JPS6157325B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a resin for anticorrosive paints, and more specifically, a method for producing a resin for anticorrosive paints, more specifically, a resin obtained by reacting an epoxidized oleyl alcohol monovinyl ester with at least one compound selected from orthophosphoric acid, orthophosphorous acid, and orthophosphoric acid monoester. The present invention relates to a method for producing a resin for anticorrosive paint with excellent corrosion resistance, which is characterized by copolymerizing monovinyl phosphoric acid epoxy ester and a polymerizable vinyl monomer. Conventionally, many researches have been made to develop resins that provide coating films with excellent corrosion resistance, but there has been no resin that has excellent corrosion resistance, adhesion, water resistance, weather resistance, etc. Therefore, in order to impart anticorrosion properties to the coating film, we have resorted to adding additives and changing the composition of pigments. In particular, it often depended on the pigment composition. Among these pigments, chromium pigments are well known. However, this pigment causes social problems such as human toxicity and pollution, and there is a trend toward dechromization. The present invention overcomes the above-mentioned drawbacks of the conventional art. That is, the present invention provides epoxidized oleyl alcohol monovinyl ester and orthophosphoric acid,
Orthophosphorous acid and general formula R-O-P
Monovinyl phosphorus obtained by reacting with at least one compound selected from orthophosphoric acid monoesters represented by (OH) ₂ O (wherein R is an alkyl group or oleyl group having 1 to 20 carbon atoms) The present invention relates to a method for producing a resin for anticorrosive paints, which comprises copolymerizing 1 to 70 parts by weight of an acid epoxy ester and 99 to 30 parts by weight of a polymerizable vinyl monomer. The epoxidized oleyl alcohol monovinyl ester that can be used in the present invention is obtained by subjecting oleyl alcohol to an esterification reaction with acrylic acid or methacrylic acid, and then epoxidizing it. company), etc. The epoxidation of the esterified oleyl alcohol described above involves the 9 of the 18 carbon chains of oleyl alcohol
This occurs necessarily at the double bond position between the 1st and 10th positions. This epoxidized oleyl alcohol monovinyl ester contains orthophosphoric acid, orthophosphorous acid and the general formula R-O-P(OH) ₂ O (wherein R is an alkyl group having 1 to 20 carbon atoms or an oleyl group).
At least one compound selected from the orthophosphoric acid monoesters represented by the formula is added at a ratio of 0.9 to 1.0 mol of the former to 1 mol of the latter, while stirring, for about 60 to 60 mol.
The epoxy group and the phosphoric acid compound are reacted by heating at 150° C. for about 2 to 10 hours to obtain a monovinyl phosphoric acid epoxy ester. The end point of the reaction is determined by measuring the acid value, and is usually determined when the acid value becomes 250 or less. In this reaction, a polymerization inhibitor such as hydroquinone is usually added to prevent thermal polymerization of the epoxidized oleyl monovinyl ester.
It is desirable to add 50 to 1000 ppm. The general formula R-O-P(OH) ₂ O (where R
is an alkyl group or oleyl group having 1 to 20 carbon atoms) Examples of orthophosphoric acid monoesters include methyl, ethyl, propyl, butyl, hexyl, octyl, 2-ethylhexyl,
Examples include monoesters such as lauryl, hexadecyl, eicosyl, and oleyl. Such orthophosphoric acid monoester is prepared by reacting phosphorus pentoxide and alcohol at 0 to 10°C for 2 to 4 hours.
Then add water in the presence of an alkaline catalyst for 10 to 30 minutes.
It is obtained by reacting at ℃ for 2 to 4 hours. The monovinyl phosphate epoxy ester obtained as described above is then copolymerized with a vinyl monomer. Vinyl monomers to be copolymerized include styrene, vinyltoluene, acrylic acid,
Methacrylic acid, acrylic esters, methacrylic esters (e.g., methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, etc.), vinylpyrrolidone, vinyl acetate. One or more of acrylamide, methacrylamide, N-methylolacrylamide, diacetone acrylamide, etc. are suitable. The copolymerization composition is preferably such that 99 to 30 parts of the above vinyl monomer are used for 1 to 70 parts of the monovinyl phosphoric acid epoxy ester compound to sufficiently exhibit adhesion and rust prevention ability and to maintain good water resistance. The copolymerization reaction is carried out in an organic liquid using an azo polymerization initiator such as 2,2'-azoisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), lauryl peroxide, and benzoyl peroxide. ,
It is polymerized using a peroxide polymerization initiator such as tert-butyl peroctoate. Polymerization initiator concentration is 0.5 to 10 per 100 parts by weight of vinyl monomer
Parts by weight are preferred. The reaction temperature is 60-160°C. It is also possible to obtain a polymer solution by placing an organic liquid in a reaction container, charging the monovinyl phosphoric acid epoxy ester compound, the entire amount of vinyl monomer, and a polymerization initiator, and conducting the reaction for 1 to 15 hours.
A mixture of a vinyl monomer (the monovinyl phosphate epoxy ester compound may be wholly or partially mixed with the vinyl monomer) and a polymerization initiator is added dropwise over 1 to 7 hours, and then the reaction is continued for 2 to 7 hours. It is also possible to obtain polymer solutions. In the above reaction process, the phosphoric acid group of the monovinyl phosphoric acid epoxy ester is bonded almost to the center of the long carbon chain of the ester, so the formation of divinyl is completely prevented due to steric hindrance of the carbon chain. In the polymerization process, the reaction is extremely smooth without gelation and thickening, and the degree of polymerization can be adjusted arbitrarily. The polymer solution obtained in this way is extremely stable due to steric hindrance caused by the presence of a phosphate group in the center of a long carbon chain, has a low possibility of hydrolysis, and has excellent storage stability. The cured paint film has excellent water resistance and adhesion. The polymer solution of the present invention can be used as it is, but if necessary, colorants, plasticizers, curing agents, etc. can be mixed therein. Dye as a coloring agent,
Examples include organic pigments and inorganic pigments. Examples of the plasticizer include known ones, such as low molecular weight plasticizers such as dimethyl phthalate and dioctyl phthalate, and high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers. Examples of hardening agents include crosslinking agents such as amino resins and epoxy resins. The polymer solution of the present invention can be made into a water-soluble type or water-dispersible type by introducing a material having a carboxyl group into the copolymer composition, neutralizing the carboxyl group with ammonia or amines, and replacing the organic liquid with water. It is also possible to use a mold. The polymer solution of the present invention has the following characteristics compared to conventional vinyl polymer paint resins, polyester paint resins, epoxy paint resins, polyvinyl butyral paint resins, phenolic paint resins, etc.
Excellent coating properties such as adhesion, rust prevention, water resistance, and weather resistance. Examples will be described below. Parts mean parts by weight. Example 1 (Monovinyl phosphate epoxy ester compound solution
Synthesis of (1)) Toluene 200 parts Isopropyl alcohol 281 parts Epoxidized oleyl alcohol monoacrylic ester (“Recaresin ESA” manufactured by Shinnihon Rika Co., Ltd.)
400 parts 85% orthophosphoric acid 115 parts hydroquinone 0.5 part The above ingredients were placed in a second flask equipped with a stirrer and a thermometer and reacted at 100°C for 4 hours with stirring. The reaction end point was when the acid value reached 230. It was a clear solution with a non-volatile content of 50 wt.%. (Synthesis of polymer solution) Monovinyl phosphate epoxy ester compound solution
(1) 100 parts styrene 500 parts n-butyl acrylate 400 parts methacrylic acid 50 parts 2,2'-azoisobutyronitrile 5 parts The above mixture was placed in a refluxing flask containing 500 parts of toluene and 450 parts of isopropanol for 3 hours. The solution was added dropwise and aged for 5 hours after the addition. The resulting liquid was clear;
Gardner viscosity (25℃) at non-volatile content of 50wt.% is
It was Z-2. Example 2 (Monovinyl phosphate epoxy ester compound solution
Synthesis of (2)) Cellosolve Acetate 554 parts Epoxidized oleyl alcohol monoacrylic ester (“Recaresin ESA” manufactured by Shinnihon Rika Co., Ltd.)
400 parts orthophosphoric acid isobutanol monoester
154 parts of hydroquinone and 0.5 parts of the above were placed in a second flask equipped with a stirrer and a thermometer and reacted at 100°C for 4 hours with stirring. It was a clear solution with a non-volatile content of 50%, with the end point being when the acid value was 110 or less. (Synthesis of polymer solution) Monovinyl phosphate epoxy ester compound solution
(2) 200 parts styrene 450 parts 2-hydroxyethyl methacrylate 100 parts n-butyl acrylate 300 parts methacrylic acid 50 parts 2,2'-azoisobutyronitrile 50 parts The above mixture was refluxed with xylene 500 parts isopropanol 400 parts. The mixture was added dropwise into a flask over 3 hours, and aged for 5 hours after the addition. The resulting liquid was clear;
Gardner viscosity (25℃) at non-volatile content of 50wt.% is
It was G. Example 3 (Monovinyl phosphate epoxy ester compound solution
Synthesis of (3)) Cellosolve acetate 610 parts Orthophosphoric acid 2-ethylhexanol monoester 210 parts Epoxidized oleyl alcohol monoacrylic ester (“Recaresin ESA” manufactured by Shinnihon Rika Co., Ltd.)
400 parts Hydroquinone 0.5 parts The above mixture was placed in a second flask equipped with a stirrer and a thermometer and reacted at 100°C for 5 hours with stirring. The reaction end point was when the acid value reached 100. It was a clear solution with a non-volatile content of 50 wt.%. (Synthesis of polymer solution) Monovinyl phosphate epoxy ester compound solution
(3) 300 parts styrene 350 parts n-butyl acrylate 350 parts methyl methacrylate 100 parts methacrylic acid 50 parts ditertiary butyl peroxide 5 parts The above mixture was placed in a refluxing flask containing 500 parts of toluene and 350 parts of n-butanol for 4 hours. The solution was added dropwise and aged for 5 hours after the addition. The resulting liquid was transparent, had a non-volatile content of 50 wt.%, and had a Gardner viscosity (at 25°C) of Z-
It was 4. Comparative Example 1 Orthophosphoric acid-2-hydroxyethyl methacrylate monoester 25 parts Styrene 455 parts N-butyl acrylate 470 parts Methacrylic acid 50 parts 2.2'-Azoisobutyronitrile 5 parts The above mixture was mixed with toluene 500 parts Isopropanol 500 parts was added dropwise over 3 hours into a refluxing flask, and aged for 5 hours after the addition. The resulting liquid was transparent, had a non-volatile content of 50 wt.%, and had a Gardner viscosity (at 25°C) of Z-
It was 5. Example 4 In place of styrene, n-butyl acrylate and methacrylic acid monomers in Example 1 (synthesis of polymer solution), 250 parts of vinyl acetate and 250 parts of styrene were used.
A polymer solution was obtained in the same manner as in Example 1 except that 250 parts of methyl methacrylate and 200 parts of vinylpyrrolidone were used. The resulting liquid was transparent, had a volatile content of 50 wt.%, and had a Gardner viscosity (at 25°C) of Z-4.
It was hot. Example 5 50 parts of methacrylamide was used in place of 50 parts of methacrylic acid in Example 1 (synthesis of polymer solution), and this methacrylamide was mixed in advance in a flask in which 500 parts of toluene and 450 parts of isopropanol were refluxed. A polymer solution was obtained in the same manner as in Example 1 except for this. The resulting liquid is clear and contains no volatile components.
At 50 wt.%, the Gardner viscosity (25°C) was Z-1. Comparative Example 2 Styrene 450 parts n-butyl acrylate 500 parts Methacrylic acid 50 parts 2,2'-azoisobutyronitrile 5 parts The above mixture was added dropwise over 3 hours into a flask containing 500 parts toluene and 500 parts isopropanol. After dropping, aging was carried out for 5 hours. The resulting liquid was clear;
Non-volatile content is 50wt.% and Gardner viscosity (25℃) is Z
It was -3. Comparative Example 3 Orthophosphoric acid-2-hydroxyethyl methacrylate monoester 60 parts Styrene 450 parts 2-hydroxyethyl methacrylate 100 parts n-butyl acrylate 340 parts Methacrylic acid 50 parts 2.2'-Azoisobutyronitrile 50 parts Mixture of the above was added dropwise over 3 hours into a flask in which 500 parts of xylene and 500 parts of isopropanol were refluxed, and the mixture was aged for 5 hours after the addition. The resulting liquid was clear;
Gardner viscosity (25℃) at non-volatile content of 50wt.% is
It was I. Comparative Example 4 Styrene 500 parts 2-hydroxyethyl methacrylate 100 parts n-butyl acrylate 350 parts Methacrylic acid 50 parts The above mixture was added dropwise over 3 hours into a flask in which 500 parts xylene and 500 parts isopropanol were refluxed. It was matured. The resulting liquid was clear;
Gardner viscosity (25℃) at non-volatile content of 50wt.% is
It was G. The results of a salt spray resistance test performed on the coating films formed using the polymer solutions obtained in the above Examples and Comparative Examples are shown below.

[Table] For Examples 1 and 3 and Comparative Examples 1 and 2, the coating was applied to a polished mild steel plate to a dry film thickness of 20μ, and the test was conducted after drying at room temperature for 2 days.
5. For Comparative Examples 3 and 4, 30 wt. % of commercially available butylated melamine resin was applied so that the film thickness after baking was 20 μm, and the test was conducted after baking at 140° C. for 20 minutes. The adhesion deterioration width of the cut part is measured by cutting a cut into the test coating with a razor and performing a cellophane adhesive tape peeling test on the cut part after salt spraying. This is an observation of other rust occurrence conditions.

Claims (1)

[Claims] 1 Epoxidized oleyl alcohol monovinyl ester, orthophosphoric acid, orthophosphorous acid and the general formula R-O-P(OH) ₂ O (wherein R is an alkyl group having 1 to 20 carbon atoms or an oleyl group) 1 to 70 parts by weight of monovinyl phosphoric acid epoxy ester obtained by reacting with at least one compound selected from orthophosphoric acid monoesters, styrene monomer, (meth)acrylic acid ester monomer, (meth)acrylic acid 1. A method for producing a resin for anticorrosive paints, which comprises copolymerizing 99 to 30 parts by weight of a polymerizable vinyl monomer selected from a (meth)acrylamide monomer, vinylpyrrolidone, and vinyl acetate.