JPS63286403A - Production of nonaqueous dispersible type resin - Google Patents

Abstract

PURPOSE:To obtain a resin, having excellent dispersion stability and useful as a temporary protecting coating, by inverting the phase from a homogeneous polymerization system of a polymer having polymerizable unsaturated bonds and specific functional groups with a carboxyl group-containing monomer, etc., into a nonaqueous dispersion type with a specific solvent. CONSTITUTION:(A) A polymer [e.g. glycidyl (meth)acrylate], having one or more ethylenically unsaturated bonds and/or functional groups (e.g. glycidyl or isocyanate groups) reactive with carboxyl groups in one molecule and 2,000-30,000mol.wt. and soluble in aliphatic hydrocarbon based solvents (e.g. n-heptane) and/or alicyclic hydrocarbon based solvents (e.g. cyclohexane) in an amount of 3-93pts.wt. is homogeneously polymerized with (B) 7-30pts.wt. carboxyl group-containing ethylenically unsaturated monomer (e.g. crotonic acid or fumaric acid) and (C) 0-90pts.wt. ethylenically unsaturated monomer [e.g. methyl (meth)acrylate] in an organic solvent and the organic solvent in the resultant homogeneous polymerization system is then replaced with the above-mentioned hydrocarbon solvent. The phase of the system is subsequently inverted into a nonaqueous dispersion type.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a new and useful non-aqueous dispersion resin, and more particularly, to The polymer is produced in an aliphatic and/or alicyclic hydrocarbon solvent by inverting the homogeneous polymerization system of a polymer and a carboxyl group-containing monomer to a non-aqueous dispersion type using a specific solvent. The present invention relates to a method for producing a non-aqueous dispersible resin in which the particles are stabilized against agglomeration.

As described above, the present invention provides a technique for stabilizing polymer particles containing a high concentration of carboxyl groups by inverting the phase from a homogeneous system to a non-aqueous dispersion system, and is particularly suitable for coating. Among these, the present invention aims to provide a non-aqueous dispersion type resin that can be used as a coating material useful for applying a temporary protective coating, and a non-aqueous dispersion thereof.

[Problems to be solved by conventional technology and invention]

That is, the present invention is particularly useful for temporarily protecting the surface of an article by depositing a coating on the surface of the article that can be easily removed by a simple dissolution operation when removal becomes necessary. The present invention provides a method for producing a non-aqueous dispersion type resin.

This temporary protective coating is applied to the painted surface (painted surface).
or by applying a coating to polished or polished surfaces that can be deposited and easily removed afterwards without detrimentally affecting these painted or polished surfaces.
It is already well known that painted or polished metal articles provide temporary protection against weather or atmospheric pollution, chemical attack or accidental damage.

Such protection is natural, for example, if a newly completed car is parked outdoors in the open for a period of time, such as while waiting for transport, or if the car is provided to the customer in its original condition. This is particularly desirable in the automobile industry, where dealers engaged in transportation have a need to drive or transport vehicles over certain distances while transporting them to their yards.

By the way, a commonly used method of protection is to apply wax to a newly painted car body.

Although this wax application forms a coating that is both waterproof and somewhat scratch resistant, it may be necessary to remove it later by applying a solvent or, in some cases, a jet of water vapor. use, which may pose risks in terms of flammability and toxicity, or may require special equipment.

Another type of temporary protective coating that is widely used to compensate for these drawbacks is one that uses a dispersion of a carboxyl group-containing synthetic polymer in the proportion necessary for dissolution.

This type does indeed have the considerable advantage that it can be easily prepared by treatment with dilute alkali and subsequent washing with water, for example aqueous lattes obtained by conventional aqueous emulsion polymerization methods.

The most common type of polymer is a wood-based polymer.

However, in the method of creating this type of carboxyl base using synthetic polymers, amines are used,
In some cases, aqueous solvents such as alcohols and cellosolves are used, which causes the problem of odor generation, and since they are water-based, there is also the disadvantage that drying properties are inferior to organic solvent types. .

Therefore, the present inventors used a high-boiling point aliphatic and/or alicyclic hydrocarbon solvent that has drying properties comparable to typical wax-based materials as a conventional temporary protective coating material and is relatively low in toxicity. As a result of extensive research into dispersion type resins, that is, non-aqueous dispersion type resins, the present invention was completed by discovering a method for producing non-aqueous dispersion type resins with sharp particle diameters.

By the way, in the conventional manufacturing method of non-aqueous dispersion type resin, the monomer is soluble in the solvent in which the dispersing resin is dissolved, but the polymer obtained from the monomer is Although it is common to polymerize a mixture of such monomers in which the monomers are insoluble to form particles, monomers having a carboxyl group are not soluble in aliphatic and/or alicyclic hydrocarbon solvents. Paints using such dispersion resins often have poor solubility in the paint film, and therefore have difficulty obtaining uniform particle sizes when polymerized in these types of solvents. It appears as a single piece.

[Means for solving problems]

However, in view of the drawbacks of the prior art as described above, particularly in the case of using this type of aliphatic and/or alicyclic hydrocarbon solvent, the present inventors developed a method for using this type of solvent. As a result of extensive research in search of a method that would yield non-aqueous dispersion resins with uniform particle diameters, we found that a specific polymer containing an unsaturated bond or a specific functional group A carboxyl group-containing monomer is an essential component, and if necessary, a monomer copolymerizable with this carboxyl group-containing monomer is also used, and a polar solvent such as alcohols or ketones is used as the main component. By using a method of uniformly polymerizing in an organic solvent, and then replacing the organic solvent with an aliphatic and/or alicyclic hydrocarbon solvent under stirring, particles with a uniform particle size were obtained. The present invention was completed by discovering that a dispersed resin liquid consisting of particles can be obtained.

That is, as an essential component (A) an aliphatic and/or alicyclic carbonized compound having one or more ethylenically unsaturated bonds and/or one or more functional groups capable of reacting with a carboxyl group in one molecule; 3 to 93 parts by weight of a polymer that is soluble in a hydrogen-based solvent and has a molecular weight within the range of 2.000 to 30.000, and (B) 7 parts by weight of a carboxyl group-containing ethylenically unsaturated monomer. ~30 parts by weight, and optionally further including (C) 0 to 90 parts by weight of an ethylenically unsaturated monomer copolymerizable with the monomer (B). homogeneously polymerizing in an organic solvent, then the organic solvent in the homogeneous polymerization system thus obtained,
A method for producing a non-aqueous dispersible resin having particles with a uniform particle size, characterized by phase inversion to the desired non-aqueous dispersible type by substitution with an aliphatic and/or alicyclic hydrocarbon solvent. This is what we are trying to provide.

Here, first of all, the above-mentioned polymer (A> refers to a vinyl copolymer having an ethylenically unsaturated double bond at the terminal or side chain, and representative examples thereof include: After obtaining a vinyl copolymer containing a thiol group by polymerizing a vinyl monomer in the presence of a mercaptan, this is reacted with an unsaturated monomer containing an epoxy group such as glycidyl (meth)acrylate. Alternatively, a vinyl polymer containing a terminal carboxyl group obtained by polymerizing a vinyl polymer in the presence of an initiator having a carboxyl group is reacted with an unsaturated monomer containing an epoxy group such as glycidyl (meth)acrylate, Examples include polymers in which two double bonds are introduced.

The above-mentioned functional group capable of reacting with a carboxyl group refers to a glycidyl group or an isocyanate group, and representative monomers containing such a functional group include glycidyl (meth)acrylate, Examples include methylglycidyl (meth)acrylate, vinyl isocyanate or isocyanate ethyl (meth)acrylate, and by use of these monomers, the polymer (A) used in the present invention can be obtained.

The polymer (A) contains at least one functional group capable of reacting with an unsaturated double bond and/or a carboxyl group, but it is preferable that the polymer contains at most two functional groups. If there are three or more functional groups, the system will become gelled, so special care must be taken.

Rather, it is recommended to limit the number to two.

In addition, the molecular weight of the polymer (A) is 2,000 to
30,000, preferably within the range of 2.500 to 20,000; if it is less than 2.000, the stability of the particles after phase inversion by solvent substitution tends to be insufficient; If it exceeds 30,000, the reactivity of the functional groups that can react with unsaturated double bonds or carboxyl groups will be poor, making it difficult to obtain the desired resin with sufficient particle stability. Both are unfavorable because the viscosity of the system becomes too high and the coating workability becomes poor.

The appropriate amount of the polymer (A) to be used is 3 to 93 parts by weight, preferably 5 to 50 parts by weight, and if it is less than 3 parts by weight, the stability of the particles and the uniformity of the particle size may deteriorate. On the other hand, if it exceeds 93 parts by weight, the viscosity of the system will increase and the coating workability will be significantly reduced, which is not preferable.

Next, typical examples of the carboxyl group-containing ethylenically unsaturated monomer (B) include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid,
Monoalkyl (C3-C4) ester of maleic acid, monoalkyl/L/(C1-Ca) ester of fumaric acid or monoalkyl (CI-C4) itaconate ester; or β-hydroxyethyl (meth)acrylate, β
- Examples include adducts of hydroxyl group-containing vinyl monomers such as hydroxypropyl (meth)acrylate, β-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate and acid anhydrides such as succinic anhydride. .

The amount of the monomer (B) used is 7 to 30 parts by weight,
A suitable range is preferably 12 to 20 parts by weight.

If the amount is less than 7 parts by weight, the resin tends to be difficult to remove with a dilute aqueous alkali solution, while if it exceeds 30 parts by weight, the resin tends to have poor water resistance as a protective film, and therefore, the resin tends to be difficult to remove with a dilute aqueous alkali solution. Both are undesirable since they tend to remain as "water droplets" when removed.

On the other hand, typical examples of ethylenically unsaturated monomers (C) copolymerizable with the above-mentioned polymers (A) and monomers (B) include methyl (meth)acrylate and ethyl (meth)acrylate. , n-propyl (meth)acrylate,
i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, 5
ec-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethylaminoethyl (meth)acrylate or various (meth)acrylic acid esters such as diethylaminoethyl (meth)acrylate; dialkyl (c+ -C4) of unsaturated dibasic acids such as dimethyl maleate, dimethyl fumarate, dibutyl maleate, dibutyl fumarate or dibutyl itaconate; Esters; cyano group-containing monomers such as acrylonitrile; various vinyl esters such as vinyl acetate, vinyl benzoate or "Beoba" (branched resin group carboxylic acid vinyl esters manufactured by Shell, Netherlands); “Viscoat 8F, 8FM
, 3F or 3FMJ (fluorine-containing (meth)acrylic acid esters manufactured by Osaka Organic Chemical ■) (per)fluoroalkyl group-containing monomers; vinyl chloride, vinyl butoxide, vinylidene chloride, vinylidene butoxide or chlorotrifluoride. Halogenated olefins such as fluoroethylene; or aromatic vinyl monomers such as styrene, α-methylstyrene, pt-butylstyrene or vinyltoluene.

The organic solvents used in solution radical polymerization using the various monomers listed above include esters such as methyl acetate, ethyl acetate, n-butyl acetate, or amyl acetate. ; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, or cyclohexanone; or alcohols such as methanol, ethanol, i-propyl alcohol, or n-butanol; furthermore, toluene or Of course, an aromatic hydrocarbon solvent such as xylene and an alcohol solvent such as those mentioned above can be used in combination.

In addition, such solution radical polymerization can be carried out using organic solvents such as those listed above, and various azo compounds such as azobisisobutyronitrile or peroxide compounds such as benzoyl peroxide. It can be carried out by a conventional method using a radical polymerization initiator, and at that time,
Furthermore, it is of course possible to use various chain transfer agents such as lauryl mercaptan, octyl mercaptan, or α-methylstyrene dimer as a molecular weight regulator, if necessary.

Thus, while removing the organic solvent from the homogeneous polymerization solution obtained using the raw materials listed above, the aliphatic and/or alicyclic hydrocarbon solvent is added dropwise in parallel with the solvent removal operation. It is necessary to perform the replacement.

By the way, the viscosity of the system is determined by the ratio of the alcohol, ketone or ester solvent that is a good solvent to the aliphatic and/or alicyclic hydrocarbon solvent that is a poor solvent (depending on the type of solvent and the resin). ), the viscosity of the system increases most rapidly, and
Beyond that point, the viscosity of the system decreases as the amount of aliphatic and/or alicyclic hydrocarbon solvent increases.

Here, representative aliphatic hydrocarbon solvents include n-hebutane, ``Rose'' (a product of Shell Company, Netherlands), ``Isopar E or GJ (a product of Exxon Chemical Company, America),'' Naphtha No. 5 or No. 6” (product of the same company), rlP turben l-1
620J (Idemitsu Petrochemical Product) or "White Sol" [Kyodo Oil Product], and the present invention also includes mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. In that case, the amount of the aliphatic solvent used should be 50% by weight or more.

On the other hand, typical examples of the alicyclic hydrocarbon solvent include cyclohexane, methylcyclohexane, and ethylcyclohexane, but the alicyclic hydrocarbon solvent and the aliphatic hydrocarbon solvents listed above are Of course, the present invention also includes the combined use of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent. When such an alicyclic solvent and an aromatic solvent are used in combination, the amount of the alicyclic solvent used should be 50% by weight or more.

Needless to say, the polymerization solvent used in carrying out the method of the present invention, that is, the organic solvent, and the dispersion solvent, that is, the aliphatic and/or alicyclic hydrocarbon solvent, are of course The greater the difference in boiling point, the more advantageous it can be expected that the desired dispersion can be obtained in a shorter time in the manufacturing process.

Incidentally, when combining i-propyl alcohol or methyl ketone with "loose" or "isopar E," such advantages in the manufacturing process can be expected.
On the other hand, if the boiling point difference is less than 20°C and the combinations are close, it will take a long time to replace the solvent, so the combination of solvents should be selected at 20°C or higher. It is desirable to have a boiling point difference of .

Thus, the desired non-aqueous dispersion type resin obtained by the method of the present invention can have a high carboxyl group content and have an average particle size of about 0.1 to 0゛, 8μ. Moreover, it has excellent stability.

As a non-aqueous dispersion type resin having such various characteristics, as mentioned above, the product obtained according to the method of the present invention can be used as a coating composition for temporarily coating automobile bodies, industrial vehicles, parts of agricultural equipment, etc. Particularly useful for applying protective coatings.

The products of the present invention can also be used as coating compositions on various products having polished metal surfaces, such as stainless steel sink units, or other articles made from copper, brass or aluminum, or on plastic-like products. It is also useful as a temporary protective coating for surfaced articles and even glassware.

Thus, coatings using non-aqueous dispersible resins obtained by the method of the present invention are significantly harder and tougher than temporary protective coatings using conventional waxes.

Furthermore, the product obtained according to the method of the present invention can be used not only as a coating but also as an adhesive, a sealant, and the like.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, parts and percentages are all based on weight unless otherwise specified.

Reference Example 1 [Preparation example of unsaturated bond-containing polymer (A)] 66.7 parts of "Wax" and di-
Add 0.2 parts of t-butyl peroxide to 120
When the temperature reached the same temperature, a mixture of 97 parts of n-butyl methacrylate, 7 parts of -butyl peroctoate, and 2 parts of thioglycolic acid was added dropwise over 5 hours. After completion of the reaction, the same temperature was maintained for 5 hours to continue the reaction. Next, 13 parts of glycidyl methacrylate was added and the reaction was carried out at 125°C for 4 hours, so that the nonvolatile content was 60%, the viscosity (Gardner viscosity at 25°C; hereinafter the same) was U-V, and the number average molecular weight was 3. ,50
A high molecular weight polymeric monomer of 0 was obtained. Hereinafter, this will be abbreviated as (A-1).

Reference Example 2 [Example of Preparation of Epoxy Group-Containing Polymer (A)] Into the same flask as in Reference Example 1, 100 parts of "Isopar E" and 0.2 parts of di-t-butyl peroxide were charged and heated at 120°C. When the temperature reached that temperature, a mixture consisting of 98 parts of i-butyl methacrylate, 2 parts of glycidyl methacrylate, and 8 parts of t-butyl peroctoate was added dropwise over 6 hours. When kept at the same temperature for 5 hours, the non-volatile content is 50% and the viscosity is B-C.
A desired polymeric monomer having a number average molecular weight of s, ooo was obtained. Hereinafter, this will be abbreviated as (A-2).

Reference Example 3 [Example of preparation of unsaturated bond-containing polymerization #(A)] In a flask similar to Reference Example 1, 1.000 g of "naphtha No. 5" was added.
and 7. of “Befcosol P-470-704 [polyester polyol manufactured by Dainippon Ink & Chemicals ■]”.
After charging 2 parts, 50 parts of i-butyl methacrylate
A mixture of 45 parts of n-butyl acrylate and 1.0 parts of t-butyl peroctoate was added dropwise over 4 hours, and after the addition was completed, the same temperature was maintained for another 7 hours until the nonvolatile content was 50 parts. %, a viscosity of XY and a number average molecular weight of 15.000 was obtained.

Hereinafter, this will be abbreviated as (A-3).

Reference Example 4 [Example of Preparation of Polymer (A) Having Both Unsaturated Bonds and Isocyanate Groups] In a flask similar to Reference Example 1, 49% of "Isoper E" was added.
The temperature was raised to 80℃, and "Beccosol P-47
3.5 parts of 0-70J, 7 of i-butyl methacrylate
A mixture of 7.5 parts of n-butyl acrylate, 2 parts of isocyanate ethyl methacrylate, and 8 parts of t-butyl peroctoate was added dropwise over 8 hours. After completion of the dropwise addition, the reaction was continued by maintaining the same temperature for 8 hours to obtain the desired polymeric monomer having a nonvolatile content of 50%, a viscosity of B-C, and a number average molecular weight of 5.200. Hereinafter, this will be abbreviated as (A-4).

Example 1 In a flask similar to Reference Example 1, 66.7 parts of i-propyl alcohol and 2 parts of di-t-butyl peroxide were added.
After raising the temperature to 80°C, 20 parts of methyl methacrylate, 40 parts of ethyl acrylate, 20 parts of methacrylic acid, and 33 parts of the polymeric monomer (A-1) obtained in Reference Example 1 were added. A mixture consisting of 3 parts of t-butyl peroctoate and 2 parts of i-propyl alcohol was added dropwise over 6 hours, and after the addition was completed, the mixture was kept at the same temperature for 5 minutes.
After holding for a period of time, a vinyl resin solution with a nonvolatile content of 50% and a viscosity of X was obtained.

Next, the i-propyl alcohol was distilled out of the system while gradually increasing the temperature from 80°C, and at the same time "wax" was dropped into the system. When this outflow amount reaches 100 copies,
The dropwise addition of 100 parts of the i-propyl alcohol was completed, and when the temperature reached 108°C, the distillation of 100 parts of the i-propyl alcohol was completed.

In this way, the desired non-aqueous dispersion type resin, that is, a non-aqueous dispersion liquid of vinyl resin was obtained, which had a non-volatile content of 5.
It was a milky white non-aqueous dispersion with a viscosity of 0% and a viscosity of R.

In addition, the average particle size of this material is
“Sub Micron Particle Analyzer (Sub+*1 cronparti) manufactured by Electro-X
cle analyzer) J Coulter model (
As a result of measurement using Coul-ter Model) N-4 (the same applies hereinafter), it was 0.15 μ-.

Example 2 Into the same flask as in Reference Example 1, 66.7 parts of i-propyl alcohol and 0.0 parts of di-t-butyl peroxide were added.
．． After charging 2 parts, the temperature was raised to 80°C, and then 20 parts of methyl methacrylate, 40 parts of ethyl acrylate,
A mixture consisting of 20 parts of methacrylic acid, 33.3 parts of the polymeric monomer (A-1) obtained in Reference Example 1, and 3 parts of t-butyl peroctoate was added dropwise over 6 hours, and the addition was completed. After that, it was kept at the same temperature for 5 hours, and the nonvolatile content was 5 hours.
A vinyl resin solution with a viscosity of 0% and a viscosity of X was obtained.

Next, the i-propyl alcohol was distilled out of the system while gradually increasing the temperature from 80° C., and at the same time, a mixed solvent of "wax"/methylhexane = 50,150 (parts by weight) was dropped into the system. When the flow rate reached 100 parts, the dropping of 100 parts of the wax/methylhexane mixed solvent was completed, and finally, when the temperature reached 100°C, 100 parts of i-propyl alcohol was added. Distillation is complete.

In this way, the desired non-aqueous dispersion resin, that is, a non-aqueous dispersion of vinyl resin, was obtained, but the characteristic values of this were as follows:
As shown in the table.

Examples 3 to 7 Each resin solution was obtained in the same manner as in Example 1, except that the organic solvents, monomers, and initiators shown in Table 1 were used.

The characteristic values (nonvolatile content, viscosity, and number average molecular weight) of each resin solution are shown in the same table.

Alternatively, a milky white non-aqueous dispersion was obtained in the same manner as in Example 1, except that an alicyclic hydrocarbon solvent was used.

The property values (nonvolatile content, viscosity, and average particle diameter) of each nonaqueous dispersion are shown in the same table.

Comparative Example 1 Into the same flask as in Reference Example 1, 66.7 parts of "wax" and the polymeric monomer (A-1) obtained in Reference Example 1 were added.
After charging 33.3 parts of
A mixture of 20 parts of methacrylic acid and 3 parts of t-butyl peroctoate was added dropwise over a period of 6 hours, and after the addition was completed, the same temperature was maintained for 5 hours to carry out the reaction, and the nonvolatile content was 50%. A control non-aqueous dispersion having a viscosity of Y-Z was obtained, but the formation of "bubbly" was observed in the system.

Just to be sure, I measured the average particle diameter and found that it was 5μ-
25% of the particles had a particle diameter of 20μ or more.

Comparative Example 2 Into the same flask as in Reference Example 1, 85% of “Isopar E” was added.
Part and the polymeric monomer obtained in Reference Example 2 (A-2
) and heated to 80°C, then 35 parts of methyl methacrylate and 3 parts of n-butyl acrylate were charged.
3 parts of methacrylic acid and 2 parts of t-butyl peroctoate were added dropwise over 6 hours.
After the completion of the dropwise addition, the reaction was continued by maintaining the same temperature for 6 hours to obtain a control non-aqueous dispersion having the properties shown in Table 1, but this dispersion contained particles of 20 g or more. diameter of “
The existence of “Bu” was recognized.

Comparative Example 3 A product was prepared in the same manner as Comparative Example 1, except that the amount of methacrylic acid used was changed to 2 parts and the amount of methyl methacrylate used was changed to 38 parts, and the properties were as shown in Table 1. A control non-aqueous dispersion was obtained.

The performance of each non-aqueous dispersion type resin obtained in each Example and Comparative Example was evaluated.

The results are summarized in Table 1.

The performance evaluation was conducted in the following manner.

Alkali removability: Each non-aqueous dispersion resin was applied separately onto a glass plate using a 6 mil applicator, and then each coating was immersed in a 1% ammonia aqueous solution for 1 minute. It was lifted up, then exposed to running water, and visually evaluated.

○...The roots are not stopped at all and are completely removed.

Δ...The roots are stopped in a very small part.

x: Almost no paint film was removed and remained.

Stability: Collect 12 g of each non-aqueous dispersion type resin in a screw tube and centrifuge it in a centrifuge for 4 hours at 2+00 Or, p, 100 ml, then remove the supernatant and precipitate. A visual evaluation was conducted for both the object and the object.

◎・・・Supernatant layer is 0II11, uniformly dispersed O...
...Supernatant layer is less than 211111, good dispersion △...
...The skim layer is within the range of 2 to ioam x...The skim layer exceeds 10 mm.

〔Effect of the invention〕

As is clear from the results in Table 1, the non-aqueous dispersion obtained by the method of the present invention has excellent dispersion stability, and when used as a temporary protective coating for paints and ( It is known that it has excellent alkali removal properties.

Claims (1)

Scope of Claims: (A) having one or more ethylenically unsaturated bonds and/or one or more functional groups capable of reacting with carboxyl groups in one molecule, and having a molecular weight of 2,000 to 30,000; in,
and 3 to 93 parts by weight of a polymer soluble in an aliphatic hydrocarbon solvent and/or an alicyclic hydrocarbon solvent, and (B) 7 parts by weight of an ethylenically unsaturated monomer containing a carboxyl group.
~30 parts by weight and (C) 0 to 90 parts by weight of an ethylenically unsaturated monomer copolymerizable with the above monomer (B) are uniformly polymerized in an organic solvent, and then the resulting homogeneous A method for producing a non-aqueous dispersion resin, which comprises replacing the organic solvent in the polymerization system with the aliphatic hydrocarbon solvent and/or alicyclic hydrocarbon solvent, thereby inverting the phase to a non-aqueous dispersion type. .