JPH0129387B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin paint that is easy to spray coat. Allyl group-containing unsaturated polyester resin obtained by reacting polybasic acid, polyhydric alcohol, and polyhydric alcohol allyl ether can be used as an air-drying paint for general woodworking, as well as putty for automobile repair and joints in buildings. It is useful as a sealant for parts, around sashes, insets in glass, etc. The paint can be applied to the substrate by any method such as spatula coating, brush coating, or spray coating, but spray coating has a significantly simpler application process compared to spatula coating and brush coating. Furthermore, since it has the advantage of greatly shortening the polishing process, its demand has increased in recent years, and it is also described in, for example, Japanese Patent Publication No. 56-23664. However, in order to use unsaturated polyester resin paints for spray painting, more stringent physical properties of the paint are required. The conventional paints mentioned above are made by mixing fillers and vinyl monomers with ordinary air-drying unsaturated polyester resin obtained by reacting polybasic acid, polyhydric alcohol, and polyhydric alcohol allyl ether, and the mixing ratio is Although efforts have been made to improve sprayability, such as by controlling the has been done. It is necessary to improve the adhesion or water-resistant adhesion to base materials, especially metals. It is necessary to provide quick drying properties. It is necessary to improve the sprayability, that is, increase the solids content of the coating material with little increase in viscosity and provide good sprayability. However, as a result of intensive research in order to solve this problem, the present inventors found that (1) General formula [

Tricycloalkanes, tertiary nitrogen-containing alcohols, polybasic acids, polyhydric alcohols, and polyhydric alcohols represented by the formula 10 to 45 parts by weight of an air-drying unsaturated polyester resin obtained by reacting alcohol allyl ether, (2) 50 to 70 parts by weight of a filler, and (3) 5 to 20 parts by weight of a vinyl monomer. The present inventors have discovered that an unsaturated polyester resin coating material that satisfies the above requirements and have completed the present invention. In the present invention, as described above, by introducing the above-mentioned tricycloalkanes and tertiary nitrogen-containing alcohol into the air-drying unsaturated polyester resin, while taking advantage of the inherent characteristics of the air-drying unsaturated polyester resin, Adhesion (water-resistant adhesion), speed, and sprayability can be greatly improved. Tricycloalkanes are compounds represented by the above general formula, and various types are used, but in practical use tricyclodecanes are used.

The formula is most advantageously used. In the above, the position of X is arbitrary, but usually

【formula】

【formula】

[Formula] or

[Formula] and these can be used alone or as a mixture. X is a hydroxyl group, a carboxyl group, or a hydroxyalkyl group (eg, a hydroxymethyl group, a hydroxyethyl group, etc.). Examples of the tertiary nitrogen-containing alcohol include those represented by the following formula. However, R ₁ is an alkyl group or an aryl group, R ₂ is
R ₃ is an alkylene group), such as N,N-di(β-hydroxyethyl)aniline, N,N-di(γ-hydroxypropyl)aniline, N,N-di(β-hydroxypropyl)aniline , N,N-di(β-hydroxyethyl)-
m-toluidine, N,N-di(γ-hydroxypropyl)-m-toluidine, di(β-hydroxyethyl)-p-toluidine, N,N-di(β-hydroxypropyl)-p-toluidine, N, N-
Di(β-hydroxyethyl)-2,5-dimethoxyaniline, N,N-di(β-hydroxyethyl)-2,5-diethoxyaniline, N,N-di(β-hydroxyethyl)-p-cresidine ,N,
N-di(β-hydroxyethyl)-O-anisidine, N,N-di(β-hydroxyethyl)-O-
Phenetidine, N,N-di(β-hydroxyethyl)-amino-m-acetanilide, 3-(N,N
-di-β-hydroxyethyl)-amino-4-methoxyacetanilide, N-butylethanolamine, N-benzyldiethanolamine, N-butyl-bis(γ-hydroxypropyl)amine,
N-hexyl-bis(β-hydroxypropyl)
amine etc. or formula (However, R ₂ , R ₃ , and R ₄ are alkylene groups.) Compounds such as triethanolamine, tripropanolamine, etc. can also be used. In producing the unsaturated polyester resin of the present invention using the above tricycloalkanes and tertiary nitrogen-containing alcohol, polybasic acids, polybasic alcohols, polyhydric alcohol allyl ethers, tricycloalkanes and tertiary nitrogen-containing alcohols are used. A nitrogen-containing alcohol may be reacted in a conventional manner. Tricycloalkanes are classified into dihydric carboxylic acids and dihydric alcohols depending on the type of X. Of course, these dihydric carboxylic acids and dihydric alcohols may be used in combination during the production of unsaturated polyester. Furthermore, when using it as an alcohol, it is also possible to omit the use of other polyhydric alcohols, and when using it as an acid, it is also possible to omit the use of other polybasic acids. The tricycloalkanes are used in a proportion of 0.3 to 0.6 mol based on the total acid content when used as a divalent carboxylic acid, and in a proportion of 0.25 to 0.97 mol based on the total glycol content when used as a dihydric alcohol. used. When used within this range, the effects of improving metal adhesion, water resistance, etc., and improving spray suitability are particularly remarkable. Tertiary nitrogen-containing alcohols are
It is used in a range of 0.001 to 0.1 mol%, preferably 0.002 to 0.05 mol%. If it is less than 0.001 mol%, the quick-drying effect is poor, while if it is more than 0.1 mol%, the stability of the coating material is reduced. As the polybasic acid, an unsaturated acid is used, and if necessary, a saturated acid is used in combination. Examples of unsaturated acids include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, etc., and saturated acids include phthalic anhydride,
Examples include phthalic acid, terephthalic acid, isophthalic acid, hettic acid, adipic acid, telerahydrophthalic anhydride, and the like. In addition, examples of polyhydric alcohols to be polycondensed with the acid include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-butylene glycol, and 2,3-butylene. glycol, neopentyl glycol, trimethylolpropane,
Examples include glycerin. Examples of polyhydric alcohol allyl ethers used in condensation polymerization include pentaerythritol triallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether,
Examples include trimethylolethane diallyl ether and glycerin diallyl ether. Both are ethers containing at least one hydroxyl group in the molecule. The content of allyl group is preferably 0.05 to 2 mol as allyl group per 1 mol of acid component.
A suitable amount is 0.1 to 1.5 mol; if it is less than 0.05 mol, air-drying properties will not be sufficient, and if it is 2 mol or more, the blister resistance will deteriorate. The coating material of the present invention is prepared by mixing the resin with (2) a filler and (3) a vinyl monomer. Fillers include calcium carbonate, clay, talc, mica, asbestos powder, finely divided silica, barium sulfate, zinc stearate, lithobon, titanium white, cyanine blue, chrome yellow, watching red, red iron, carbon black, aniline black, etc. can be given. As the vinyl monomer, any of the known radical crosslinkable monomers for unsaturated polyesters can be used, including styrene, vinyltoluene, monochlorostyrene, diallyl phthalate, methyl methacrylate, vinyl acetate, and glycidyl methacrylate. The mixing ratio of (1) unsaturated polyester resin, (2) filler, and (3) vinyl monomer is 10 to 45 parts by weight for (1) and 10 to 45 parts by weight for (2).
50 to 70 parts by weight, and 5 to 20 parts by weight of (3). In such paint compositions, the solids content, i.e. (1)
Although the total amount of (2) and (2) is considerably higher than that of conventional unsaturated polyester resin paints, the viscosity of the paint is only about 200 to 800 cps, which allows easy spray painting. The major reason for imparting such properties is thought to be due to the tricycloalkanes present in the unsaturated polyester resin. In the above composition, if the content of (1) is less than 10 parts by weight, curing is slow and blister resistance is poor.
If it exceeds 45 parts by weight, the viscosity will be high and the sprayability will be poor. Furthermore, if (2) is less than 50 parts by weight, the blister resistance will be poor, and if it is more than 70 parts by weight, the disadvantage of reduced sprayability will become noticeable. Furthermore, if (3) is less than 5 parts by weight, curing and spray properties will be poor, and if it is more than 20 parts by weight, blister resistance will be poor and impractical. Other paint additives such as a photopolymerization initiator, curing agent, curing accelerator, diluent, thermoplastic resin, etc. may be added as necessary. Examples of the curing agent include methyl ethyl ketone peroxide, cyclohexane peroxide, benzoyl peroxide, dicumyl peroxide, and tert-butyl perbenzoate. Examples of the curing accelerator include cobalt octenoate, cobalt naphthenate, and manganese naphthenate. Examples of diluents include ethyl acetate, toluene, xylene, methanol, ethanol, butanol, acetone, MIBK, MEK, cellosolve, and diacetone alcohol. Examples of the thermoplastic resin include cellulose acetate butyrate, nitrocellulose, salt vinyl acetate resin, vinyl acetate resin, acrylic resin and copolymers thereof, butylated melamine, butylated urea, and the like. Other additives include phosphoric acid, tartaric acid, phosphorous acid, oils and fats, silicone oil, surfactants,
Examples include paraffin wax. The paint of the present invention is particularly useful as a putty for automobile repair, a sheet metal putty for heavy vehicles, a primer for steel furniture, a sealant for other parts of buildings, around sash, glass insets, etc., but also for general woodworking, etc. Of course, it can also be used for painting. As a coating method, any method such as spray coating, spatula coating, brush coating, etc. may be employed, but the coating of the present invention exhibits remarkable effects when spray coating is performed. Spray coating can be performed by air spraying using a paint gun with a nozzle diameter of about 0.7 to 2.0 mm at an air pressure of about 1 to 4 kg/cm ² or by airless spraying at a pressure of about 2 to 6 kg/cm ² . When used as a putty for repairing automobiles, a top coat can be applied. The top coat is a conventionally used colored paint or metallic paint, and examples thereof include acrylic urethane resin, acrylic alkyd nitrified cotton resin, acrylic cellulose, acetate butyrate resin, alkyd resin, and alkyd melamine resin. Next, the coating material of the present invention will be explained in more detail by giving examples. Example 1 249.5 g of maleic anhydride and tetrahydrophthalic anhydride were placed in two flasks equipped with a stirrer and a reflux condenser.
96.8g, tricyclodecane (

[Formula] and

mixture with [formula]) 623.3g, di(β-hydroxyethyl)-p-
Toluidine 5.5g, triallylpentaerythritol 130.4g, xylene 33g, hydroquinone
Prepare 0.22g at 150-195℃ for 3 hours, then further at 195℃
After the reaction, xylene was distilled off under reduced pressure at 150°C for 1 hour. acid value
An unsaturated polyester resin containing 20 KOHmg/g was obtained.
Dilute this with styrene to obtain a solid content of 75% viscosity.
A resin liquid of 400 CPS (measured at 20°C) was obtained. Also, Example 1 except that ethylene glycol was used instead of tricycloalkanes as Control Example 1.
The acid value is 22KOHmg/g and the viscosity is
A resin liquid of 1200 CPS and 75% solid content was obtained. Further, as Control Example 2, a resin liquid with an acid value of 18 KOH mg/g, a viscosity of 500 CPS, and a solid content of 75% was obtained in the same manner as in Example 1 except that the use of di(β-hydroxyethyl)-p-toluidine was omitted. . 20 g of styrene, 300 g of talc, and 60 g of titanium oxide for 320 g of resin liquid of Example 1 and Control Examples 1 and 2.
g, cobalt octenoate (8% cobalt content) 6
g and kneaded in a kneader to produce a putty for automobile repair, and to this putty cyclohexanone peroxide (manufactured by Cypotx PL Kawaguchi Pharmaceutical Co., Ltd.) was added.
1.0% was added and painted on a polished mild steel plate using a spray gun. The viscosity of each paint is 500CPS in Example 1;
Control example 1 is 3000CPS, control example 2 is 600CPS,
Control Example 1 was quite difficult to spray coat.
The drying properties, water resistance, and metal adhesion of the resulting coating films were examined. Evaluation method: Salt spray, 24 hours, 48 hours
The time, the presence or absence of blisters after 96 hours, and the quality of metal adhesion by bending were compared. Furthermore, adhesion was also compared using the Excelin test.

[Table] Examples 2 to 3 Unsaturated polyester resin paints as shown in Table 2 were produced according to Example 1. The results are shown in Table 2.

[Table] Examples 4 to 5 The same method as in Example 1 was carried out except that the mixing amounts of unsaturated polyester resin, filler, and styrene were changed as shown in Table 3. The results are shown in Table 3.

[Table] Example 6 A paint for troweling was prepared with a composition consisting of 320 g of the resin of Example 1, 565 g of talc, 55 g of titanium oxide, and 60 g of styrene. The results are shown in Table 4.

【table】

Claims (1)

[Scope of Claims] 1 (1) Tricycloalkanes represented by the general formula [[Formula] (where X is a hydroxyl group, a carboxyl group, or a hydroxyalkyl group, and n is an integer of 0 to 8)], tertiary nitrogen 10 to 45 parts by weight of an air-drying unsaturated polyester resin obtained by reacting the containing alcohol, polybasic acid, polyhydric alcohol, and polyhydric alcohol allyl ether, (2) 50 to 70 parts by weight of a filler, (3) An unsaturated polyester resin paint made by mixing 5 to 20 parts by weight of a vinyl monomer.