JPH0580277B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a method of forming a coating film using a coating material whose main ingredient is a specific unsaturated polyester. Prior Art Unsaturated polyesters containing polyhydric alcohol allyl ether, hydroxylated dicyclopentadiene, or tetrahydrophthalic anhydride are air-drying, have a desirable luster and texture, and give a beautiful finish, so they are generally used. It is useful as a raw material for wood coatings or as a raw material for sealants. Such as air-drying unsaturated polyester,
For example, Japanese Patent Publication No. 42-6261 discloses a resin composition in which a vinyl monomer is mixed with an unsaturated polyester containing hydroxylated dicyclopentadiene, and Japanese Patent Publication No. 50-27830 discloses Disclosed is a coating composition comprising an unsaturated polyester containing as a modifying component at least one member selected from the group consisting of polyhydric alcohol allyl ether, hydroxylated dicyclopentadiene, and tetrahydrophthalic anhydride, and a vinyl monomer containing glycidyl methacrylate. has been done. Problems to be Solved by the Invention However, in the coating industry, there is a desire to further improve the properties of unsaturated polyesters in terms of curing speed, water resistance, smoothness, and the like. Therefore, the present inventors conducted research not only on unsaturated polyesters containing polyhydric alcohol allyl ether, hydroxylated dicyclopentadiene, and tetrahydrophthalic anhydride individually, but also on the use of these air-drying components in combination. However, it has not been possible to obtain an unsaturated polyester that satisfactorily meets the above requirements. In view of such gloss, the present invention aims to improve the curing speed,
This was achieved through intensive research to further improve properties such as water resistance, smoothness, and hardness. Means for Solving the Problems The method for forming a coating film of the present invention uses an unsaturated polyester (AB) containing a polyhydric alcohol allyl ether component (a) and a polybasic acid tricyclodecenyl component (b). Or, the main ingredient is a mixture of an unsaturated polyester (A) containing a polyhydric alcohol allyl ether component (a) and an unsaturated polyester (B) containing a polybasic acid tricyclodecenyl component (b). It is characterized by applying the paint to the base material and then irradiating it with light or heating it at a temperature of 50°C or higher. The present invention will be explained in detail below. The unsaturated polyester used in the present invention is (i) an unsaturated polyester (AB) containing a polyhydric alcohol allyl ether component (a) and a polybasic acid tricyclodecenyl component (b), or (ii) It is a mixture of an unsaturated polyester (A) containing a polyhydric alcohol allyl ether component (a) and an unsaturated polyester (B) containing a polybasic acid tricyclodecenyl component (b). That is, the above components (a) and (b) may be contained within the same molecule, or may be in the form of a mixture in which each is contained within another molecule. However, when comparing (i) above and (ii) above,
(i) gives more favorable results. Here, polyhydric alcohol allyl ether component (a)
Examples include pentaerythritol triallyl ether, pentaerythritol triallyl ether,
Trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether, trimethylolethane diallyl ether, trimethylolethane monoallyl ether, glycerin diallyl ether, glycerin monoallyl ether, tetramethylolcyclohexanol diallyl monocrotyl ether, hexamethylolmelamine diallyl dicrotyl Examples include allyl ethers having at least one hydroxyl group in the molecule, such as ether, hexanetriol diallyl ether, pentaerythritol diallyl crotyl ether, tetramethylolcyclohexanol triallyl ether, tetramethylolcyclohexanone diallyl ether, and hexamethylolmelamine tetraallyl ether. As the tricyclodecenyl polybasic acid component (b),
Examples include tricyclodecenyl maleate, tricyclodecenyl fumarate, tricyclodecenyl adipate, tricyclodecenyl phthalate, tricyclodecenyl isophthalate, tricyclodecenyl trimellitate, etc. be done. Among these, tricyclodecenyl maleate is the most practical in consideration of raw material cost, reactivity, etc. Note that even if a hydroxylated dicyclopentadiene such as hydroxyl tricyclodecenyl or polyhydric alcohol tricyclodecenyl is used in place of the above component (b), the effect as excellent as that of the present invention cannot be achieved. However, hydroxylated dicyclopentadiene may be used in combination with the above component (a) and component (b). The unsaturated polyester is composed of a polybasic component and a polyhydric alcohol component in addition to components other than the above (a) and (b). As the polybasic acid component, unsaturated polybasic acids such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, fumaric acid, citraconic anhydride, and citraconic acid are used. Along with polybasic acids, phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hettic acid, trimellitic anhydride,
Trimethic acid, pyromellitic anhydride, pyromellitic acid, 4-methylcyclohexane-1,2,3-
Saturated polybasic acids such as tricarboxylic anhydride, trimesic acid, adipic acid, and sebacic acid can also be used in combination. Polyhydric alcohol components include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-butylene glycol, 2,3-butylene glycol, and 1,6-hexanediol. ,
2-ethyl-1,3-hexanediol, 22,4
-Trimethyl-1,3-pentanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, etc. are used. In the case of (i) above, unsaturated polyester (AB)
The proportion of the polyhydric alcohol allyl ether component (a) in the unsaturated polyester (AB) is selected from the range of 2 to 40 mol%, preferably 5 to 30 mol%, based on the polybasic acid component. The proportion of tricyclodecenyl acid component (b) is selected from the range of 5 to 50 mol%, preferably 10 to 40 mol%, based on the polybasic acid component. In the case of (ii) above, the proportion of the polyhydric alcohol allyl ether component (a) in the unsaturated polyester (A) is 5 to 50 mol%, preferably 10 to 40% by mole based on the polybasic acid component.
Unsaturated polyester selected from a range of mole%
The proportion of the polybasic acid tricyclodecenyl component (b) in (B) is selected from the range of 10 to 60 mol%, preferably 20 to 50 mol%, based on the polybasic acid component. and,
The ratio of polyhydric alcohol allyl ether component (a) to the total amount of polybasic acid components in the mixture of unsaturated polyester (A) and unsaturated polyester (B) is 2 to 40 mol%, preferably 5 to 30 mol%. Similarly, the proportion of the tricyclodecenyl polybasic acid component (b) is set to 5 to 50 mol%, preferably 10 to 40 mol%. In both cases (i) and (ii) above, too little amount of component (a) will cause a delay in curing speed and drying performance, while even if component (a) is introduced beyond this range, the effect will be beyond a certain limit. However, it is disadvantageous in terms of cost and lacks practicality. Furthermore, too little component (b) leads to insufficient water resistance, while too much component (b) leads to a delay in curing speed. Unsaturated polyester (AB), (A) or (B) is
It is produced by reacting a polybasic component, a polyhydric alcohol component, and the above-mentioned components (a) and/or (b) at a temperature of about 150 to 250° C. in an inert gas atmosphere according to a conventional method. By blending the unsaturated polyesters (i) and (ii) above with crosslinking monomers and necessary additives,
Paint is prepared. After applying this paint to a base material, a paint film is formed by irradiating it with light or heating it at a temperature of 50°C or higher. In other words, in the present invention, the specific resin mentioned above is used as the resin, and the specific curing method of light irradiation or heating at a temperature of 50°C or higher is used as the curing method, which makes it possible to obtain a coating with excellent performance for the first time. Since we were able to obtain the membrane,
Even if the above-mentioned specific resin is used, the intended purpose cannot be achieved by normal room temperature curing or heat curing at less than 50°C. Comparing light irradiation as a curing means and heating at a temperature of 50° C. or higher, the former is preferable because it can further shorten the curing time and further improve properties such as the smoothness of the coating film. Examples of crosslinking monomers include styrene, vinyltoluene, monochlorostyrene, α-methylstyrene, diallyl phthalate, triallyl cyanurate, alkyl acrylate, alkyl methacrylate, glycidyl methacrylate, 2-hydroxymethacrylate glycidyl ether, and vinyl acetate. , vinyl chloride, methylenebisacrylamide,
Divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate,
Known crosslinking monomers for unsaturated polyesters are used, including 1,6-hexanediol diacrylate and vinylcyclohexene monooxide. Next, various additives will be explained. When curing by light irradiation, a photopolymerization initiator is added. As a photopolymerization initiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, benzyl ketal, acetophenone, 1,
1-dichloroacetophenone, para-t-butylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-dichloro-4-phenok Cyacetophenone, benzophenone, anthraquinone, naphthoquinone, pivaloin ethyl ether,
Various photopolymerization initiators are used, including 2-chlorothioxanthone, 2-methylthioxanthone, phenylglyoxylate, Michler's ketone, and α-hydroxyisobutylphenone. When curing is attempted by heating, preferably a curing agent and a curing accelerator are blended. Examples of curing agents include methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, and t-butyl perbenzoate. Examples of curing accelerators include cobalt octenoate and naphthene. cobalt acid,
Examples include manganese octenoate, manganese naphthenate, zinc octenoate, and zinc naphthenate. In addition, pigments (titanium white, cyanine blue, chrome yellow, watching red, red iron black, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansared, chrome yellow, chrome green, etc.), as necessary. Fillers (calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder, finely divided silica, barium sulfate, lithopone, gypsum, perlite, etc.), abrasives (zinc stearate, finely divided talc, etc.), leveling agents (silicone) , cellulose acetate butyrate,
surfactants, etc.), diluents (ethyl acetate, toluene, xylene, methanol, ethanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol, etc.), thermoplastic resins (nitrocellulose,
Vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, butylated melamine, butylated urea, etc.), greening inhibitors (phosphoric acid, phosphorous acid, tartaric acid, etc.), drying aids (oils and fats, paraffin wax, etc.) (such as Tsukusu) can be blended. As a method for applying the prepared paint, a roller coating method, a spray coating method, a flow coating method, a brush coating method, a dipping method, etc. are adopted. Various substrates can be coated, including wood products, metals, concrete, glass, plastics, painted surfaces, and particle boards. As a light source for curing by light irradiation after coating, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light, etc. are used. The irradiation time varies depending on the type of light source, the distance between the light source and the coating surface, and other conditions, but several tens of seconds is sufficient at most, and usually several seconds, sometimes a fraction of a second. But that's fine. After coating, when curing by heating, use hot air,
Heat the coated surface to a temperature of 50°C or higher using an infrared lamp or similar device. Curing will proceed at room temperature or below 50℃, but the curing speed will be faster if heated above 50℃.
The physical properties of the coating film also become better. Effect The polyhydric alcohol allyl ether component (a) and the polybasic acid tricyclodecenyl component (b) introduced into the unsaturated polyester have a synergistic effect, so that when the coated surface is irradiated with light or heated, It has the effect of increasing the curing speed and improving the hardness, water resistance, smoothness, etc. of the coating film. Examples Next, examples will be given to further explain the method of the present invention. Hereinafter, "%" means % by weight. Example 1 In a flask equipped with a stirrer, a gas inlet tube and a reflux condenser, 1.0 mol of maleic anhydride and 0.4 mol of water were added.
mole, dicyclopentadiene 0.25 mole, propylene glycol 0.25 mole, diethylene glycol
0.65 mol, triallylpentaerythritol 0.15
A condensation reaction was carried out by charging 3% (by mole) xylene (based on the system) and 0.02% (based on the system) of hydroquinone (polymerization inhibitor). However, first, 0.3 mol of maleic anhydride, 0.4 mol of water, and 0.25 mol of dicyclopentadiene were charged into a flask to produce tricyclodecenyl maleate, and then the remaining raw materials were charged to carry out the reaction. For the condensation reaction, the temperature was raised from 150°C to 200°C in a nitrogen gas stream over 3 hours, the reaction was further carried out at 200°C for 4 hours, and after the reaction, xylene was heated at 150°C under reduced pressure for 1 It was distilled off under the condition of time. Acid value 12.0KOHmg/g obtained in this way
The unsaturated polyester was diluted with styrene monomer to obtain a resin liquid with a solid content of 70% and a viscosity of 2300 cps/20°C. This resin liquid was further diluted with styrene monomer to a spray viscosity, benzoin isopropyl ether was added at 3.0% to the system, and this was then sprayed onto the veneer surface at a concentration of 300 g/m ² using a high-pressure mercury lamp (80 w/cm). The light was irradiated from a distance of 10 cm. The results are shown in Table 1. Comparative Example 1 In a flask equipped with a stirrer, a gas inlet tube, and a reflux condenser, 1.0 mol of maleic anhydride, 0.25 mol of hydroxyl tricyclodecenyl, 0.25 mol of propylene glycol, and diethylene glycol were added.
0.65 mol, triallylpentaerythritol 0.15
A condensation reaction was carried out by charging 3% (by mole) of xylene (based on the system) and 0.02% (based on the system) of hydroquinone (polymerization inhibitor) at once. For the condensation reaction, the temperature was 3°C from 150°C to 200°C in a nitrogen gas stream.
The reaction was carried out for 4.5 hours at a temperature of 200°C, and after the reaction, xylene was heated at 150°C under reduced pressure for 1 hour.
It was distilled off under the condition of time. Acid value 12.5KOHmg/g obtained in this way
The unsaturated polyester was diluted with styrene monomer to obtain a resin liquid with a solid content of 70% and a viscosity of 2200 cps/20°C. This resin liquid was further diluted with styrene monomer to a spray viscosity, and then benzoin isopropyl ether was added, sprayed, and light irradiated in the same manner as in Example 1. The results are also shown in Table 1.

[Table] Example 2 Solid content 70% and viscosity obtained in Example 1
The resin liquid at 2300 cps/20°C was further diluted with styrene monomer to a spray viscosity, and cobalt octenoate (Octex Co manufactured by Nippon Kagaku Sangyo Co., Ltd.) was added.
Mix 0.5% (contains 8% cobalt) and 1.0% methyl ethyl ketone peroxide (Permek-N, manufactured by NOF Corporation), then spray this onto the veneer surface at a concentration of 300 g/m ² at a temperature of 60°C.
It was heated and dried. The results are shown in Table 2. Comparative Example 2 Solid content 70% and viscosity obtained in Comparative Example 1
The resin liquid at 2200 cps/20° C. was further diluted with styrene monomer to a spray viscosity, and then cobalt octenoate and methyl ethyl ketone peroxide were added, sprayed, and dried by heating in the same manner as in Example 2. The results are also shown in Table 2. Comparative Example 3 Acid value obtained in the same manner as Comparative Example 1 except that the use of hydroxyl tricyclodecenyl was omitted and the amount of propylene glycol used was 0.4 mol.
11.0KOHmg/g of unsaturated polyester was diluted with styrene monomer to give a solids content of 70% and a viscosity of
A resin liquid of 2000 cps/20°C was obtained. This resin liquid was further diluted with styrene monomer to a spray viscosity, and then cobalt octenoate and methyl ethyl ketone peroxide were added, sprayed, and dried by heating in the same manner as in Example 2. The results are also shown in Table 2. Comparative Example 4 Acid value obtained in the same manner as Comparative Example 1 except that the use of triallylpentaerythritol was omitted and the amount of propylene glycol used was 0.3 mol.
11.5KOHmg/g of unsaturated polyester was diluted with styrene monomer to give a solids content of 70% and a viscosity of
A resin liquid of 2100 cps/20°C was obtained. This resin liquid was further diluted with styrene monomer to a spray viscosity, and then cobalt octenoate and methyl ethyl ketone peroxide were added, sprayed, and dried by heating in the same manner as in Example 2. The results are also shown in Table 2.

[Table] Example 3 Maleic anhydride, 1.0 mol, and water were placed in a flask equipped with a stirrer, a gas inlet tube, and a reflux condenser.
A condensation reaction was carried out by charging 0.5 mol of dicyclopentadiene, 0.4 mol of propylene glycol, 0.65 mol of diethylene glycol, 3% (based on the system) of xylene, and 0.02% (based on the system) of hydroquinone (polymerization inhibitor). However, first, add 0.5 mol of maleic anhydride, 0.5 mol of water to the flask,
0.4 mol of dicyclopentadiene was charged to produce tricyclodecenyl maleate, and then the remaining raw materials were charged to carry out the reaction. For the condensation reaction, the temperature was raised from 150°C to 200°C in a nitrogen gas stream over 3 hours, and the reaction was further carried out at 200°C for 4 hours.
It was distilled off for 1 hour. Acid value 12.0KOHmg/g obtained in this way
The unsaturated polyester (A) was diluted with styrene monomer to obtain a resin liquid with a solid content of 70% and a viscosity of 2300 cps/20°C. In a flask equipped with a stirrer, gas inlet tube and reflux condenser, 1.0 mol of maleic anhydride, 0.35 mol of propylene glycol, 0.65 mol of diethylene glycol, and triallylpentaerythritol.
A condensation reaction was carried out by charging 0.30 mol of xylene 3% (based on the system) and hydroquinone (polymerization inhibitor) 0.02% (based on the system) at once. During the condensation reaction, the temperature in a nitrogen gas stream is
The temperature was raised from 150°C to 200°C over 3 hours, and the reaction was further carried out at 200°C for 5 hours. After the reaction, xylene was distilled off under reduced pressure at 150°C for 1 hour. Acid value 13.0KOHmg/g obtained in this way
The unsaturated polyester (B) was diluted with styrene monomer to obtain a resin liquid with a solid content of 70% and a viscosity of 2400 cps/20°C. Next, the above two types of resin liquids were mixed in a weight ratio of 1:1, further diluted with styrene monomer to a spray viscosity, benzoin isopropyl ether was added to the system at a concentration of 3.0%, and this was then applied to the surface of the veneer at a rate of 300%.
g/m ² and irradiated from a distance of 10 cm with a high-pressure mercury lamp (80 w/cm). The results are shown in Table 3. Comparative Example 5 An experiment similar to Example 3 was conducted except that the unsaturated polyester (A) in Example 3 was used alone.
The results are also shown in Table 3. Comparative Example 6 An experiment similar to Example 3 was conducted except that the unsaturated polyester (B) in Example 3 was used alone.
The results are also shown in Table 3.

【table】

[Table] Same as footnotes in Table 1.
Effects of the Invention In the present invention, a polyhydric alcohol allyl ether component and a polybasic acid tricyclodecenyl component are introduced into an unsaturated polyester, and the coated surface is irradiated with light or heated at a temperature of 50°C or higher. By adopting this method, a coating film can be obtained that has a high curing speed and has outstanding properties such as hardness, water resistance, and smoothness.

Claims (1)

[Claims] 1 Unsaturated polyester (AB) containing polyhydric alcohol allyl ether component (a) and polybasic acid tricyclodecenyl component (b), or unsaturated polyester containing polyhydric alcohol allyl ether component (a) After applying a paint based on a mixture of polyester (A) and unsaturated polyester (B) containing polybasic acid tricyclodecenyl component (b) to the base material, irradiate it with light or heat it at 50℃ or above. A method for forming a coating film characterized by heating at a temperature of .