JPS6031332B2 - Method for producing water-dispersed resin composition - Google Patents

Description

Detailed Description of the Invention The present invention uses a resin solution synthesized in an organic solvent, which has excellent dispersion power and does not adversely affect the coating film and performance, as a dispersant, and further removes a hydrophobic organic solvent. This invention relates to the production of a water-dispersed resin using a wet granulation method.

In recent years, development research has been progressing on powder coatings, water-soluble coatings, and water-dispersible coatings as a pollution control measure, and among water-sensitive coatings, the development and research on emulsion coatings and slurry coatings is particularly remarkable.

Emulsion paints inherently have the decisive drawback of poor coating durability due to the use of large amounts of emulsifiers, and as a means of improving this, emulsion polymerization methods using reactive dispersants are being actively investigated. However, there is a major drawback in that the emulsifying effect is not sufficient and it is not possible to obtain a stable emulsion, and at present no emulsion paint with excellent dispersion stability and good coating performance has been developed. In addition, although powder coatings have excellent film properties, they have problems with the coating surface such as pinholes, craters, and orange skin when heated and melted, and the manufacturing method of powder coatings is complicated. Moreover, the coating process requires equipment specific to powder, which requires a large capital investment, and there is also the risk of dust explosion, which is a major obstacle to its use.

On the other hand, slurry paints use water as a medium, so there is no risk of explosion, and since the melting point of the particles can be lowered compared to powder, the coating surface is smoother, and conventional painting equipment can be used as is. Alternatively, it has a number of advantageous features, such as being usable with only partial improvements and leading to reduced capital investment.

This slurry paint is basically a water-dispersible powder paint in which powder paint is dispersed in water, and research and development are progressing, and many patent applications have been filed. However, the process of manufacturing powder, so-called resin particles, is similar to the manufacturing method of powder coatings, and is complicated by manufacturing complexity, particle size,
Particle distribution control is difficult, and in most cases where powder coatings are dispersed in water, particles settle violently, resulting in only slurry coatings with extremely poor dispersion stability. Furthermore, this results in a vicious cycle in which wetting agents and emulsifiers are used to promote wetting of the powder with water, and the characteristics of the slurry paint cannot be fully demonstrated. In order to improve these drawbacks, a method has been proposed in which a resin solution dissolved in a hydrophilic organic solvent is precipitated in water and the hydrophilic organic solvent is transferred into water to obtain resin particles. In such cases, only non-uniform and coarse particles are obtained, and improvement measures have been taken such as neutralizing the carboxyl groups in the resin with an alkaline substance to make the particles finer. However, due to neutralization with an alkali substance, the durability of the coating film is lost, and a large amount of hydrophilic solvent is contained in the aqueous dispersion. There are also difficulties in reusing the distillate. The present invention solves these problems and relates to the production of a slurry resin that has particularly excellent storage stability, good painting workability, and good coating film properties, and it enables the reuse of the organic solvent and water distilled off by solvent removal. It has the feature of being easy to perform.

That is, the present invention uses an organic solvent having an acid value of 20 to 300, a hydroxyl value of 0 to 150, and a number average molecular weight of 100.
A resin solution containing a resin having an acid value of 0 to 15,000 and neutralizing 40 to 100 mol% of the carboxyl groups in the resin, and a hydrophobic organic solvent containing a resin having an acid value of 0 to 90 and a hydroxyl value of 20. An organic solvent-containing resin aqueous dispersion is obtained by using a resin solution containing a resin of 50 to 100 oo as an essential component, and then the organic solvent is added under normal pressure or reduced pressure to
The present invention provides a method for producing a thermosetting water-dispersed resin composition, which comprises distilling off the composition.

In the present invention, the acid value is 20 to 300, and the hydroxyl value is o.
~150 and a number average molecular weight of 1000 to 15000
A resin solution (hereinafter referred to as a dispersant solution) containing a resin in an organic solvent, in which 40 to 100 mol% of the carboxyl groups in the resin is neutralized, and a hydrophobic organic solvent containing an acid value A resin solution containing a resin having a hydroxyl value of 0 to 90 and a hydroxyl value of 20 to 200 (hereinafter referred to as a dispersant solution) is used.

The dispersant solution used in the present invention is composed of an organic solvent and a specific resin, and the organic solvents used at that time include, for example, n- or/and IS0-hexane, n-
or/and hydrocarbons such as iso-pentan, isooctane, cyclohexane, benzene, toluene, xylene, ethylbenzene, etc. and mixtures thereof such as gasoline, ligroin, mineral spirits, solvent naphtha, methylene chloride, dichlorobentane, chloroform , carbon tetrachloride, chlorinated hydrocarbons such as trichlorethylene, ketones such as methylisobutylketone, diisobutylketone, methylcyclohexanone, isophorone, ethyl acetate, butyl acetate, amyl acetate, methylamine acetate, 2-ethylhexyl acetate Hydrophobic organic solvents include esters such as, ethers such as isopropyl ether, phthyl ether, and 2-ethylhexyl ether: methanol, ethanol, n-f.

Hydrophilic organic solvents include bro/gnol, isopro/gnol, te-pylptanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosol acetate, cellosolve acetate, etc., and each of hydrophobic and hydrophilic organic solvents. There is no problem in using two or more types. As described above, the dispersant solution used in the method of the present invention has an acid value of 20 to 300.
and has a hydroxyl value of 0 to 150 and a number average molecular weight of 10
40 to 15,000 carboxyl groups in the resin
The resin contains 100 mol% of neutralized resin as an essential component, but the resin before such neutralization exhibits hydrophobicity, and this carpoxyl group is removed by alkaline substances that are evaporated. By being neutralized, it exhibits water solubility and exhibits dispersion power, and in the subsequent coating film formation stage, it evaporates or is separated, regaining its hydrophobicity, and as a result, the coating film becomes more hydrophobic. It is desirable that water resistance be maintained.

The carboxyl group content for imparting optimal water solubility is 20 to 300, preferably 30 to 150, expressed in acid value.
It is. When the acid value is lower than 20, it is difficult to make the dispersant solubilized in water even when neutralized with an alkali, and the dispersant loses its effectiveness. Also,
If it exceeds 300, the chemical properties of the coating film will deteriorate, which is not preferable. The introduction of hydroxyl groups gives the composition thermal crosslinkability,
The amount of hydroxyl groups, that is, the hydroxyl value, which improves coating film properties, particularly water resistance and chemical resistance, is from 0 to 150, preferably from 0 to 80.

When the hydroxyl value exceeds 150, the crosslinking reaction between the dispersant and the crosslinking agent proceeds preferentially, which inhibits the crosslinking reaction with the Shinryu group in the dispersed particles, and further reduces the smoothness of the coating film due to thermal melting of the particles. As a result, the gloss and transparency are adversely affected, which is undesirable.The number average molecular weight is 1000 to 15000,
Preferably it is 2,000 to 10,000; if it is lower than 1,000, coating film suitability will decrease, and if it exceeds 150 mo, the dispersion effect will decrease and thermal fusion with dispersed particles will not be able to be carried out smoothly, resulting in an uneven coating film. This results in an adverse effect on the coating film properties. The carboxyl groups contained in such a resin are neutralized by 40 to 100 mol%, and an alkaline substance is used for neutralization, such as ammonia; n-propylamine, hexylamine, Octylamine, cyclohexylamine 2-amino-2-methyl-1mpro/gnol, 2
- Primary amines such as aminobutanol and monoethanolamine; Secondary amines such as dipropylamine, dibutylamine, diphenylamine, diethanolamine, and morpholine.
Class amines: tripropylamine, tributylamine,
Triethylamine, 2-dimethylamino-2-methyl-
Tertiary amines such as 1-bro/g/ol, N,N'-dimethylethanolamine, triethanolamine; Na
, K, and other metal hydroxides and oxides. These alkaline substances can be used alone or in combination of two or more. Further, in order to neutralize the carboxyl groups in the resin, if the amount of neutralization is less than 40 mol %, sufficient water solubilization cannot be obtained, which is not desirable. Incidentally, examples of the resin in the dispersant solution include acrylic resin, polyester resin, polyether polyester resin, and alkyd resin.

By the way, the resin in the dispersant solution of the present invention has an acid value of 20 to 3.
00, preferably 30-150; hydroxyl value 0-150,
Preferably 0-80: number average molecular weight 1000-1500
0, preferably 2000 to 10000.

Further, as the organic solvent, either a hydrophobic organic solvent or a hydrophilic organic solvent, or a mixture of two or more thereof, is used. The dispersion solution used in the present invention consists of a hydrophobic organic solvent and a specific resin, and the hydrophobic organic solvent used in this case is the same as that used in the above-mentioned dispersant solution.

In addition, the resin in the dispersion solution has an acid value of 0 to 90 and a hydroxyl value of 2.
0 to 200, and if the acid value exceeds 90, water solubilization due to carpoxyl groups tends to occur, the final product does not become water-dispersible, and moreover, it tends to cause particle aggregation, and furthermore, the coating film It is not preferable because it has an adverse effect on the water resistance, durability, etc. If the hydroxyl value is lower than 20, the crosslinking density will be low and it will be difficult to maintain the coating properties. Since the hydroxyl group exhibits hydrophilicity, it is not preferable because it will have an adverse effect on the water resistance of the coating film. Molecular weight has a great influence on coating film properties, and the range of number average molecular weight is usually as follows:
2000-20000, preferably 5000-1500
A value within the range of 0 is appropriate. If the molecular weight is lower than the number average molecular weight of 2,000, the water-dispersed particles tend to fuse together, which is a negative factor in the strength and durability of the coating film. 20
If it exceeds 000, the coating film will have poor flexibility, poor flow properties during hot melting, and the smoothness of the coating film will be reduced, which is not preferable.

Resins used in such dispersion solutions include acrylic resins, alkyd resins, polyester resins, epoxy resins,
polyether resin, vinyl chloride resin, vinyl acetate resin,
Examples include melamine resin. In the present invention, the dispersant solution/dispersant solution ratio is preferably 5/100 to 50/100 (solid content weight ratio).

If it is lower than 5/100, the dispersion effect of the dispersant solution will be weakened, and particles will tend to aggregate and fuse during the solvent removal process, which will have an adverse effect on the storage stability of the aqueous dispersion, which is not preferable.

When the ratio exceeds 50/100, the granulation property is good and a water solution with extremely excellent storage stability can be obtained, but there are disadvantages of so-called water-soluble resins such as the aqueous property and chemical resistance of the alkali-neutralized composition. is undesirable because it inhibits the characteristics of the moisture-enabled resin.

Therefore, a range of 5/100 to 50/100 is desirable because it allows the preparation of an aqueous dispersion with good dispersion stability and excellent coating properties. The aqueous dispersion thus obtained has a wide range of composition selectivity depending on its purpose of use, which is a major factor in further expanding the range of uses as a coating material. In the method of the present invention, an organic solvent-containing resin aqueous dispersion is first prepared using the essential components of the dispersant solution and dispersion solution as described above, but such an aqueous dispersion can be obtained by various means. This can be done by

Namely, (1) a method in which a dispersant solution is dispersed or dissolved in water and a dispersion solution or a dispersion of the solution in water is dispersed; (2) a method in which a mixture of a dispersant solution and a dispersion solution is dispersed in water; Examples include method (1) in which a dispersant solution is dispersed in a dispersion solution in water. The dispersant solution and the dispersion solution can be dispersed by a conventional emulsion polymerization method in the case of O/W type dispersion. In order to actually perform this dispersion method, known dispersion equipment can be used, and the degree of dispersion at the initial stage of dispersion is important. It is desirable to use a device. Normally, when obtaining an average particle size of 5 to 100, a propeller type, turbine type, one-curved turbine type, Ikari type, etc., is used.
Dispersion may be performed at a rotation speed of ~1000 rotations. or,
It can also be applied to W/O type dispersion, and this method has the advantage of obtaining fine particle dispersion type with low speed rotation. At this time, a phenomenon of thickening is observed during the dispersion, but the viscosity can be lowered by adding water, which is the dispersed soot. The resulting organic solvent-containing resin aqueous dispersion is then treated with the organic solvent contained therein under normal pressure or reduced pressure.
It is subjected to a so-called organic solvent removal operation in which it is distilled off at a temperature of 50 to 10,000 ml. The specific method for removing the organic solvent is, for example, when using a curved turbine-type suspension blade, under normal pressure or 150 to 250 Hg reduced pressure while maintaining a rotation speed of 300 to 500 rotations. , 50-100
00, the hydrophobic solvent was distilled off by co-keying with water, and the distillation rate was 95.
Completed with % or more. According to the method of the present invention, foaming during solvent removal is extremely small and the solvent can be easily distilled off, so that it is useful for preventing the dispersion particles from forming blocks due to fusion. A water-dispersed resin composition that has undergone solvent distillation by solvent removal has a great feature that it can be used as it is as a slurry resin without going through complicated steps such as powder manufacturing steps.

Residual solvents in slurry resins can affect long-term storage stability, and organic solvents in hydrophobic resins can lower the softening point of particles and induce fusion between particles. It is necessary to increase the removal rate, and the removal rate that does not cause fusion between particles is 95% by weight or more, preferably 9% by weight or more. Furthermore, when a hydrophilic solvent is used in the dispersant solution, even if the solvent remains, it has the effect of acting as a protective colloid and improving long-term storage stability. % by weight or less, and the distillation rate is 6% by weight, preferably 8% by weight, and the above-mentioned solvent removal method easily achieves the objective. The aqueous dispersion thus obtained has a nonvolatile content of 30 to 60
%, average particle size 1 to 10 French, pH 7.5 to 9.0, no sedimentation of particles was observed even after being left at room temperature for 1 month, especially when the average particle size was 1 to 5 r, it was left at room temperature for 6 months. An aqueous dispersion with extremely good storage stability and no particle sedimentation is obtained.

In the present invention, it is most preferable that the dispersant solution is obtained using a hydrophobic organic solvent for the following reasons.

That is, when such a dispersant solution is used, the time required to remove the solvent and water by the solvent removal method after granulation can be significantly shortened, the residence time of the solvent in the aqueous dispersion can be shortened, and the granulation process can be improved. It is effective in destroying particles and preventing them from becoming blocked.

Therefore, the generation of coarse particles can be reduced to a very small amount, or even not detected at all, resulting in a narrow particle distribution.
Therefore, an aqueous dispersion (aqueous dispersion resin composition) with uniform particle size can be prepared. The water-dispersed resin composition of the present invention allows the pigment to be present in the particles and can provide a coated surface with excellent gloss.

This pigment mixing method is most useful when mixing the dispersant solution and the dispersion solution, and this can be carried out in exactly the same way as the mixing method for solution-based paints. . Also useful is a method in which the pigment is mixed into an organic solvent-containing aqueous dispersion, that is, a water content teaching solution before the solvent is distilled off. Conventional kneading methods such as ball mills, ball mills, sand mills, homomixers, and jet mixers are effective methods, as they allow the pigment to be mixed into the resin particles and also have the effect of making the water-dispersed particles ultra-fine. be. In addition, the method of kneading the pigment after solvent distillation causes the pigment to surround the particles, which impedes the thermal flow properties of the particles, which makes it difficult to obtain a smooth coating surface. Moreover, it is not preferable because it tends to result in a coated surface with extremely low gloss. These drawbacks of enamelization in emulsion paints have been a major obstacle to the development of emulsion-based enamel paints. The water-dispersed resin composition thus obtained by the method of the present invention can be used and applied for various purposes, but is particularly useful as a paint.

When used as such a coating, the composition obtained by the method of the invention is usually thermally cured using a curing agent. As curing agents in this case, when the functional group in the resin is a hydroxyl group, examples include amino resins such as hexamethoxymethylmelamine and tetrabenzoguanamine, flock polyisocyanate, etc., and when the functional group is a carboxyl group, examples include epoxy resin. . The ratio of these curing agents used is 3 to 3 parts by weight of the curing agent to 70 to 97 parts by weight of the resin in the water dispersion (shown below), preferably 80 parts by weight of the former.
~95 parts, the latter range of 5 to 2 dark B is appropriate.
The composition obtained by the method of the present invention may further contain a well-known and commonly used catalyst for accelerating the curing reaction, if necessary.
A curing accelerator) may be added as appropriate, and an acrylic acid long-chain alkyl ester polymer, a fluorine compound, etc. may be added as a fluidity regulator to prevent the occurrence of craters on the painted surface and improve smoothness.

Since the aqueous dispersion obtained by the production method of the present invention is a fine particle dispersion with a high non-volatile content, it can be coated thickly with very little sagging or foaming by regular painting methods such as spray painting, roll painting, brush painting, and electric painting. By heating and curing at a temperature of 140 to 19,000, a strong coating film with good gloss and smoothness is formed.

The present invention will be described in detail below using specific examples. Manufacturing example 1 (
Production of dispersant solution) Pour 50 grams of toluene into a two-necked four-necked flask equipped with a thermometer, a Nadayo machine, and nitrogen gas, and add 20 grams of styrene, 20 grams of n-butyl methacrylate, and B while refluxing the toluene. -Hide.

5 parts of xyethyl methacrylate, 5 parts of acrylic acid,
A premix consisting of 1 part of azobisisobutyronitrile, 5 parts of ditertiary butyl peroxybenzoate, and 5 parts of ditertiary butyl peroxide was added dropwise over 5 hours and polymerized for one additional period. The obtained resin solution had a nonvolatile content of 50%, a gun donor viscosity of Z5 to Z6,
Acid value 38.9, hydroxyl value 21.6, number average molecular weight 720
It was 0. Furthermore, 2-dimethylaminoethanol 4 Nobe was added to the resin solution to neutralize the carboxyl groups in the resin by 80 mol%, thereby obtaining a dispersant solution A-1. Production Example 2 (same as above) 400 parts of toluene and 2 parts of ditertiary chill peroxide were placed in a 2-necked 4-necked flask equipped with a thermometer, rope scaler, and nitrogen gas, and 18 parts of methyl methacrylate was added under reflux of toluene. , 14 parts of ethyl acrylate, 4 parts of 8-hydroxyethyl methacrylate, 12 parts of n-octyl acrylate, 28 parts of acrylic acid, 4 parts of azobisisobutyronitrile, 6 parts of ditertiary butyl peroxybenzoate, 20 parts of toluene. The premix consisting of Ikarito was added dropwise over 5 hours and allowed to polymerize for an additional hour.

The resulting resin solution had a nonvolatile content of 40% and a Gardner viscosity of U.
-V, an acid value of 21.8, a hydroxyl value of 17.3, and a number average molecular weight of about 7,000. Further, 27.7 parts of 2-dimethylaminoethanol was added to the resin solution to neutralize the carboxyl groups in the resin by 80 mol %, thereby obtaining a dispersant solution A-2. Production example 3 (same as above) Put the ethyl cellosolve 100 base into a four-loaf flask equipped with a thermometer, rope strainer, dropping funnel, and nitrogen gas.
The temperature was raised to 120 qo over 3 nights.

Add 40% styrene while keeping the temperature inside the flask at 120qo.
3 parts of a premix consisting of 0 parts of n-butyl methacrylate, 400 parts of 2-hydroxyethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 34 parts of azobisisobutylonitrile, and 2 parts of ditertiary butyl peroxide. After being allowed to drip over a period of time and polymerized for an additional hour, the nonvolatile content was 50%, Gardner viscosity Z, acid value 38.9, hydroxyl value 43.1 (resin solid content), and Gardner color number 2 to 3.
A viscous resin solution A-3 was obtained.

Furthermore, in order to impart water solubility, 7.4 parts of 2-dimethylaminoethanol was added, and the carboxyl groups were neutralized by stirring for 80 minutes. The resulting resin solution A-3 had a water tolerance of 2000% or more. there were. Manufacturing example 4 (
Same as above) In a four-necked flask equipped with a thermometer, stirrer, and nitrogen gas, 600 parts of isophthalic acid, 70 parts of adipic acid, 15 parts of trimethylolpropane, 30 parts of neobentyl glycol, and 0.2 parts of dibutyltin oxide. The temperature of the part was raised to 230 oo over 3 hours, the integrated reaction was carried out for another 4 hours, the mixture was diluted with ethyl cellosolve to a nonvolatile content of 60°C, and then the resin was diluted with 2-dimethylaminoethanol to make it water-soluble. The carboxyl group of was neutralized to 100 mol% to obtain water-droppable resin A-4.

The resulting resin had a water tolerance of 2000% or more.
Production Example 5 (Production of dispersion solution) 800 parts of toluene, 8 parts of styrene, 77 parts of n-butyl methacrylate, and 8-hydroxyethyl methacrylate were placed in a 3-4-necked flask equipped with a thermometer, flywheel, and nitrogen gas. 4 parts of Ikari acid, 3 parts of acrylic acid, and 2 parts of ditertiary butyl peroxybenzoate were charged, and the temperature was raised to 90°C in 1 hour. After polymerization for 1 hour, the temperature was raised to 11,000°C in 1 hour, and 20 parts of toluene, 20 parts of styrene were added. A premix consisting of 308 parts of n-butyl methacrylate, 160 parts of 3-hydroxyethyl methacrylate, 12 parts of acrylic acid, 8 parts of ditertiary butyl peroxybenzoate, and 1 part of azobisisobutyronitrile was The mixture was added dropwise over a period of time, and polymerization was further carried out for one hour.

The resulting resin solution B-1 had a nonvolatile content of 50%, a Gardner viscosity of XY, an acid value of 5.8, a hydroxyl value of 43.1, and a number average molecular weight of 7,700. Production Example 6 (same as above) 570 parts of toluene and 1 part of ditarsia leaf chill peroxide were charged into a 3-necked 4-necked flask equipped with a thermometer, condenser, and nitrogen gas, and 4 parts of methyl methacrylate was added under reflux of toluene.
A premix consisting of 5 parts of ethyl acrylate, 335 parts of ethyl acrylate, 20 parts of 8-hydroxyethyl methacrylate, 15 parts of acrylic acid, 6 parts of azobisisoputilonitrile, and 23 parts of toluene was prepared in 3. Immediately dripping, then 1 hour
Immediate polymerization yielded a slightly crab-colored dispersion solution B-2 having a nonvolatile content of 50%, a Gardner viscosity of Z5 to Z, an acid value of 5.8, a hydroxyl value of 43.2, and a number average molecular weight of 7,500.

Production Example 7 (same as above) 100 parts of toluene was charged into a flask equipped with a thermometer, a dropper, a dropping funnel, and nitrogen gas, and the temperature was raised to reflux temperature. A premix consisting of 150 parts of hydroxyethyl methacrylate, 15 parts of acrylic acid, 17 parts of azobisisobutyronitrile, and 1 part of ditertiary butyl peroxide was added dropwise over 3 hours, and then heated under reflux for an additional 1 hour. Resin solution B- obtained by polymerization
3 has a nonvolatile content of 50%, a Gardner viscosity W-X, and an acid value of 5.
8, hydroxyl value 32.4, Gardner color number 1 or less.

Production Example 8 (same as above) In a flask equipped with a thermometer, condenser, and nitrogen gas, 40 parts of isophthalic acid, 40 parts of adipic acid, 185 parts of trimethylolpropane, 313 parts of neobentyl glycol,
0.2 part of dibutyltin oxide was heated in 3 hours to 2
The resin obtained by further reaction at 30°C for 5 hours was diluted with methyl isobutyl ketone so that the nonvolatile content was 60%.
A resin solution B-4 having a Gardner viscosity of V-W, an acid value of 6, a hydroxyl value of 84.3, and a Gardner color number of 2 was obtained.

Example 1 Put 40 parts of 50 ounces of water into a suitable container, and gradually add 12 parts of the A-1 solution obtained in Production Example 1 while stirring at 8,000 revolutions using a homomixer and disperse uniformly. death,
Further, 400 parts of the B-1 solution obtained in Production Example 2 was gradually added and dispersed for 30 minutes to obtain a uniform dispersion with a particle size of 1 French or less.

The base portion of the dispersion liquid 92 was placed in a separable flask equipped with a thermometer, a sieve machine, and a solvent removal device, and the temperature was gradually raised to 75 m while rotating at 300 rpm.

Reduce the pressure by 250 to 180 skin Hg using a decompression device,
By azeotroping toluene with water, 99% of toluene is produced in 2 hours.
The above was distilled off, non-volatile content was 40%, viscosity was 0.5 poise, p
650 parts of a slurry resin having a H8.7 and an average particle diameter of 4.3 mm was obtained. Further, 250 parts of toluene was distilled off. Even after the obtained slurry resin was left at room temperature for one month, no agglomeration or sedimentation of particles was observed. Above slurry resin 2
When 38 parts of methyl etherified melamine resin (Watersol S-683: trade name manufactured by Dainippon Ink Chemical Co., Ltd., non-volatile content 70%) was uniformly dispersed and applied to a tin plate by spray painting, it was sprayed with a spray gun. There was no foaming, and there was very little sagging due to vertical painting. Further, phosphorization was performed at 160oo for 30 minutes, and the film thickness was 5.
A tough coating film with good gloss and smoothness was obtained. Next, 200 parts of the above slurry paint was dispersed with 7.7 parts of scaly aluminum powder (Albeest 110 Hoko: trade name manufactured by Toyo Aluminum Co., Ltd., non-volatile content 65%) with 5 parts of ethyl cellosolve, and then mixed at high speed with a homomixer. Add it gradually and disperse it uniformly to make a metallic slurry paint.
When the resulting paint was left at room temperature for one week, aluminum sedimentation was observed, but it was easily redispersed by shaking.
Furthermore, when spray painting was carried out using air pressure &tm/, the aluminum had good adhesion. Another 1600
By baking for 0.03 minutes, a coating film with a film thickness of 40 mm, excellent gloss with a metallic appearance, and good smoothness was obtained. Example 2 125 parts of A-2 solution obtained in Production Example 2 and B obtained in Production Example 6
The procedure was carried out in the same manner as in Example 1, except that the resin solution mixed with 40 parts of solution 2 was gradually added to 266 parts of water. Obtained Buddha's slurry resin.

The resulting slurry resin had extremely excellent dispersion stability, with no particle aggregation or sedimentation observed even after it was left at room temperature for 6 months.

Watersol S-6834 to 200 parts of slurry resin
When 7.6 parts and 2 $ of water were added, the mixture was uniformly dispersed, and the mixture was applied by spray painting, it exhibited excellent coating suitability without clogging the spray gun or foaming. Further, 160003 coating was applied, and a strong coating film with a film thickness of 50 mm and good gloss and smoothness was obtained. Example 3 Except for using 24 parts of B-1 solution obtained in Production Example 5, 40 parts of white enamel obtained by uniformly dispersing 9 parts of titanium dioxide and 9 parts of toluene into bran in a sand mill as a dispersion. A slurry resin having a nonvolatile content of 40%, a viscosity of 0.65 poise, a pH of 8.9, and an average particle size of 5.6 poise was obtained in the same manner as in Example 1.

The above slurry resin showed slight sedimentation even after being left at room temperature for one week, and was easily redispersed by stirring. When 20 parts of white slurry resin and 5.4 parts of Watersol S-6832 were uniformly dispersed and applied by spray painting, there was no clogging of the spray gun or foaming, and the coating was suitable for vertical painting without sagging. showed that. Baking was further carried out for 1,600,030 minutes to obtain an extremely strong coating film with a film thickness of 60 mm, gloss of 92 (60 o specular reflectance), and good smoothness. Example 4 125 parts of the A-2 solution obtained in Production Example 2 was uniformly dispersed in 38 county water, and 280 parts of the B-2 solution obtained in Production Example 6 was mixed with butyl etherified melamiso resin (Super Beckamine J). −
820-60: Trade name manufactured by Dainippon Ink Chemical Co., Ltd., non-volatile content 60%) 10 parts (nonvolatile content 60%) was gradually added to obtain a few liquids of water, but the same method as Example 1 was used to remove the solvent at 50oo As a result, the non-volatile content was 40% and the viscosity was 1.0.
A slurry resin having a pH of 0 poise, a pH of 8.9 liters, and an average particle diameter of 7.2 was obtained.

No agglomeration or sedimentation of particles was observed in this slurry resin even after it was left at room temperature for one week, and although it settled very slightly even after it was left for one month, it was easily redispersed by scattering. When the slurry resin was directly applied by spray coating, there was no clogging of the spray gun or foaming, and the coating was baked in 14 to 30 minutes, resulting in a strong coating film with a thickness of 50 ridges and good gloss and smoothness. Example 5 1. Pour 15 parts of water into a container, gradually add 12 parts of resin solution A-3 obtained in Production Example 3 while dissolving it uniformly, and then mix with a homomixer at 10,000 rpm. Gradually add 200 parts of resin solution B-3 obtained in Production Example 7 to
After continuing to stir for 0 minutes, an emulsified aqueous dispersion having an average particle size of 5 mm or less was obtained.

The above-mentioned watery liquid was transferred to a separable flask equipped with a thermometer, a rope strainer, and a shedding agent device, and the temperature was raised to 8,000 °C by rotating the fly at 1,000 revolutions using a turbine bent lamp. .

Next, the hydrophilic organic solvent and the hydrophobic organic solvent were gradually distilled off by co-weaving with water under a reduced pressure of 250 to 150 Hg. More than 98% of the hydrophobic organic solvent and 70% or more of the hydrophilic organic solvent were removed after about 2 hours of removal. The water-dispersed resin thus obtained had an average particle size of 5 French (calculated from the Coulter counter cumulative weight percentage), and when the nonvolatile content was adjusted to 60% with water, the Gardner viscosity was J,
The pH was 7.8. Further, the obtained water-dispersed resin showed no change in viscosity even after being left at room temperature for one month, and no sedimentation of particles was observed. Furthermore, 28.5 parts of methyl etherified melamine resin (Dainippon Ink Chemical ■: Watersol S-683 non-volatile content 70%) was added to 100 parts of the above water-dispersed resin, and the mixture was uniformly dispersed and spray-painted, resulting in excellent coating workability. 1
A tough coating film was obtained by heating and curing for 60,003 minutes. Example 6 Into a separable flask equipped with a thermometer, a pseudo Azusa machine, and a solvent removal device, 12 parts of the resin solution A-3 obtained in Production Example 3 and 20 parts of water were charged, and heated to 80°C while bowing. The temperature is raised to
The punch speed was adjusted to 1000 revolutions, and 20 parts of resin solution B-3 obtained in Production Example 7 were dropped over 30 minutes to obtain an emulsified water teaching solution.

Thereafter, in the same manner as in Example 6, the hydrophilic and hydrophobic organic solvents were distilled off, the speed was reduced to 300 revolutions, and the mixture was cooled to room temperature. The resin solution thus obtained has a non-volatile content of 60%.
Adjust with water so that Gardner viscosity W, pH 8.2
, the average particle diameter was 12〃.

Furthermore, no sedimentation of particles was observed even after being left at room temperature for one week.
Slight sedimentation was observed after being left for one month, but it was easily redispersed by using artificial water. Upper water dispersion resin 10 Ikaribe's methyl etherified melamine resin (Dainippon Ink Chemical Watersol S-68 non-volatile content 70%) 27
When spray painting was performed, a tough coating film was obtained with excellent coating workability and 16,000, 3 powder success, 0 heat curing. Example 8 1. Add 20 parts of water to a container and add resin solution A-4 obtained in Production Example 4.
The resin solution B-4 obtained in Production Example 8 was gradually added, and mixing was continued for 30 minutes, resulting in an emulsified water with an average particle size of 5 degrees or less. A dispersion was obtained.

Claims (1)

[Claims] 1 An organic solvent with an acid value of 20 to 300 and a hydroxyl value of 0
~150 and a number average molecular weight of 1000 to 15000
4 of the carboxyl groups in the resin.
A resin solution obtained by neutralizing 0 to 100 mol% and a hydrophobic organic solvent having an acid value of 0 to 90 and a hydroxyl value of 20 to 2.
00 as an essential component to obtain an organic solvent-containing resin aqueous dispersion, and then distilling off the organic solvent at 50 to 150°C under normal pressure or reduced pressure. A method for producing a water-dispersed resin composition.