JPS60208307A - Anticorrosive material - Google Patents

Abstract

PURPOSE:An anticorrosive material of nonsolvent type that contains, as photosetting component, an ester from tricyclodecanedimethylol and an alpha,beta-unsaturated carboxylic acid, thus curing in a short time to give coating films of resistance to water and corrosion. CONSTITUTION:The objective anticorrosive material is obtained by adding, as a photosetting component, a diester from tricyclodecanedimethylol such as 3,8-bis (hydroxymethyl)tricyclo[5,2,1,0<2>,<6>]decane and an alpha,beta-unsaturated carboxylic acid, preferably acrylic acid. EFFECT:Protection of iron and carbon steel.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photocurable antirust material that is cured by ultraviolet light, electron beams, or the like.

Drying oils, alkyd resins, phenolic resins, vinyl chloride resins, acrylic resins, epoxy resins, etc. are generally used as rust-preventing materials to prevent rust from forming on steel and other metal materials and maintain their quality and appearance. There is. However, these materials either require a large amount of heating energy to dry the coating film, or require a very long drying time in the case of regular curing, and the solvents they contain can contaminate the working environment. Economic efficiency, workability, and safety (1)
) There was a problem.

Therefore, recently, as a method to solve all of these problems,
Solvent-free photocurable antirust materials that harden in a short time by irradiation with ultraviolet light or electron beams are being considered. Materials used for this purpose are generally required to have a fast photocuring speed and to have excellent water resistance and corrosion resistance. but,
There are few conventional photocurable resins that meet this purpose, and it has been extremely difficult to satisfy all of the above properties, especially in systems containing photocurable diluents for purposes such as viscosity adjustment.

Therefore, the present inventors conducted intensive studies to improve all the drawbacks of the prior art, and found that among the known photocurable components, photocurable components have been used as coating materials for resin molded products and for printing inks. It was known as a component (%Kasho 56-23511
(No. 57-164163) It was discovered that a tricyclodecane dimethylol-based material has a uniquely excellent performance gold layer, and the present invention was completed.

Thus, the present invention provides a photocurable antirust material containing /QX tricyclodecane dimethylols and a diester of α,β-unsaturated caldicic acid as a photocurable component. .

The above tricyclodecane dimethylols are those obtained by oxo reaction of dicyclopentadiene or its lower alkyl substituted product, specifically Kij3,8-bis(hydroxymethyl)tricyclo[:5,2,1.0 ”
6] decane, 4,9-bis(hydroxymethyl)tricyclo[5,2,1,02°6]decane, and the like.

On the other hand, specific examples of the above α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, croton li! Acrylic acid is also praised for its curing speed.

The tricyclodecane dimethylol diester used in the present invention can be synthesized according to conventional methods. For example, α, β- for the hydroxyl group of tricyclodecanedimethylol
Using 1 to 3 times the molar amount of unsaturated carboxylic acid, sulfuric acid, p-
80~ in the presence of an acid catalyst such as toluenesulfonic acid etc.
At a reaction temperature of 120°C, hydroquinone, if necessary,
It can be easily obtained by reacting with the addition of a polymerization inhibitor such as hydroquinone monomethyl ether.

In the present invention, such tricyclodecane dimethylol diester is used as a photocurable component of a rust preventive material. When used, such tricyclodecane dimethylol diester may be used alone or in combination with other commonly used photocurable resins. Specific examples of photocurable resins that can be used in combination include epoxy resins, polyurethane, polyesters, silicone resins, polybutadiene, alkyd resins, phenolic resins,
Examples include acrylate-modified products and methacrylate-modified products based on petroleum resins. Although the proportion of the combined use can be selected as appropriate, it is appropriate that the amount of tricyclodecanemethylol diester Th is usually 10% by weight or more, preferably 15% by weight or more, based on the entire curable component.

Since the tricyclodecane dimethylol diester used in the present invention has an extremely low viscosity, it does not necessarily require any other photocurable diluent, but when it is combined with other photocurable resins to increase the viscosity, etc. If necessary, all commonly used photocurable diluents can be blended, and specific examples include methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate,
Tricyclodecane monomethylol acrylate, 1.4
-Butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, nopentaerythritol hexaacrylate, corresponding to these compounds All examples include methacrylate and N-vinylpyrrolidone. However, even in this case, it is appropriate that the amount of tricyclodecane dimethylol diester be at least 910% by weight of the total curable component, preferably at least 15% by weight.

t-) In the present invention, a commonly used photopolymerization initiator is blended to promote photocuring by ultraviolet rays or the like. Specific examples of such photopolymerization initiators include benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, penzoin isoglobyl ether, benzyl, benzyl dimethyl ketal, and hyl-'
Examples include carbonyl compounds such as roxycyclohexyl phenyl ketone, diacetyl, acetophenone, jetoxyacetophenone, and anthraquinone, sulfide compounds such as diphenyl disulfide, and halocyanides such as pentachlorobutadiene, based on 100 parts by weight of the photocurable component. It is usually used in a proportion of 0.1 to 10 parts by weight.

If necessary, a photosensitizer can also be added. Specific examples include n-butylamine, di-n-butylamine, triethylamine, 2-methylaminoethanol, N-methylnoethanolamine, and triethanol. Examples include amines, and if necessary, other additives, such as lead (6), rust preventives such as red, lead zinc oxide, and dicytachromate, and various metals such as photocurable organic phosphate esters. Adhesion agents, pigments, fillers, plasticizers, thermal initiators, etc. may be added.

The photocurable antirust material according to the present invention is used to protect steel materials such as iron, carbon steel, and stainless steel. It can be applied to plates, wires, rods, pipes, and various other molded materials without any restrictions on the shape of steel materials.

In addition, the steel material must be undercoated with another paint beforehand.
It can be applied directly to untreated steel.

As a light source for light curing, ultraviolet light +18 such as high-pressure water lamps and metal halide lamps can be used! Although generators are commonly used, electron beams, X1Ii! , gamma ray generators, etc. can also be used. Further, as the coating method, any of the coating methods such as gray, shower, dipping, roll, and ironing can be used.

Thus, according to the present invention, a coating film with excellent water resistance and corrosion resistance can be obtained in a short curing time. In addition to improving economy and workability by omitting the drying step, it is also possible to improve safety by being solvent-free.

Next, the present invention will be explained in more detail with reference to Examples.

Note that parts in the examples represent parts by weight.

Example 1 50 parts of tricyclodecane dimethylol diacrylate,
Bifunctional oligoester acrylate)・(Aloex M-620002,000~3,000cpa/25
°C, manufactured by Toagosei Kagaku (So)) 50 parts Methyl benzoyl formate (Bicure 55, Stouffer Chapin Co., Ltd.)
A photocurable rust-preventive material was prepared by thoroughly mixing 3 parts of the same product (manufactured by Mikuni, Ltd.), and this was applied to a cold-rolled steel plate that had been degreased and cleaned with toluene.
The irradiation distance was 1 using a 2kW high-pressure mercury lamp H2O00L/6 (manufactured by Arika Paper Co., Ltd.) with an intensity of 0 W/cm.
It was irradiated and cured at a conveyor speed of 6 m/min at 0 m.

For comparison, the same curing was performed using various difunctional diluents instead of the tricyclodecane dimethylol diacrylate. The curing speed and characteristic values of the cured product are summarized in Pl.

(9) From the results of Part 1, the rust preventive material of the present invention cures faster and has excellent water resistance and salt spray resistance compared to those using other bifunctional diluents. I understand.

Example 2 Tricyclodecane dimethylol diacrylate and difunctional urethane acrylate (Aloex M-1200
, 200,000 to 300,000 cps 750℃, Toagosei Chemical Co., Ltd.
1-(4-isozolobylphenyl)-2-hydroxy-
2-methylpropan-1-one (Darocur 1116,
A rust-preventing material was prepared by blending 3 parts of the following products (manufactured by Merck & Co., Ltd.). Next, a test was conducted in the same manner as in Example 1 to evaluate water resistance and salt spray resistance. The results are shown in Figure 2.

(11) (I2) As shown in the results for Cloth 2, it can be seen that the photocurable antirust material containing tricyclodecane dimethylol diacrylate has excellent water resistance and side food properties.

Patent applicant: Zeon Corporation (13)

Claims (1)

[Claims] 1 Tricyclodecane dime fo- as a photocurable component
p,, kind,! : A photocurable antirust material containing a diester of α,β-unsaturated carboxylic acid.