JPS5939444B2 - Method for producing vinyl resin water dispersion for coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a vinyl resin aqueous dispersion for coating, particularly a resin aqueous dispersion applicable to thermosetting coating materials.

As a method for producing a vinyl resin aqueous dispersion for coating, for example, a water-soluble or water-dispersible resin (emulsion stabilizing resin) is used as an emulsion stabilizer, and various ethylenically unsaturated monomers are mixed in an aqueous medium. Methods of polymerization are already known.

When the aqueous resin dispersion obtained by this method is applied to a thermosetting coating material, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, etc. are used as a component of the ethylenically unsaturated monomer to be subjected to polymerization. Ethylenically unsaturated monomers containing hydroxyl groups have been used. However, such monomers are generally miscible with water and migrate to the aqueous layer during polymerization where they polymerize to form water-soluble or water-dispersible polymers that can be dissolved or dispersed in the aqueous layer or incorporated into resin particles. Adsorbs to the surface. Therefore, the amount of the hydroxyl group-containing ethylenically unsaturated monomer distributed within the micelles produced during polymerization decreases, and the number of effective crosslinkable functional groups in the resin produced within the micelles decreases. Therefore, the baked film formed by adding a crosslinking agent to the resin aqueous dispersion has a low crosslinking density and good solvent resistance, water resistance,
Hardness, stain resistance, and other physical properties tend to be inferior.
The present inventors have conducted intensive research to solve the above problems and provide a method for producing a vinyl resin aqueous dispersion useful as a thermosetting coating material. A vinyl resin with a value of
The present inventors have discovered that the desired resin aqueous dispersion can be obtained by employing a slightly miscible hydroxyl group-containing monomer (hereinafter abbreviated as "hardly miscible hydroxyl group-containing monomer"), and have completed the present invention.

That is, the gist of the present invention is that the acid value is 30 to 200K0Hη/y
In the presence of a vinyl resin in a neutralized state, 5 to 40% (by weight, the same shall apply hereinafter) of a monomer represented by the following general formula as the hardly miscible hydroxyl group-containing monomer and other ethylenic inorganic resins are added. The present invention relates to a method for producing a vinyl resin aqueous dispersion for coating, which comprises polymerizing a monomer mixture consisting of 60 to 95% of saturated monomers in an aqueous medium.

[In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a propylene group or a hexamethylene group, and n represents 2 to 10.

] The vinyl resin in the present invention has an acid value of 30
~200K0H immediately/y1 preferably 35~150K0H
It is important that it is set within the range of η/7.

If the acid value is less than 30K0Hη/7, even if the vinyl resin is neutralized and used as an emulsion stabilizer, its emulsification or dispersion function will be insufficient, making it impossible to obtain the desired resin aqueous dispersion in a stable state. If it exceeds 200K0Hη/1, it will adversely affect the physical properties of the target resin aqueous dispersion, especially the water resistance and corrosion resistance, and is not practical. The specific synthesis method for vinyl resin with such acid value is as follows:
For example, (a) the vinyl resin has an acid value of 30 to 200K.
Ethylenically unsaturated carboxylic acid blended to give 0H7r9/7, (b) hydroxyl group-containing vinyl monomer 0 to 40%, and (c) other vinyl monomers are solution polymerized or bulk polymerized according to a conventional method. The typical method is The above ethylenically unsaturated carbon compound a) is
Any substance that simultaneously has one ethylenically unsaturated group and one or more carboxyl groups in its molecule is sufficient; specific examples include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. , monooctyl maleate, monobutyl maleate, monooctyl itaconate, and reaction products obtained by adding 2-hydroxyethyl methacrylate and phthalic anhydride at a molar ratio of 1:1, etc. A mixture of more than one species may be used.

Examples of the hydroxyl group-containing vinyl monomer (b) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 1-methyl-2-acrylate.
Examples include hydroxyethyl, 2-hydroxyethyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, glycerol monomethacrylate, allyl alcohol, etc., and these may be used alone or in a mixture of two or more. .

Such monomers, due to the hydrophilic nature of their hydroxyl groups,
Together with the ethylenically unsaturated carboxylic acid mentioned above, it contributes to the emulsion stabilizing effect of the vinyl resin. In addition, when applying the target tree water dispersion to a thermosetting coating material, an appropriate amount is used to compensate for the insufficient crosslinking density with carboxyl groups alone. The amount used may be selected within the range of 0 to 40%, preferably 5 to 30% of the total monomers. Examples of the other vinyl monomers (c) include ethyl acrylate, methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, styrene, vinyltoluene, acrylamide, N-butoxymethylacrylamide, etc. It may be used as one type or a mixture of two or more types. In addition, since the vinyl resin has an emulsion stabilizing effect and constitutes a part of the film formed, the types of the constituent monomers (a-c) and their resin compositions should be selected with due consideration given to the required film properties. There is a need to.

The above solution polymerization may be carried out according to usual conditions, for example, the vinyl monomers (a-c) in the above predetermined ratio are added all at once in a suitable solvent (e.g. diethylene glycol monobutyl ether) set at a certain polymerization temperature. They may be mixed and reacted in a batch manner, or they may be reacted in a continuous dropwise manner.

The polymerization temperature is 50 to 150°C, and the polymerization time is 1 to 10
Time may be adopted. The vinyl resin aqueous dispersion for coating according to the present invention is prepared by adding the above-mentioned hardly miscible hydroxyl group-containing monomer and It is produced by polymerizing a mixed monomer consisting of other ethylenically unsaturated monomers in an aqueous medium (hereinafter referred to as emulsion polymerization).

The vinyl resin itself has an emulsion stabilizing effect, but in order to be used in a polymerization system, it is necessary to neutralize some or all of its carboxyl groups and dissolve or disperse it in water. This neutralization treatment does not need to be completed before being subjected to the polymerization system, and can be achieved by using the vinyl resin and a neutralizing agent together. As the neutralizing agent, usual ones may be used, such as alkaline inorganic compounds (ammonia, potassium hydroxide, sodium hydroxide, potassium carbonate, etc.) and organic amines (monomethylamine, dimethylamine, trimethylamine, monomethylamine, etc.). Water-soluble amines represented by ethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, etc., monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine , water-soluble oxime amines represented by monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, etc., polyvalent amines represented by ethylenediamine, diethylenetriamine, etc.), and selected from these groups. They may be used alone or as a mixture of two or more.

Examples of the hardly miscible hydroxyl group-containing monomer represented by the above general formula include polypropylene glycol monoacrylate in which n is 2 to 3 or 8 to 9, n is 2 to 3, 5 to 6
or polypropylene glycol monomethacrylate with n of 8 to 9, polyhexamethylene glycol monomethacrylate with n of 2, 4 to 5, 7 to 8, or 9 to 10, etc., and one or a mixture of two or more of these may be used. May be provided.

Since these monomers are difficult to mix with water, they are efficiently introduced as a component of the resin produced within the micelles, and as a result, when the target resin water dispersion is applied as a thermosetting coating material, solvent resistance is improved. , water resistance, hardness, and other physical properties.The amount used is 5 to 4% of the total ethylenically unsaturated monomers (hereinafter referred to as total monomers) used for emulsion polymerization.
0%, preferably in the range of 10 to 30%. 5%
If it is less than this, the crosslinking density of the baked film obtained will be low, and the solvent resistance, water resistance, weather resistance, hardness, etc. will be insufficient.

If it exceeds 40%, the resulting baked coating will have a high crosslinking density, and the coating will become brittle or unreacted hydroxyl groups will remain, resulting in a decrease in water resistance.
Other ethylenically unsaturated monomers to be used in the emulsion polymerization include the ethylenically unsaturated carboxylic acid used in the synthesis of the vinyl resin described above and Hydroxyl group-containing vinyl monomer, and any one from the following groups ((a) to (n))
A species or a combination of two or more species may be employed.

(a) Esters of acrylic acid or methacrylic acid and C1-18 monoalcohols (e.g. ethyl acrylate,
n-butyl acrylate, 1-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, 1-butyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc.).

Such monomers are used to maintain good gloss, transparency, mechanical properties, chemical resistance, weather resistance, flexibility, etc. of the coating, and the amount used is 30% or more of the total monomers. It is sufficient to select within the range of . (b) Alkenyl aromatic monomers (eg, styrene, α-methylstyrene, chlorostyrene, vinyltoluene, paratertiary butylstyrene, etc.).

Such monomers improve the gloss and transparency of the coating, but it is desirable to use them in an amount of 40% or less of the total monomers. 40%
If it exceeds this, the weather resistance of the film will deteriorate.

Amides of ethylenically unsaturated carboxylic acids and substituted amides thereof (e.g., acrylamide, methacrylic acid amide, maleic acid amide, N-methylol acrylamide, N-butoxymethyl acrylamide, diacetone acrylamide, hydroxymethyl diacetone acrylamide, etc.) .

Such a monomer can make the target resin aqueous dispersion self-crosslinking, and the amount used may be selected within a range of 30% or less based on the total monomers. (d) Nitriles of ethylenically unsaturated carboxylic acids (eg, acrylonitrile, meta, acrylonitrile, etc.).

(e) Ethylenically unsaturated dicarboxylic acid diester (for example, dibutyl maleate, etc.). (f) Addition reaction product of glycidyl acrylate or glycidyl methacrylate and fatty acid.

(g) Acrylic acid or methacrylic acid and epoxy resin (
Addition reaction product with Ciel (trade name: "Cardilla E").

One isocyanate group of an ethylenically unsaturated monomer containing an isocyanate group (for example, diisocyanate such as tolylene diisocyanate or isoborone diisocyanate is blocked with a blocking agent such as lactam or oxime, and the other isocyanate group is blocked with a blocking agent such as lactam or oxime). (compounds in which an ethylenically unsaturated monomer containing an active hydrogen group such as 2-hydroxyethyl methacrylate is added to the isocyanate group of

Such a monomer also has the same function as the monomer described above, and may be used in an amount of 30% or less of the total monomers. Ethylenically unsaturated monomers containing phosphoric or sulfonic acid groups (e.g. acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, sulfonic acid ethyl methacrylate, 2-
acrylamide-2-methylpropanesulfonic acid, etc.).
Although such monomers can also impart an emulsion stabilizing effect, it is desirable to use them in an amount of 3% or less based on the total monomers, particularly in order to accelerate curing. Among these, 3-chloro-2-
Particularly preferred are those that are poorly miscible with water, such as acid phosphooxypropyl methacrylate. (x) Others include vinyl chloride, vinylidene chloride, vinyl acetate, ethylene, methoxypolyethylene glycol methacrylate, etc.

In the above emulsion polymerization, since the vinyl resin in a neutralized state can be used as an emulsion stabilizer as described above, any known emulsion polymerization method can be used, except that ordinary emulsifiers and surfactants are not used. Legal can be applied.

For example, in an aqueous medium (water or a suitable hydrophilic solvent) set at the polymerization temperature in the presence of a polymerization catalyst,
The reaction components (specifically, the vinyl resin, neutralizing agent, and ethylenically unsaturated monomer) can be mixed all at once and reacted in batches, or each reaction component can be appropriately distributed and reacted separately and continuously. It may be added dropwise to react. The polymerization temperature is O~1
00°C, preferably 30-90°C, polymerization time 1-10
Time may be employed. During emulsion polymerization, the amount of the emulsion stabilizer used is determined by the following:
The weight ratio of the emulsion stabilizer to the total amount of ethylenically unsaturated monomers to be subjected to polymerization is usually 15/85 to 90/10, preferably 20/80. It is sufficient if it is selected within the range of ~70/30. Examples of the polymerization catalyst include inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide, and sodium percarbonate; organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; Examples include azo compounds such as -2,4-dimethylvaleronitrile, and redox catalysts in which peroxide is combined with reducing agents such as potassium pyrosulfite, sodium bisulfite, and triethanolamine. A mixture of two or more types may be used.

The amount used may be normally selected within the range of 0.01 to 5% based on the total amount of reaction components. In this emulsion polymerization, if necessary, mercaptans such as n-octyl mercaptan and t-dodecyl mercaptan, disulfides such as diisopropylsantogen disulfide, and ordinary chains of rogenides, etc. A transfer agent may be used, and modifying resins such as alkyd resins and acrylic resins that do not have or have graft active groups, curing agents such as aminoplast resins and polyfunctional pro-isocyanates, pigments, etc. may be blended. Emulsion polymerization can also be carried out.

The aqueous vinyl resin dispersion produced as described above can be used as it is, or if necessary, can be treated with curing agents such as aminoplast resins, polyfunctional protoxysocyanates, and epoxy resins, pigments, antifoaming agents, and surface conditioning agents. It is sufficient to add agents and other water-based resins to form a paint.

Coating is carried out by commonly used methods such as spray coating, dipping coating, electrodeposition coating, roll coating, brush coating, etc., and is dried and cured at room temperature or by heating to improve solvent resistance, water resistance, hardness, etc. Forms a coating film with excellent physical properties (e.g. gloss, transparency, mechanical strength, boiling water resistance, corrosion resistance, chemical resistance (acid resistance, alkali resistance), stain resistance, heat resistance, weather resistance, etc.) be able to. From this, it can be said that the aqueous resin dispersion obtained by the method of the present invention is suitable for use in high-grade top coatings. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples.

In the example sentences, "parts" means "parts by weight." Example
1 80 parts of 2-hydroxypropyl methacrylate, 120 parts of acrylic acid, 80 parts of methyl methacrylate, 116 parts of n-butyl methacrylate, 160 parts of n-butyl acrylate, 240 parts of styrene, and 4 parts of 2-acrylamido-2-methylpropanesulfonic acid. polypropylene glycol monomethacrylate (number of repeating units of propylene oxide n): about 2-3) 156 parts, methyl methacrylate 264 parts, n-butyl methacrylate 174 parts,
240 parts of n-butyl acrylate, 360 parts of styrene, 3
-6 parts of chloro-2-acid phosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine,
500 parts of melamine-formaldehyde resin (trade name "Cymel 303" manufactured by American Cyanamid Company) and 2
・2'-Azobis-2,4-dimethylvaleronitrile 3
6 parts were added to form a homogeneous solution (hereinafter referred to as solution A).

Next, 3656 parts of deionized water was charged into a reactor equipped with a cooler, an inert gas inlet tube, a dropping device, and a stirrer, and the temperature was maintained at 70°C with stirring. It takes 3 hours to drip.

After completing the dropwise addition, the reaction was carried out at the same temperature for 2 hours to reduce the non-volatile content to 39.
5%, viscosity (using a B-type viscometer, the same applies below) 580 cps
A milky white vinyl resin aqueous dispersion for coating is obtained. The above resin water dispersion was applied onto an iron plate to a dry film thickness of about 40 μm,
A film is formed by baking and drying at 160° C. for 30 minutes.

The performance test results for such coatings are shown in Table 1. Example 2 To a vinyl resin having an acid value of 111 and a number average molecular weight of 4,800 as in Example 1, 156 parts of polypropylene glycol monoacrylate (number of repeating units of propylene oxide (b): about 2 to 3) and 264 parts of methyl methacrylate were added. , n-butyl methacrylate 174 parts, n-butyl acrylate 2
40 parts, 360 parts of styrene, 6 parts of 3-chloro-2-acidophosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine, 500 parts of melamine-formaldehyde resin "Cymer 303" and 2.2'
Add 36 parts of -azobis-2,4-dimethylvaleronitrile to form a homogeneous solution (hereinafter referred to as solution B).

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 39.4%, the viscosity was 590c, and the same conditions and methods were followed except that the above solution B was used instead of solution A.
ps to obtain a milky white resin water dispersion.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Example 3 Same acid value as Example 1, 111. Polypropylene glycol monomethacrylate (number of repeating units of propylene oxide (n): about 8 to 9) to a vinyl resin with a number average molecular weight of 4800.
156 parts, methyl methacrylate 264 parts, n-butyl methacrylate 174 parts, n-butyl acrylate 240 parts,
360 parts of styrene, 6 parts of 3-chloro-2-acid phosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine, 500 parts of melamine-formaldehyde resin "Cymer 303" and 2,2/-azobis-2,4- Add 36 parts of dimethylvaleronitrile to form a homogeneous solution (hereinafter referred to as solution C).

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 39.6%, the viscosity was 565c, and the same conditions and method were followed except that the above solution C was used instead of solution A.
ps to obtain a milky white resin water dispersion.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Example 4 Polypropylene glycol monomethacrylate (number of repeating units of propylene oxide (5): about 2 to 3) was added to a vinyl resin with an acid value of 111 and a number average molecular weight of 4,800 as in Example 1.
468 parts, methyl methacrylate 185 parts, n-butyl methacrylate 122 parts, n-butyl acrylate 168 parts,
252 parts of styrene, 4 parts of 3-chloro-2-acid phosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine, 500 parts of melamine-formaldehyde resin "Cymer 303" and 2,2'-azobis-2,4- Add 36 parts of dimethylvaleronitrile to form a homogeneous solution (hereinafter referred to as solution D).

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 39.2%, the viscosity was 585c, and the same conditions and method were followed except that the above solution D was used instead of solution A.
ps to obtain a milky white resin water dispersion.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Example 5 Polypropylene glycol monomethacrylate (number of repeating units of propylphoxide (n): approximately 5 to 6) was added to a vinyl resin having the same acid value of 111 and number average molecular weight of 4,800 as in Example 1.
360 parts, 212 parts of methyl methacrylate, 140 parts of n-butyl methacrylate, 193 parts of n-butyl acrylate,
290 parts of styrene, 5 parts of 3-chloro-2-acid phosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine, 500 parts of melamine-formaldehyde resin "Cymer 303" and 2,2'-azobis-2,4- Add 36 parts of dimethylvaleronitrile to form a homogeneous solution (hereinafter referred to as solution E).

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 39.5%, the viscosity was 575c, and the same conditions and methods were followed except that the above solution E was used instead of solution A.
ps to obtain a milky white resin water dispersion.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Example 6 Polypropylene glycol monoacrylate (number of repeating units of propylene oxide (n): about 8 to 9) was added to a vinyl resin with an acid value of 111 and a number average molecular weight of 4,800 as in Example 1.
2 parts, 285 parts of methyl methacrylate, n-methacrylate
188 parts of butyl, 259 parts of n-butyl acrylate, 389 parts of styrene, 6.5 parts of 3-chloro-2-acidphosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine, melamine-formaldehyde resin [Cymer 303] 500 parts and 36 parts of 2,2/-azobis-2,4-dimethylvaleronitrile are added to form a homogeneous solution (hereinafter referred to as solution F).

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 39.6%, the viscosity was 565c, and the same conditions and methods were followed except that the above solution F was used instead of solution A.
ps to obtain a milky white resin water dispersion.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Comparative Example 1 156 parts of 2-hydroxyethyl methacrylate, 264 parts of methyl methacrylate, and 17 parts of n-butyl methacrylate were added to a vinyl resin having the same acid value of 111 and number average molecular weight of 4,800 as in Example 1.
4 parts, n-butyl acrylate 240 parts, styrene 360 parts
parts, 6 parts of 3-chloro-2-acidphosphooxypropyl methacrylate, 148 parts of diethylethanolamine.
Part 3, melamine-formaldehyde resin "Cymer 3"
03'' and 36 parts of 2-Cuazobis-2,4-dimethylvaleronitrile were added to form a homogeneous solution (hereinafter referred to as G
solution).

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 38.5%, the viscosity was 640c, and the same conditions and method were followed except that the above solution G was used instead of solution A.
ps to obtain a milky white resin water dispersion. Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Comparative Example 2 A milky white resin water with a nonvolatile content of 38.9% and a viscosity of 620 cps was prepared in the same manner as in Comparative Example 1, except that 156 parts of 2-hydroxypropyl methacrylate was used in place of 156 parts of 2-hydroxyethyl methacrylate. Obtain a dispersion.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Comparative Example 3 The number of repeating units (n) of propylene oxide is approximately 2 to 3
polypropylene glycol monomethacrylate 156
Example 1 was repeated, except that 156 parts of polypropylene glycol monomethacrylate having a repeating unit n) of about 11 to 12 was used instead of 156 parts, with a non-volatile content of 39.3 parts.
%, a milky white resin water dispersion with a viscosity of 560 cps is obtained.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Comparative Example 4 600 parts of polypropylene glycol monoacrylate (number of repeating units of propylene oxide (n): about 2 to 3) and 132 parts of methyl methacrylate were added to a vinyl resin having an acid value of 111 and a number average molecular weight of 4,800 as in Example 1. , n-butyl methacrylate 87 parts, n-butyl acrylate 12 parts
0 parts, 180 parts of styrene, 3 parts of 3-chloro-2-acid phosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine, 500 parts of melamine-formaldehyde resin "Cymer 303" and 2.21-
Add 36 parts of azobis-2,4-dimethylvaleronitrile to form a homogeneous solution (hereinafter referred to as H solution).

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 39.0%, the viscosity was 600c, and the same conditions and methods were followed except that the above solution H was used instead of solution A.
ps to obtain a milky white resin water dispersion.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Comparative Example 5 Same acid value as Example 1, 111. Polypropylene glycol monomethacrylate (number of repeating units of propylene oxide (n): about 8 to 9) to a vinyl resin with a number average molecular weight of 4800.
36 parts, methyl methacrylate 294 parts, methacrylic acid n
-194 parts of butyl, 268 parts of n-butyl acrylate, 401 parts of styrene, 6.7 parts of 3-chloro-2-acidphosphooxypropyl methacrylate, 148.3 parts of dimethylethanolamine, melamine-formaldehyde resin "Cymer 303" ] 500 parts and 36 parts of 2,21-azobis-2,4-dimethylvaleronitrile were added,
A homogeneous solution (hereinafter referred to as I solution) is prepared.

Next, in the production of the resin aqueous dispersion of Example 1, the non-volatile content was 39.6%, the viscosity was 555 cp, and the same conditions and method were followed except that the above solution was used instead of solution A.
A milky white resin water dispersion is obtained in s.

Table 1 shows the performance test results of a film formed under the same conditions as in Example 1 for this resin water dispersion. Example 7 135 parts of 2-hydroxyethyl methacrylate, 135 parts of acrylic acid, 287 parts of methyl methacrylate, 225 parts of n-butyl methacrylate, 225 parts of n-butyl acrylate, 112.5 parts of styrene and 2-acrylamide-2 - Polyhexamethylene glycol monomethacrylate (number of repeating units of hexamethylene oxide (n): approx. 2)1
65 parts, N-butoxymethylacrylamide 192.5
392 parts of methyl methacrylate, 206 parts of n-butyl methacrylate, 275 parts of n-butyl acrylate, 137.5 parts of styrene, 6.9 parts of 3-chloro-2-acidphosphooxypropyl methacrylate, and dimethylethanolamine. Add 166.9 parts of homogeneous solution (hereinafter referred to as J
solution).

Next, 3304 parts of deionized water was charged into the same reactor as in Example 1, and the temperature was maintained at 70°C while stirring, and the entire amount of the J solution and 13.7 parts of deionized ammonium persulfate were added to this in a nitrogen gas stream. A solution dissolved in 300 parts of water was added separately and simultaneously over a period of 3 hours.

After completing the dropwise addition, the reaction was carried out at the same temperature for 2 hours to reduce the non-volatile content to 39.
A milky white aqueous vinyl resin dispersion for coating is obtained with a viscosity of 8% and a viscosity of 720 cps. A mixture of 100 parts of the above resin water dispersion and 10 parts of melamine-formaldehyde resin "Cymel 303" is applied to an iron plate in the same manner as in Example 1, and then baked and dried to form a film.

Performance test results for such coatings are shown in Table 2. Example 8 509 parts of polyhexamethylene glycol monomethacrylate (number of repeating units of hexamethylene oxide (n): about 4 to 5), N -138 parts of butoxymethylacrylamide, 281 parts of methyl methacrylate, 147 parts of n-butyl methacrylate, 197 parts of n-butyl acrylate, 98 parts of styrene, 3-chloro-
2-Acid phosphooxypropyl methacrylate 4.
9 parts and 166.9 parts of dimethylethanolamine are added to form a homogeneous solution (hereinafter referred to as K solution).

Next, in the production of the resin aqueous dispersion of Example 7, the non-volatile content was 39.5%, the viscosity was 730c, and the same conditions and methods were followed except that the above K solution was used instead of the J solution.
ps to obtain a milky white resin water dispersion.

Table 2 shows the performance test results of a film formed under the same conditions as in Example 1 using a mixture of 100 parts of the resin aqueous dispersion and 10 parts of the melamine-formaldehyde resin Cymer 303. Example 9 Same acid value as Example 7, 90
, 96 parts of polyhexamethylene glycol monomethacrylate (number of repeating units of hexamethylene oxide (n): about 7 to 8), 203 parts of N-butoxymethylacrylamide, 4 parts of methyl methacrylate to a vinyl resin with a number average molecular weight of 5500.
14 parts, n-butyl methacrylate 218 parts, n-butyl acrylate 291 parts, styrene 145 parts, 3-chloro-
2-Acid phosphooxypropyl methacrylate 7.
3 parts and 166.9 parts of dimethylethanolamine are added to form a homogeneous solution (hereinafter referred to as L solution).

Next, in the production of the resin aqueous dispersion of Example 7, the non-volatile content was 39.7%, the viscosity was 700c, and the same conditions and method were followed except that the above L solution was used instead of the J solution.
ps to obtain a milky white resin water dispersion.

Table 2 shows the performance test results of a film formed under the same conditions as in Example 1 using a mixture of 100 parts of the resin aqueous dispersion and 10 parts of the melamine-formaldehyde resin Cymer 303. Example 10 Same acid value as Example 7 9
0, a vinyl resin with a number average molecular weight of 5500, 412 parts of polyhexamethylene glycol monomethacrylate (number of repeating units of hexamethylene oxide (n): about 9 to 10), 153 parts of N-butoxymethylacrylamide, and 312 parts of methyl methacrylate. 164 parts of n-butyl methacrylate, 219 parts of n-butyl acrylate, 109 parts of styrene, 5.5 parts of 3-chloro-2-acidphosphooxypropyl methacrylate and 166.9 parts of dimethylethanolamine were added, and the mixture was homogenized. solution (hereinafter referred to as M solution).

Next, in the production of the resin aqueous dispersion of Example 7, the nonvolatile content was 39.8%, the viscosity was 710c, and the same conditions and method were followed except that the above M solution was used instead of the J solution.
ps to obtain a milky white resin water dispersion.

Table 2 shows the performance test results of a film formed under the same conditions as in Example 1 using a mixture of 100 parts of the resin aqueous dispersion and 10 parts of the melamine-formaldehyde resin Cymer 303. Comparative Example 6 Same acid value as Example 7, 90
, a vinyl resin with a number average molecular weight of 5500, 41 parts of 1,6-hexanediol monomethacrylate, 212 parts of N-butoxymethylacrylamide, 432 parts of methyl methacrylate, 227 parts of n-butyl methacrylate, 3 parts of n-butyl acrylate.
0.3 parts, 152 parts of styrene, 7.6 parts of 3-chloro-2-acidphosphooxypropyl methacrylate, and 166.9 parts of dimethylethanolamine were added to form a homogeneous solution (hereinafter referred to as N solution).

Next, in the production of the resin aqueous dispersion of Example 7, the non-volatile content was 40.0%, the viscosity was 725c, and the same conditions and methods were followed except that the above N solution was used instead of the J solution.
ps to obtain a milky white resin water dispersion.

Table 2 shows the performance test results of a film formed under the same conditions as in Example 1 using a mixture of 100 parts of the resin aqueous dispersion and 10 parts of the melamine-formaldehyde resin Cymer 303. Comparative Example 7 Same acid value as Example 7, 90
, 41 parts of polyhexamethylene gtycol monomethacrylate (number of repeating units of hexamethylene oxide (n): about 4 to 5), 212 parts of N-butoxymethylacrylamide, 4 parts of methyl methacrylate to a vinyl resin with a number average molecular weight of 5500.
32 parts, n-butyl methacrylate 227 parts, n-butyl acrylate 303 parts, styrene 152 parts, 3-chloro-
2-Acid phosphooxypropyl methacrylate 7.
6 parts and 166.9 parts of dimethylethanolamine are added to form a homogeneous solution (hereinafter referred to as O solution).

Next, in the production of the resin aqueous dispersion of Example 7, the non-volatile content was 39.4%, the viscosity was 700c, and the same conditions and methods were followed except that the above 0 solution was used instead of the J solution.
ps to obtain a milky white resin water dispersion.

Table 2 shows the performance test results of a film formed under the same conditions as in Example 1 using a mixture of 100 parts of the resin aqueous dispersion and 10 parts of melamine-formaldehyde resin [Cymail 303]. Comparative Example 8 Same acid value as Example 7, 90
, 688 parts of polyhexamethylene glycol monomethacrylate (number of repeating units of hexamethylene oxide (n): approximately 2), 109 parts of N-butoxymethylacrylamide, and 22 parts of methyl methacrylate to a vinyl resin with a number average molecular weight of 5500.
3 parts, n-butyl methacrylate 117 parts, acrylic acid n
-156 parts of butyl, 78 parts of styrene, 3-chloro-2-
Add 3.9 parts of acid phosphooxypropyl methacrylate and 166.9 parts of dimethylethanolamine,
A homogeneous solution (hereinafter referred to as P solution) is prepared.

Next, in the production of the resin aqueous dispersion of Example 7, the non-volatile content was 39.2%, the viscosity was 740c, and the same conditions and methods were followed except that the above P solution was used instead of the J solution.
ps to obtain a milky white resin water dispersion.

Table 2 shows the performance test results of a film formed under the same conditions as in Example 1 using a mixture of 100 parts of the resin water dispersion and 10 parts of melamine-formaldehyde resin Cymer 303.Comparative Example 9 Same acid value as Example 7: 90
, 165 parts of polyhexamethylene glycol monomethacrylate (number of repeating units of hexamethylene oxide (n): about 11 to 12), 192.5 parts of N-butoxymethylacrylamide, and methyl methacrylate to a vinyl resin with a number average molecular weight of 5500. 392 parts, meta★n-butyl nonacrylate 206
parts, n-butyl acrylate 275 parts, styrene 137 parts.
5 parts, 6.9 parts of 3-chloro2-acidphosphooxypropyl methacrylate and 166.9 parts of dimethylethanolamine were added to form a homogeneous solution (hereinafter referred to as Q solution).
shall be.

Next, in the production of the resin aqueous dispersion of Example 7, the non-volatile content was 39.5%, the viscosity was 690c, and the same conditions and method were followed except that the Q solution was used instead of the J solution.
ps to obtain a milky white resin water dispersion.

Claims (1)

[Scope of Claims] 1 In the presence of a neutralized vinyl resin having an acid value of 30 to 200 KOHmg/g, a hydroxyl group-containing ethylenically unsaturated monomer 5 to 40, which is difficult to mix with water and is represented by the following general formula.
1. A method for producing an aqueous vinyl resin dispersion for coating, which comprises polymerizing a monomer mixture consisting of 60-95% by weight of other ethylenically unsaturated monomers in an aqueous medium. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom or a methyl group, R_2 is a propylene group or hexamethylene group, and n is 2 to 1
Represents 0. 2. The method according to item 1 above, wherein the weight ratio of the neutralized vinyl resin to the mixed monomer is in the range of 15/85 to 90/10.