoxy ester resin will gel.

In the reaction, as an addition catalyst, zinc chloride, halides such as lithium chloride, dimethyl sulfide, sulfides such as methylphenyl sulfide, dimethyl sulfoxide, methyl sulfoxide, sulfoxides such as methyl ethyl sulfoxide, N-N dimethylaniline, Tertiary amines such as pyridine, triethylamine and hexamethylenediamine and their hydrochlorides or bromates; quaternary ammonium salts such as tetramethylammonium chloride and trimethyldodecylbenzylammonium chloride; sulfonic acids such as paratoluenesulfonic acid; Mercaptans such as mercaptan and propylmercaptan are used.

The modified unsaturated epoxy ester resin (A) used in the present invention comprises 30 to 90 parts by weight of a modified unsaturated epoxy ester and 70 to 10 parts by weight of an unsaturated monomer.
When the amount of the unsaturated epoxy ester used is outside this range,
That is, if it is less than 30% by weight, the viscosity is too low, and if it exceeds 90% by weight, the viscosity becomes too high to obtain a flaking composition.

As unsaturated monomers, styrene, vinyl toluene,
Ethyl vinyl benzene, isopropyl styrene, tertiary butyl styrene, α-methyl styrene, sec-butyl styrene, divinyl benzene, halogenated styrene,
Examples include diallyl phthalate, triallyl cyanurate, acrylic acid, vinyl acetate, acrylates such as methyl acrylate and ethyl acrylate, and methacrylates such as methyl methacrylate and ethyl methacrylate.

The glass flake (B) used in the present invention has an average thickness of 0.5 to 10 microns, preferably 3 to 5 microns,
And the average size is 100-4000 microns, preferably 1
It is a flat glass material that is 50-300 microns. Since the glass flakes are laminated in layers in the coating film in parallel, the strength of the coating film is improved, and steam from the outside,
It has the effect of delaying the transmission of moisture and other corrosive substances. If the thickness of the glass flakes is less than 0.5 micron, the strength of the flakes is low and breakage occurs when mixed with the resin.If the thickness exceeds 10 microns, the number of parallel-oriented layers in the coating film decreases, and external steam and moisture The effect of preventing permeation of other corrosive substances is reduced. If the size of the glass flakes is less than 100 μm, it is 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 flake surface by the resin becomes poor. Glass flakes are CCF-04 from Nippon Glass Fiber Co., Ltd.
8, CCF-150, CCF-325, GF-C15 from Asahi Fiber Co.
It is marketed under the trade name 0. The amount of the glass flake (B) used is the same as that of the modified unsaturated epoxy ester resin (A).
It is 10 to 60 parts by weight for 100 parts by weight. If the amount is less than 10 parts by weight, penetration of steam, moisture and other corrosive substances from the outside cannot be prevented, and if it exceeds 60 parts by weight, the flexibility of the coating film is reduced, and the adhesion to the material is reduced. Worsens, causing blisters.

In the composition of the present invention, N, N-dimethylparatoluidine (C) is used as an accelerator. As the accelerator for the unsaturated epoxy ester resin, usually, amines are used.In the present invention, in order to improve the storage stability of the modified unsaturated modified epoxy ester resin, N, N-dimethyl paratoluidine is used as an accelerator. Must be used as The amount used is 0.01 to 2 parts by weight based on 100 parts by weight of the modified unsaturated epoxy ester resin. If the amount is less than 0.01 part by weight, there is no effect as an accelerator, and if it exceeds 2 parts by weight, curing of the modified unsaturated epoxy ester resin becomes too fast to be practical.

In the composition of the present invention, it is preferable to use cobalt octenoate or cobalt naphthenate in addition to the accelerator. The use amount is preferably 0.1 to 2 parts by weight based on 100 parts by weight of the modified unsaturated epoxy ester resin. If the amount is less than 0.1, the effect as an accelerator cannot be exhibited, and if it exceeds 2 parts by weight, a retarding effect occurs, so that it may not be practically used.

In the composition of the present invention, it is preferable to use a thixotropic agent such as silicon oxide and organic bentonite, and the amount used is 1 to 10 parts by weight based on 100 parts by weight of the modified unsaturated epoxy ester resin. Is preferred. 1 usage
If the amount is less than 10 parts by weight, thixotropic properties are insufficient, so that "sagging" may occur when applied to a vertical surface. If the amount exceeds 10 parts by weight, the viscosity of the resin may be too high to be practically used.

Furthermore, in the composition of the present invention, hydroquinone, tertiary butyl catechol, p-benzoquinone, 2,5-ditertiary butyl hydroquinone and the like are used as polymerization inhibitors.

Fillers such as calcium carbonate, barium hydroxide, aluminum hydroxide, talc and the like can be added to the composition of the present invention.

The flaking composition according to the present invention can be cured at room temperature using an organic peroxide suitable for redox polymerization, particularly methyl ethyl ketone peroxide.In addition to redox polymerization, thermal polymerization, ultraviolet polymerization, A curing method by electron beam polymerization can also be employed.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition,
In the examples, “parts” means “parts by weight”.

Example 1 1) Production of Modified Unsaturated Epoxy Ester Resin (A) Diglycidyl ether of 4,4'-isopropylidene diphenol (Ep-828, manufactured by Shell Chemical Company, epoxy equivalent: 1)
88) 376 parts, 172 parts of methacrylic acid, 2 parts of benzylmethylamine and 0.05 part of hydroquinone were charged and reacted at 115 ° C. When the acid value becomes 0 or 24 parts of maleic anhydride are added to the kettle, the reaction is stopped when the acid value becomes 24, and 70 parts of the obtained reaction product is dissolved in 30 parts of styrene. A modified unsaturated epoxy ester resin (A-1) was obtained.

2) Preparation and Evaluation of Flake Lining Composition Using the obtained resin (A-1), the inside of the flaking lining composition was prepared as follows according to the blending amounts and blending amounts (parts by weight) shown in Table 1.

First, an organic bentonite is added to the resin (A-1) and rolled to impregnate the organic bentonite into the resin. Thereafter, N, N-dimethylparatoluidine and cobalt naphthenate are added and dispersed, and the glass flakes ( Average thickness: about 3 microns, average size: 140 microns, Nippon Glass Fiber Co., Ltd. CCF-150) and titanium oxide were dispersed therein.

The obtained composition was placed in a 1000 ml can, covered, and placed in a drier at 40 ° C., and the time required for gelation (storage stability) was examined. Further, 1% by weight of methyl ethyl ketone peroxide was added to the composition, and the pot life was measured at 25 ° C.
The results are shown in Table 1.

Comparative Examples 1-4 Unsaturated epoxy ester resin (A-2) was prepared in the same manner as in Example 1 except that maleic anhydride was not used, and the results are shown in Table 1. The composition and the amount (parts by weight) of the composition were used to prepare a flaking composition, and the composition was prepared and evaluated in the same manner as in Example 1-2). The results are shown in Table 1.

Table 1 shows that the storage stability of the flaking composition containing the modified unsaturated epoxy ester resin, N, N-dimethylparatoluidine and glass flake according to the present invention is improved as compared with the comparative example.

Example 2 1) Production of Modified Unsaturated Epoxy Ester Resin 940 parts of Ep1001 (manufactured by Shell Chemical Co., epoxy resin, epoxy equivalent: 470), 172 parts of methacrylic acid, 4 parts of benzyldimethylamine, and 0.1 part of hydroquinone were charged at 115 ° C. The reaction took place. When the acid value becomes 0, maleic anhydride
24 parts were further added to the kettle, and the reaction was stopped when the acid value reached 12, and 60 parts of the obtained reaction product was dissolved in 40 parts of styrene to obtain a modified unsaturated epoxy ester resin (B-1). I got

2) Preparation and Evaluation of Flake Lining Composition Using the obtained resin (B-1), the composition and the amount (parts by weight) shown in Table 2 were used to prepare the flaking composition as in 2) of Example 1. And evaluated. The results are shown in Table 2.

Comparative Examples 5 to 8 Unsaturated epoxy ester resin (B-2) was prepared in the same manner as in Example 2, 1) except that maleic anhydride was not used. The composition and the amount (parts by weight) indicated were used to prepare a flaking composition, and the composition was prepared and evaluated in the same manner as in 2) of Example 2. The results are shown in Table 2.

Table 2 shows that the storage stability of the flaking material composition containing the modified unsaturated epoxy ester resin, N, N-dimethylparatoluidine and glass flake according to the present invention is improved as compared with the comparative example.

〔The invention's effect〕

ADVANTAGE OF THE INVENTION According to the flaking composition of this invention, since the storage stability of a composition is excellent, gelation during storage can be reduced.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-53-22575 (JP, A) JP-A-56-87474 (JP, A) JP-A-50-35285 (JP, A) JP-A-1- 240509 (JP, A) JP-A-54-137088 (JP, A)

Claims (1)

(57) [Claims] (1) α · β which is almost equivalent to (A) polyepoxide
A modified unsaturated epoxy ester obtained by reacting an unsaturated epoxy ester obtained by reacting an unsaturated basic acid with 2 to 10 mol% of an acid anhydride based on hydroxyl groups of the unsaturated epoxy ester; 100 parts by weight of a modified unsaturated epoxy ester resin composed of 90 parts by weight and 70 to 10 parts by weight of an unsaturated monomer; (B) an average thickness of 0.5 to 10 microns and an average size of 100 to 100 parts by weight 10-60 parts by weight of glass flakes of 4000 micron and (C) N, N-dimethyl paratoluidine 0.01 as an accelerator
A flare lining composition comprising ２2 parts by weight.