JPS6021606B2 - Manufacturing method of resin for anti-corrosion paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a rust-preventing paint resin, and more specifically, the present invention relates to a method for producing a rust-preventing paint resin, and more specifically, a monovinyl phosphate epoxyester compound obtained by reacting an organic monocarboxylic acid, a diglycidyl compound, and a monovinyl phosphate ester with a polymerizable inorganic resin. The present invention relates to a method for producing a resin for rust-preventing paint, which is characterized by copolymerizing a resin with a saturated monomer.

Conventionally, homopolymers of monovinyl phosphate esters represented by the above general formula or copolymers with other copolymerizable monomers have been known.

However, these polymers themselves have strong hydrophilic properties, and therefore have poor water resistance, anticorrosion properties, etc., and have defects such as the resin itself being attacked by moisture, resulting in poor adhesion. The present inventors conducted extensive research to improve the above-mentioned conventional defects, developed a method for producing an anticorrosion resin free of conventional defects, and completed the present invention.

That is, the present invention provides benzoic acid or alkylbenzoic acid represented by the general formula (in which R or R2 represents hydrogen or an alkyl group having 1 to 4 carbon atoms) or the general formula C (CH2)m (CH= C.H.C.
Q) n(CH2)pCOOH (where m is 0, 1, 4
, 7 or 10, n is 0 to 6, p is 0 to 24, and O
one or more organic monocarboxylic acids selected from aliphatic monocarboxylic acids represented by Sm+n+p≦24), 2
A diglycidyl compound having epoxy groups and the general formula (wherein R is hydrogen or a methyl group, R is a hydrogen or a methyl group, n is an integer from 1 to 6, and x represents P- or P03-) monovinyl phosphate ester)
The present invention relates to a method for producing a rust-preventing paint resin, which comprises copolymerizing 1 to 70 parts by weight of a monovinyl phosphate epoxyester compound obtained by equimolar reaction with 99 to 3 parts by weight of a polymerizable unsaturated monomer.

Examples of benzoic acid or alkylbenzoic acid represented by the general formula (in which R or R2 represents hydrogen or an alkyl group having 1 to 4 carbon atoms) that can be used in the present invention include tolydylic acid, dimethylbenzoic acid, etc. acid, p-lso-propylbenzoic acid, p-rt
-butylbenzoic acid, etc., and any of these can be used.

The general formula C (CH2) m (CH=CHC 5) n (CH2) pC that can also be used in the present invention
Examples of aliphatic monocarboxylic acids represented by OOH (where m is 0, 1, 4, 7 or 10, n is 0 to 6, p is 0 to 24, and OSm+n+p≦24) are: ,
For example, acetic acid, propionic acid, caprylic acid, capric acid,
Lauric acid, myristic acid, palmitic acid, stearic acid, n-heptaconic acid, dodecenoic acid, tetradecenoic acid,
Examples include linoleic acid, linolenic acid, icosenoic acid, etc.
It does not have radically polymerizable double bonds or conjugated double bonds.

These benzoic acids, alkylbenzoic acids, or aliphatic monocarboxylic acids can be used alone or in combination of two or more.

Examples of diglycidyl compounds having two epoxy groups that can be used in the present invention include aliphatic diglycidyl ethers (e.g., polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc.), aromatic diglycidyl These include ethers (for example, diglycidyl ethers of bisphenol A).

Monovinyl phosphoric acid represented by the general formula (wherein R is hydrogen or a methyl group, R' is hydrogen or a methyl group, n is an integer of 1 to 6, and X is P- or PQ-) that can be used in the present invention. Ester is an adduct of orthophosphoric acid or orthophosphorous acid and a monomer having a hydroxyl group and a polymerizable unsaturated group. Examples of such monomers include 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, - Acrylates or methacrylates of chloro-2-hydroxypropyl, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol (molecular weight 28 or less), polypropylene glycol (molecular weight 366 or less).

Specific examples of such monovinyl phosphate esters include, for example, Phosmer M (trade name manufactured by Yushi Products Co., Ltd.),
Kayama-PM-2 (trade name manufactured by Nippon Kayaku Co., Ltd.), Hosmer C
I (product name manufactured by Oil and Fat Products Co., Ltd.). The organic monocarboxylic acid, diglycidyl compound and monovinyl phosphate ester are used in a ratio of 1.0 to 1.1 mol of organic monocarboxylic acid and 0.9 to 1.0 mol of monovinyl phosphate to 1.0 mol of diglycidyl compound. It is better to react.

In this case, if the amount of monovinyl phosphate ester exceeds 1.0 mol, it is not preferable because gelation will occur in the next reaction step. Although the reaction can be carried out in the presence of three components, it is preferable to react the organic monocarboxylic acid and the diglycidyl compound, and then react the reaction product with the monovinyl phosphate ester. In both cases, the reaction conditions are approximately 60~
The reaction is carried out by heating at 150 pm for about 2 to 1 hours, and the end point of the reaction is determined by measuring the acid value, and the end point of the reaction is usually determined when the acid value reaches about 250 or less, preferably about 200 or less. . In this reaction, in order to prevent thermal polymerization of unsaturated groups, it is desirable to add a polymerization inhibitor such as hydroquinone at 50 to 100%. The monovinyl phosphate epoxyester compound obtained as described above is then copolymerized with a vinyl monomer.

The vinyl monomers to be copolymerized include styrene,
Pynyltoluene, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester (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, pinyl acetate, vinyl propionate, ethylene, vinyl chloride, acrylamide, methacrylamide, crotonamide, N-methylolacrylamide, diacetone acrylamide, etc. The above is appropriate. The copolymerization composition is such that the monovinyl phosphate epoxyester compound has 1 to 7 anchor parts and the vinyl monomer has 99 to 3 anchor parts to sufficiently exhibit adhesion and rust prevention ability and maintain good water resistance. preferable. 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 penzoyl bar. It is polymerized using a peroxide polymerization initiator such as oxide or tert-butyl peroctoate. The concentration of the polymerization initiator is preferably 0.5 to 1 part by weight per 100 parts by weight of the vinyl monomer.

The reaction temperature is 60-160 qo. It is also possible to obtain a polymer solution by placing an organic liquid in a reaction container and adding the monovinyl phosphate epoxyester compound, the entire amount of vinyl monomer, and a polymerization initiator, and conducting the reaction for 1 to 1 hour. A mixture of a polymerization initiator and a polymerization initiator is added dropwise over a period of 1 to 7 hours, and then the reaction is continued for 2 to 7 hours to form a polymer solution. It is also possible to obtain The polymer solution thus obtained can be used for applications such as paints, molded products, adhesives, and fillers.

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. Colorants include dyes, 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 water-soluble 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 make it distributed.

The polymer solution of the present invention has superior adhesion properties compared to conventional pinyl polymer coating resins, polyester coating resins, epoxy coating resins, polyvinyl butyral coating resins, phenolic coating resins, etc. Excellent coating film and performance such as rust prevention, water resistance, and inertia resistance.

Examples will be described below.

Parts mean parts by weight. Example 1 (Monovinyl phosphate epoxyester compound solution '11
synthesis) xylene 40
3 parts Cellosolve 40 3 parts Epiquat #828 (manufactured by Shell) 40 Eaves Coconut oil fatty acids 21 Base Tetraethylammonium bromide Pour 1.5 parts or more into 2 flasks fitted with a thermometer and stir while praying. 1
The reaction was carried out at 30 qo for 4 hours, and the end point of the reaction was defined as the time when the acid value became 0.

In the above reaction apparatus, orthophosphoric acid-2-hydroxyethyl acrylate monoester 1
96 parts Hydroquinone 0-
The mixture was added and reacted at 10,000 for 3 hours, and the end point of the reaction was when the acid value reached 75.

4g of non-volatile content. % clear solution. (Synthesis of polymer solution) Monovinyl phosphate epoxyester compound solution '1} 10 base styrene 40 anchor group n-
Butyl methacrylate 50 parts methacrylic acid 5 parts RT-butyl peroctate Mixture of 5 parts or more with toluene
50 parts of isobutanol 45 parts was added dropwise into a refluxing flask over 2 hours, and aged for 5 hours after the dropwise addition.

The resulting liquid was clear, had a nonvolatile content of 5% by weight, and a Gardner viscosity (25 qo) of Z-4. Example 2 (Synthesis of monopynyl phosphate epoxyester compound solution ■) Toluene 70 Ikarito Isopropanol Bust part Epikot #1001 (manufactured by Shell) 100 Ikarito P-
Add 178 parts of rt-butylbenzoic acid and 1.5 parts or more of tetraethylammonium bromide into two flasks equipped with a thermometer and react with a simulated pestle at 13,000 for 3 hours. When the acid value has decreased to 0.1 This was taken as the end point of the reaction.

Add 0.2 part of orthophosphoric acid mono-2-hydroxyethyl methacrylate monoester 21 base hydroquinone to the above reaction apparatus,
00 for 3 hours, and the end point of the reaction was when the acid value reached 50.

Non-volatile content 5 skin t. % clear solution. (Synthesis of polymer solution) Monovinyl lyric acid epoxyester compound solution '21 20 base styrene 30 parts 2-
Hydroxyethyl methacrylate 10 parts n-butyl acrylate 40 parts methacrylic acid
5 Base part 2,2'-Azoisoputyronitrile Add 5 parts or more of the mixture to xylene.
50 parts of isoprobanol (35$) was added dropwise into a refluxing flask over 3 hours, and aged for 5 hours after the addition.

The resulting liquid was clear and had a non-volatile content of 5 t. Gardner in %
The viscosity (25°C) was J. Example 3 (Synthesis of monovinyl phosphate epoxyester compound solution lake) Toluene 706 parts n-ptal/ol 70 base parts Epiquat #1001 (manufactured by Shell) 100 base coconut oil fatty acid 21 base tetraethylammonium bromide 1.5 More than 1000 pieces of fly lily,
2 I put it in a flask with a thermometer attached and worshiped the lantern 13
000 for 4 hours, and the time when the acid value became 0 was defined as the end point of the reaction.

196 parts of orthophosphoric acid-2-hydroxyethyl acrylate monoester was added to the above reaction apparatus.

Add 0.2 parts of quinone, 1
3 at 00qo. The reaction was allowed to proceed for an hour and the end point of the reaction was when the acid value reached 50. The non-volatile content is 5. % clear solution. (Synthesis of polymer solution) Monovinyl phosphate epoxyester compound solution glue 30 anchors styrene 25 anchors n-butyl acrylate 45 anchors methyl methacrylate 10 base methacrylic acid
5. A mixture of 5 parts or more of Ikarito ditertiary butyl peroxide and toluene.
50 basic n-butanol
The base of No. 35 was added dropwise over 4 hours into a refluxing flask, and aged for 5 hours after the dropwise addition.

The resulting liquid was transparent and had a non-volatile content of 5 t. % Gardner-viscosity (25 qo) was Z-6. Comparative Example 1 Orthophosphoric acid-2-hydroxyethyl methacrylate monoester 25 parts styrene
455 parts n-butyl acrylate 47 parts methacrylic acid
5 Anchor part 2-2'-azoisobutyronitrile Add a mixture of 5 parts or more to toluene.
50 Ikarito Iso 70 Ropanol
The mixture was added dropwise over 3 hours into a refluxing flask, and aged for 5 hours after the addition.

The resulting liquid was transparent and had a non-volatile content of 50 Wt. % Gardner viscosity (25oo) was Z-5. Comparative Example 2 Styrene No. 45
- Butyl acrylate 50 parts Methacrylic acid 5 parts 2-2
-A mixture of 5 parts or more of azoisobutyronitrile and 50 parts of toluene.

Fifty parts of Lopanol was added dropwise into a refluxing flask over 3 hours, and aged for 5 hours after the addition. The resulting liquid was clear and had a non-volatile content of 5 t. % Gardner viscosity (25°C) was Z-3. Comparative Example 3 2-Hydroxyethyl orthophosphate methacrylate mono/ester 6 styrene
45 sparse 2-hydro.

Xyethyl methacrylate 10 parts n-butyl acrylate 34 parts methacrylic acid
5 Anchors 2-2'-azoisobutyronitrile A mixture of 5 or more anchors in xylene
Isopropanol 50 was added dropwise into a refluxing flask over 3 hours, and aged for 5 hours after the dropwise addition. The resulting liquid was clear and had a non-volatile content of 5. % Gardner viscosity (25 qo) was 1. Comparative Example 4 Styrene 50 No. 2
-Hido.

xyethyl methacrylate 10 parts n-butyl acrylate 35 parts methacrylic acid
A mixture of 5 parts and more was added dropwise over 3 hours into a flask in which 50 parts of xylene, 50 parts of isopropanol, and 50 parts of the mixture were refluxed, and the mixture was aged for 5 hours after the dropwise addition.

The resulting liquid was clear and had an unexploded content of 5 skin t. The Gardner viscosity (25q0) in % was G. The results of a salt spray resistance test using the polymer solutions obtained in the above Examples and Comparative Examples are shown below.

For Examples 1 and 3 and Comparative Examples 1 and 2, the test was carried out after coating on a polished mild steel plate to a dry film thickness of 20 mm and drying at room temperature for 2 days, and for Example 2 and Comparative Examples 3 and 4. Use three commercially available butylated melamine resins. The coating was applied so that the film thickness after baking was 20%, and the test was conducted after baking for 140,002 minutes.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 or R_2 is hydrogen or has 1 to 1 carbon atoms.
benzoic acid or alkylbenzoic acid represented by the alkyl group of 4) or the general formula CH_3(CH_2)_
m(CH=CHCH_2)_n(CH_2)_pCOO
H (where m is 0, 1, 4, 7 or 10, n is 0
~6, p is 0 to 24, and 0≦m+n+p≦24); one or more organic monocarboxylic acids selected from aliphatic monocarboxylic acids represented by the following formula; a diglycidyl compound having two epoxy groups; and General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is hydrogen or methyl group, R' is hydrogen or methyl group, n is an integer from 1 to 6, It is characterized by copolymerizing 1 to 70 parts by weight of a monovinyl phosphoric acid epoxy ester compound obtained by reacting approximately equimolar amounts of monovinyl phosphoric acid ester represented by the following formula with 99 to 30 parts by weight of a polymerizable unsaturated monomer. A method for producing resin for anti-rust paint.