KR100575715B1 - Preparation method of non-aqueous dispersive resin for top coating for automobiles - Google Patents

Abstract

The present invention provides a first step of preparing a dispersion stabilizer by addition reaction of a three-dimensional repulsion layer, an adsorption layer and a solvent, and an ethylenic unsaturated containing the prepared dispersion stabilizer, an acrylic monomer, a polymerization initiator, and at least two hydroxyl groups in a molecule. In the method for producing a non-aqueous dispersion resin for automotive topcoat comprising a second step of mixing a monomer to produce a non-water dispersion resin, the acrylic resin modified with cellulose acetate butyrate in addition to the second step By further containing 5 to 20% by weight to prepare a non-water-dispersible resin for automotive topcoat, the added CAB-modified acrylic resin prevents agglomeration between resin particles, thereby excellent storage and flowability.

Non-Water Dispersion * CAB * Manufacturing Method * Storage * Flow

Description

  Preparation method of non-aqueous dispersive resin for top coating for automobiles

The present invention relates to a method for producing a non-aqueous dispersion resin for automotive topcoat, and more particularly, to preparing a dispersion stabilizer, wherein the ethylenically unsaturated monomer containing an acrylic monomer, a polymerization initiator and at least two hydroxyl groups in the molecule In the method for preparing a non-water-dispersed resin, the acrylic resin modified with cellulose acetate butylate (CAB) is further added to prepare the non-water-dispersed resin, thereby preventing agglomeration between the resin particles to prevent storage and flowability. The improved method for producing a non-aqueous dispersion resin for automotive top coat.

There are various types of resins for automobile paints according to the intended use. However, rheology control agents are used to improve orientation of pigment dispersion resins and pigment particles while using polyester, alkyd, and thermosetting resins as main materials for automotive coatings. Doing.

  As rheology regulators used in the past, CAB, microgels, SAGGING-CONTROL agents, and the like have been generally used, but these have respective problems.

For example, when CAB is used, there is a problem of poor workability due to dust during painting, and in particular, the dilution ratio of the solvent is enhanced, and thus the environmental pollution problem is seriously reluctant to be used.

In order to solve this problem, an aqueous type product such as a micro-gel has been developed. However, since the microgel type is manufactured using an emulsifier, it is necessary to grasp the characteristics of the pigment for each pigment and undergo an electrical charge evaluation. In view of compatibility with pigments and resins, there is a problem that aggregation and seed are more likely to occur during paint storage.

  Therefore, as a way to solve the above problems, many studies on the method for producing non-dispersible resins and imparting rheology are introduced in various literatures. The weather resistance and water resistance is insufficient, and the situation is used in part for the automotive top coat.

Conventional techniques for the preparation of non-water-dispersible resins include European Patent No. 0038127, which discloses that the resin itself can be used in spray coating by improving the leveling properties of the coating and the orientation of the pigments by imparting rheology to the resin itself. have. The dispersion stabilizer used herein was a graft copolymer, and a non-water-dispersible resin having a particle size of several microns or less using an organic monomer of a nonpolar aliphatic hydrocarbon type as a dispersion medium and an acrylic monomer insoluble in the dispersion medium. The method of preparing the was universalized.

However, most of the raw materials used in the non-aqueous dispersion resin thus prepared are long chain oils having good compatibility with non-polar solvents. Limits are expressed in compatibility.

In order to solve the above problems, an acrylic acid type is used instead of oils, or an attempt to reduce the content of stearic acid is attempted, but the situation is not satisfactory.

On the other hand, automotive paints, which occupy a significant portion of the paint consumption, require a beautiful coating appearance, such as high-quality signing and individualization, according to customer demand. In addition, it has to adapt to various climate changes, so the physical properties must be excellent. However, conventional non-water-dispersible resins exhibit limitations in terms of storage workability and flowability, and in terms of coating workability, including rheology of paints.

 Therefore, the inventors of the present invention, in order to obtain a balance of thermal flowability, crosslinking reaction rate, resin viscosity, and the like of the resin to develop a method for producing a non-water-dispersible resin for automotive topcoat with good appearance, heat resistance, weather resistance and workability. During the research effort, there is a limit to existing non-water-dispersible acrylic resins, so that the acrylic monomer having excellent storage and basic chemical resistance and excellent appearance and chemical resistance is used in the coating, and modified to CAB to introduce a urethane bond. As a result of the addition of the acrylic resin, as a result of forming an excellent appearance and at the same time having a rheology imparting function, it was found that the aggregation phenomenon between the resin particles can be prevented to improve storage and flow properties, thereby completing the present invention. It became.

Accordingly, it is an object of the present invention to provide a method for producing a non-water-dispersible resin for automotive top coat with excellent storage and flowability.

In order to achieve the object of the present invention, a method for preparing a non-water-dispersible resin for automotive topcoat is a first step of preparing a dispersion stabilizer by addition reaction of a three-dimensional repulsive layer, an adsorption layer, and a solvent, and the prepared dispersion stabilizer and acrylic monomer. And a second step of preparing a non-water-dispersed resin by mixing a polymerization initiator and an ethylenically unsaturated monomer containing at least two or more hydroxyl groups in a molecule. In the preparation of the non-water-dispersible resin, it is characterized in that it further comprises 5 to 20% by weight of an acrylic resin modified with cellulose acetate butyrate.

Hereinafter, the present invention will be described in detail.

The present invention provides a method for preparing a non-dispersion resin by preparing a dispersion stabilizer, and adding an acrylic monomer, a polymerization initiator, and an ethylenically unsaturated monomer containing at least two hydroxyl groups in a molecule thereto. The present invention relates to a method for producing a non-aqueous dispersion resin for automotive topcoat by further adding an acrylic resin modified with CAB.

First, the first step of preparing the dispersion stabilizer of the present invention is as follows.

That is, it is a step of preparing a dispersion stabilizer by addition reaction of the three-dimensional repulsion layer, the adsorption layer and the solvent.

The three-dimensional repulsive layer of the present invention is compatible with a solvent and uses two or more selected from epoxy copolymers, reactive methane, 1,2-hydroxy-stearic acid, soybean oil fatty acid and castor oil fatty acid. Examples of the methane used for molecular weight control include methane ethanol, methane propanol and methane propionic acid.

In addition, the compound and isocyanate are reacted to compensate for weather resistance, and isocyanates used at this time include methyl-, butyl-, propyl-, hexyl- and cyclohexyl-isocyanates.

Such a three-dimensional repulsive layer is composed of 30 to 60% by weight of the dispersion stabilizer, if the content is less than 30% by weight, it is difficult to manufacture the dispersion resin due to excessive teeing during the production of the dispersion resin, exceeding 60% by weight If you do, you will lose the properties of low viscosity and solids.

In addition, the adsorption layer of the present invention is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl copolymer, acrylic acid, methacrylic acid and fatty acid Use it.

Adsorption layer of the present invention is composed of 10 to 30% by weight, if the content is less than 10% by weight, the formation of particles may be reduced and the appearance may be inhibited, and when the content exceeds 30% by weight, the viscosity is high. The reaction can be heterogeneous.

In addition, the organic solvent used as the solvent is a non-polar aliphatic hydrocarbon-based organic solvent, for example, pentane, heptane, hexane, octane, nonane, ethyl propionate, 2-methylpentane, methyl propionate, isopentane or neo Pentane is used individually or in mixture of 2 or more types.

In the present invention, the dispersion stabilizer may be prepared by the following method.

1) Three-dimensional repulsive layer monomer, adsorption layer of methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl copolymer, acrylic acid, methacrylic acid A method in which two or more kinds of monomers are added to react to leave an acid value and an epoxy group at the end of the side chain.

2) Glycidyl methacrylate, glycidyl acrylate, etc. react with the acid value remaining at the side chain terminal of the compound prepared by the method of 1) by 0.2-0.9 equivalents with respect to the acid value. How to leave a bond.

3) A method of leaving an acid value and a double bond at a terminal by reacting 0.2-0.9 equivalents of an acid monomer with respect to an epoxy group remaining at the side chain terminal of the compound prepared by the method 1).

4) Add two or more kinds of monomers such as methyl methacrylate, acrylic acid, and methacrylic acid to the compound prepared by the method of 1), leaving only the acid value at the end of the side chain, and then again glycidyl acryl A method of reacting acid and glycidyl methacrylate with an acid monomer in an amount of 0.2 to 0.9, leaving a double bond of an acid value and an active at the end thereof.

5) By adding two or more kinds of methyl methacrylate, glycidyl acrylate, glycidyl methacrylate to the compound prepared by the method of 1), leaving an epoxy group at the end of the side chain, and then again By reacting an acid monomer by 0.2-0.9 equivalents with respect to the epoxy group monomer, it may be prepared by a method of leaving a double bond of an epoxy group and an active group at the end of the side chain.

The dispersion stabilizer prepared by the above method has an active double bond in the molecule, and the double bond forms a strong adsorption layer between the dispersed particles and the dispersion stabilizer by directly participating in the reaction by forming a chemical bond in the preparation of the dispersed particles. The dispersion stability of the acidic resin can be improved, and when applied to the paint, the chemical and physical properties of the coating can be improved.

The second step is to prepare a non-aqueous dispersion resin of the present invention by adding an acrylic monomer, a polymerization initiator, an ethylenically unsaturated monomer containing at least two hydroxyl groups in the molecule, and a CAB modified acrylic resin to the dispersion stabilizer prepared above. .

The dispersion stabilizer of the present invention is prepared in the first step is preferably 3.0 to 30% by weight of the total non-dispersible resin solid content, less than 3% by weight is impossible to prepare a stable dispersion resin, when the dispersion exceeds 30% by weight The whole viscosity rises and is liquefied so that the properties of the low viscosity, high solids, which are the properties of the dispersant, are lost.

The acrylic monomers used here are methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl (meth) acrylate, butyl isocyanate, propyl isocyanate, hexyl isocyanate, butyl isocyanate, butyl methacrylate, ethyl acrylate, Acrylonitrile, acrylamide, vinyl acetate, AA-6 (methyl meth macromer), acrylic acid, methacrylic acid, 2-ethylhexyl acrylate, 2-hydroethylethyl acrylate, 2-hydroxypropyl acrylate, normal ( Consisting of alkoxy methyl) acrylamide, normal (alkoxy methyl) methacrylamide, trimethylolpropanetriacrylate, arylmethacrylate, 1,6-hexanedioldiacrylate, diethylene glycol diacrylate and butanediol diacrylate One or two or more monomers selected from the group It can be used as 52~80.5% by weight relative to the resin solids dispersion. If less than 52% by weight of the dispersion stabilizer is a high ratio may be a problem for compatibility with other resins, if it exceeds 80.5% by weight can not be a low viscosity, solidifying.

In addition, as a polymerization initiator, benzoyl peroxide, t-butyl benzoate, or 2,2'- azobisisobutyl nitrile is used individually or in mixture of 2 or more types, and it is used at 0.3-8.0 weight% of the whole composition.

If the content of the polymerization initiator is less than 0.3% by weight, the size of the dispersed particles is enlarged, and the leveling property is decreased during the production of the coating film. When the content of the polymerization initiator is greater than 8.0% by weight, the entire dispersion system is liquefied, which is characterized by high solid content and low viscosity. You lose your talent. That is, in the above range, it has a uniform and stable particle size and can further increase the leveling property when forming the coating film to obtain a beautiful appearance of the coating film.

In addition, the present invention includes an ethylenically unsaturated monomer containing two or more hydroxyl groups in the molecule to enhance flow, for example, 2,3-dihydroxy propyl methacrylate, 2,3-dihydro Oxypropyl acrylate (manufactured by Nippon Kogyo Co., Ltd.-GMH-301, Japanese Oil and Fat GLM Line), addition product of carboxyl group-containing polyhydric alcohols and epoxy group-containing ethylenically unsaturated monomers; And 5 to 20% by weight of the macromers, cellulose methacrylates, cellulose acrylates, etc., obtained by reacting a hydroxyl group-containing copolymer derived from a carboxyl group-containing chain transfer agent with an epoxy group-containing ethylenically unsaturated monomer, and the like. .

In the present invention, it is more effective to use the hydroxyl group-containing ethylenically unsaturated monomer in copolymerization with a known ethylenically unsaturated monomer for the purpose of controlling viscosity, solubility and hardness, gloss, glass transition temperature and the like of the coating film.

In particular, in the present invention, an acrylic resin modified with CAB is used to enhance the compatibility in preparing the paint and to improve the shelf life of the resin.

The acrylic resin modified with CAB of the present invention is prepared by reacting a CAB modified acrylic monomer with an acrylic monomer. In this case, the CAB-modified acrylic monomer is a reaction of the hydroxy group and the isocyanate group-containing acrylic monomer of the CAB, the isocyanate group-containing acrylic monomer used at this time isocyanate methyl methacrylate, metaacrylonisocyanate, metaisopropenyl alpha Dimethylbenzene isocyanate etc. are used, respectively, and are represented by following Chemical formulas 1-3.

Wherein R is a methyl group or hydrogen.

Wherein R is a methyl group or hydrogen.

Wherein R is a methyl group or hydrogen.

The reaction for producing the hydroxyl group and isocyanate of such CAB is generally as follows. After mixing CAB and a solvent, an isocyanate group-containing acrylic monomer and a catalyst are added dropwise to react until unreacted NCO remains, thereby producing a CAB-modified acrylic monomer.

In addition, the CAB-modified acrylic resin thus prepared is dropped into an acrylic monomer and a polymerization initiator in a solvent, and then reacted to prepare the CAB-modified acrylic resin of the present invention.

Therefore, in the 3.0-30% by weight of the dispersion stabilizer obtained in the first step, containing 52-80.5% of the acrylic monomer, 0.3-8.0% by weight of the polymerization initiator, 5-20% by weight of the CAB-modified acrylic resin and at least two or more hydroxyl groups in the molecule Non-dispersible resin is prepared by mixing 5-20% by weight of an ethylenically unsaturated monomer.

When applying the non-aqueous dispersion resin prepared according to the present invention to a top coat for automobiles, by coating a medium coating on the primer coated primer, and then drying the coating using the non-aqueous dispersion resin 10-20 microns as a dry coating film Keep the flash time for about 10 minutes after spraying.

On top of that, the Cree paint is spray dried to 10-100 microns with a dry coating, and then maintained for 10 minutes and then heat-cured at 130-150 ° C for 20-40 minutes.

The following examples and comparative examples will be described in more detail the manufacturing method of the non-dispersible resin of the present invention and the coating composition containing the resin, but is not intended to limit the scope of the present invention.

Preparation Example 1 CAB modified acrylic resin production example

Into a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 300 g of toluene and 700 g of butyl acetate were placed and heated to the reflux temperature. Here, 600 g of methyl methacrylate, 300 g of ethyl acrylate, 16.5 g of acrylic acid, and 100 g of a CAB-modified acrylic monomer (which is a monomer prepared from CAB and an isocyanate group-containing acrylic monomer represented by Formula 1) are added to 5 g of benzoyl peroxide. Dropped for an hour and held for 2 hours. After cooling to room temperature, toluene was used to adjust the solids content to 50% by weight to prepare CAB-modified acrylic resin CAB-1.

Preparation Example 2 CAB modified acrylic resin production example

 A CAB-modified acrylic resin CAB-2 was prepared in the same manner as in Preparation Example 1, except that the CAB-modified monomer was used an isocyanate group-containing acrylic monomer represented by Formula 2.

Preparation Example 3 CAB modified acrylic resin production example

A CAB-modified acrylic resin CAB-3 was prepared in the same manner as in Preparation Example 1, except that the CAB-modified monomer was used an isocyanate group-containing acrylic monomer represented by Formula 3.

Example 1

(1) Preparation of Dispersion Stabilizer

150 g of toluene was added to a reactor equipped with a stirrer, a thermometer, a nitrogen injection tube, a separator, and a cooler, and heated to reflux temperature while injecting nitrogen gas. Then, 500 g of 1,2-hydroxy stearic acid was added and completely dissolved. 1.00 g of methanesulphonic acid was added and maintained at reflux for 3 hours.

While the reaction proceeds, the acid value is measured every 30 minutes. When the acid value reaches 36-38 (solid content), the acid value is cooled down to reflux temperature, and the mixture is refluxed with 55 g of acrylic resin (200 g of butyl acetate), followed by 20 g of styrene and glycidyl methacrylate. 169g, 5g of 2,2-azobisisobutylnitrile, and the reaction was maintained for 6 hours), and a mixture of 1.5g of dimethylethanolamine and 0.5g of pt-butylcatechol was added thereto, and then again at a limiting temperature. The reaction was maintained for 6 hours at.

When the acid value was measured every 30 minutes as described above, when the acid value was 1.0 or less, the intermediate reactant was prepared by cooling below reflux temperature and diluting by adding 300 g of Exol D-30 (manufactured by Exol Chemical Co., Ltd.).

The obtained intermediate reactant was a light brown liquid resin having a solid content of 50% and an acid value of 1 or less.

150 g of butyl acetate was added to a new reactor of the same type as above, and nitrogen gas was injected to raise the temperature to reflux, followed by 100 g of methyl methacrylate, 30 g of hydroxyethyl acrylate, and 50 g of 2,2 'azobisisobutyl. A mixed solution consisting of nitrile and 300 g of the intermediate reactant prepared by the above method was added at a constant rate for 6 hours. The reaction was carried out for 2 hours, 380 g of butyl acetate was added thereto, diluted, and cooled to room temperature. After preparing the resin, 30 g of normal butyl isocyanate, 50 g of zylene, and 0.2 g of dibutyl tin dilaurate were added, and the temperature was raised to 50 ° C. for about 3 hours to react. When the isocyanate was not detected, the reaction was cooled. To obtain a dispersion stabilizer A-1 having a solid content of 30-35%.

2) Preparation of non-water dispersion resin

200 g of heptane and 200 g of hexane were added to a reactor equipped with a stirrer, a thermometer, a nitrogen injection tube, and a cooler, and heated to the reflux temperature while injecting nitrogen gas. Then, 50 g of methyl methacrylate and 5.0 g of 2,2`- A mixed solution consisting of azobisisobutylnitrile and 10 g of the above-mentioned dispersion stabilizer A-1 was added thereto, followed by holding for 30 minutes, followed by 100 g of isobutyl methacrylate, 50 g of isobutyl acrylate, and 20 g of 2-hydroxy. Oxyethyl acrylate, 5 g acrylic acid, 20 g AA-6 (macromer of Dong-A Synthetic Chemistry) and 20 g 2,3-dihydroxy propylmethacrylate, 1.0 g 2,2-azobisisobutylnitrile and A- 1 After mixing the mixed solution consisting of 20g at a constant rate for 2 hours to maintain the reaction for 2 hours, lower the temperature to 80'C and add 70g of CAB-1 resin to cool after 2 hours holding reaction. Milky white non-aqueous dispersion resin B-1 which is 45% of solid content was obtained.

Example 2

(1) Preparation of Dispersion Stabilizer

150 g of toluene was added to a reactor equipped with a stirrer, a thermometer, a nitrogen injection tube, a separator, and a cooler, and heated to reflux temperature while injecting nitrogen gas. Then, 500 g of 1,2-hydroxy stearic acid was added to dissolve it completely. g of methanesulphonic acid was added and maintained at reflux for 3 hours.

As the reaction proceeds, the acid value is measured every 30 minutes. When the acid value reaches 36-38 (solid content), the acid value is cooled down to reflux temperature, and the mixture is refluxed with 55 g of acrylic resin (200 g of butyl acetate) and 20 g of isobutyl acryl and glycidyl meta 169 g of acrylic, 5 g of 2,2-azobisisobutylnitrile, and the reaction was maintained for 6 hours) was added thereto, and a mixed solution of 50 g of methane ethanol, 1.5 g of dimethylethanolamine and 0.5 g of pt-butylcatechol was added. After the addition, the reaction was maintained at reflux for 6 hours.

As described above, the acid value was measured every 30 minutes, and when the acid value became 1.0 or less, the temperature was cooled to reflux or lower, 50.9 g of cyclohexyl isocyanate and 0.5 g of dibutyl tin dilaunate were added, and the temperature was raised to 50 ° C. It reacted until it was not detected, and prepared dispersion stabilizer A-2 resin.

2) Preparation of non-water dispersion resin

200g of heptane and 200g of hexane were added to a reactor equipped with a stirrer, a thermometer, a nitrogen injection tube, and a cooler, and heated to reflux while injecting nitrogen gas. A mixed solution composed of 50 g of methyl methacrylate, 5.0 g of 2,2′-azobisisobutylnitrile and 10 g of the dispersion stabilizer A-2 resin prepared above was added thereto, and the reaction was carried out for 30 minutes. Then 200 g of isobutyl methacrylate, 23 g of 2-hydroxypropyl acrylate, 8 g of acrylic acid, 20 g of AA-6 (macromer of Dong-A Synthetic Chemistry), 10 g of aryl methacrylate, 2,3-dihydrate A mixed solution consisting of 10 g of oxypropyl acrylate, 1.0 g of 2,2-azobisisobutylnitrile and 20 g of A-2 resin was added at a constant rate for 2 hours, and the reaction was carried out for 2 hours. Then, 80 g of CAB-2 resin was added to the mixture for 3 hours, followed by cooling to prepare a milky non-aqueous dispersion resin B-2 having a solid content of 46% by weight.

Example 3

25 g of methane propanol and 25 g of methanol ethanol were used instead of 50 g of methane ethanol in preparing the dispersion stabilizer, and 2,3-dihydroxy propylmethacrylate was used as the hydroxyl group-containing ethylenically unsaturated monomer in the preparation of the non-aqueous dispersion resin. In the same manner as in Example 2, a dispersion stabilizer and a non-aqueous dispersion resin B-3 were prepared. Solid content of the final non-water dispersion resin B-3 is 45 weight%.

Example 4

200g of heptane and 200g of hexane were added to a reactor equipped with a stirrer, a thermometer, a nitrogen injection tube, and a cooler, and heated to reflux while injecting nitrogen gas. Then, a mixed solution composed of 50 g of methyl methacrylate, 5.0 g of 2,2′-azobisisobutylnitrile and 10 g of the dispersion stabilizer A-1 prepared in Example 1 was added thereto, and the reaction was carried out for 30 minutes. . Then, 150 g isobutyl methacrylate, 50 g isobutyl acrylate, 25 g 2-hydroxybutyl acrylate, 7 g acrylic acid, AA-6 10 g (macromer of Dong-A Synthetic Chemistry), 10 g hexanedioldi A mixed solution composed of acrylate, 15 g of 2,3-dihydroxy propyl acrylate, 1.0 g of 2,2-azobisisobutylnitrile, and 20 g of the A-1 resin was added at a constant rate for 2 hours for 2 hours. The fat and oil reaction was carried out. Then, 80 g of CAB-3 resin was added, the reaction was carried out for 90 minutes, followed by cooling to prepare a milky non-aqueous dispersion resin B-4 having a solid content of 45%.

Comparative Example 1

1) Preparation of Dispersion Stabilizer

150 g of toluene was added to a reactor equipped with a stirrer, a thermometer, a nitrogen injection tube, a separator, and a cooler, and heated to reflux temperature while injecting nitrogen gas. Then, 500 g of 1,2-hydroxy stearic acid was added to dissolve it completely. g of p-toluenesulphonic acid was added and maintained at reflux for 3 hours.

While the reaction proceeds, the acid value is measured every 30 minutes. When the acid value reaches 36-38 (solid content), the acid value is cooled to reflux or lower, 50 g of glycidyl methacrylate is added thereto, and 1.5 g of quaternary ammonium salt and 0.5 g of After adding the mixed solution of pt-butylcatechol, the reaction was again maintained at reflux for 3 hours.

When the acid value was measured every 30 minutes as described above, when the acid value was 1.0 or less, the intermediate reactant was prepared by cooling below reflux temperature and diluting by adding 300 g of Exol D-30 (manufactured by Exol Chemical Co., Ltd.).

The solid content of the obtained intermediate reactant was 50%, and the viscosity measured by the Gardner viscometer (25'C) in the light brown liquid which has an acid value of 1 or less was B-C.

50 g of butyl acetate and 50 g of ethyl acetate were added to a new reactor of the same type as above, and heated to reflux temperature while injecting nitrogen gas. Then, 100 g of methyl methacrylate, 50 g of ethyl acrylate and 50 g of 2,2 were added. A mixed solution consisting of `-azobisisobutylnitrile and 300 g of the intermediate reactant was added at a constant rate for 6 hours, and the reaction was maintained for 2 hours. 380 g of butyl acetate was added thereto to dilute and cooled to room temperature to prepare a dispersion stabilizer A`-1 having a solid content of 32-35% by weight and a Gardner viscometer A in a light brown liquid.

 2) Preparation of non-water dispersion resin

200g of heptane and 200g of hexane were added to a reactor equipped with a stirrer, a thermometer, a nitrogen injection tube, and a cooler, and heated to reflux while injecting nitrogen gas. A mixed solution composed of 50 g of methyl methacrylate, 5.0 g of 2,2′-azobisisobutylnitrile and 10 g of the dispersion stabilizer A′-1 prepared above was added thereto, and the reaction was carried out for 30 minutes. Then, 150 g of methyl methacrylate, 50 g of styrene, 20 g of 2-hydroxyethyl acrylate, 1.0 g of 2,2-azobisisobutylnitrile and 20 g of the dispersion stabilizer A`-1 prepared above The mixed solution was added at a constant rate for 2 hours to maintain the reaction for 2 hours to prepare a milky non-aqueous dispersion resin B′-1 having a solid content of 40-42 wt%.

Comparative Example 2

In preparing the non-water dispersion resin, non-water dispersion resin B′-2 was prepared in the same manner as in Comparative Example 1 except that 15 g of acrylic acid and 10 g of 1,6-hexanedioldiacrylate were used.

Comparative Example 3

In preparing the non-water dispersion resin, non-water dispersion resin B′-3 was prepared in the same manner as in Comparative Example 1 except for further adding 100 g of lauryl methacrylate and 50 g of hydroxybutyl arc relate.

      In order to measure the physical properties when the resins prepared in Examples and Comparative Examples are applied to paints, the examples and the auxiliary resins are based on 100 parts by weight of acrylic resin (solid content: 75%, fish value: 70) as the main resin. Non-dispersible resins B-1 to B-4, B`-1 to B`-3 40 parts by weight prepared in Comparative Example, 25 parts by weight of acrylic resin aluminum paste, 30 parts by weight of hexamethoxymethyl melamine, and an ultraviolet absorber To prepare a paint.

The physical properties of the paint thus prepared were tested as follows, and the results are shown in Table 1 below.

(Test Methods)

1.Appearance: Visually judge the photo by tension meter

2. Acid resistance: After dropping the solution prepared with sulfuric acid and phosphoric acid pH = 1,2,3 to 0.5ml specimen, the traces were observed after standing for 30 minutes at 50, 60, 70'C temperature.

3.Storability: Check the change in viscosity and appearance after storing paint at 60 ° C for 3 days

4.Water resistance: Check the specimen for discoloration by manufacturing 40`C X 10 days specimen.

5. Cold resistance chipping: -40'C X 3 hours

6. Workability: Visually judge the matchability and appearance with CREE paint by applying paint (10-50 ㎛) for each coating thickness.

7. Weather resistance: Color discoloration and crack check after QUV test (2000,4000 hours)

8.COLD-CRCK CAST (After 4 repainting)

  : -40`C X 2hr + 110'C X 2hr + -40'C X 2hr + 110'C X 2hr

   + -40 `C X After 2 hours, immerse in 40'C hot water for 14 hours to detect cracks in the coating after 30CYCLE

9.Yellow yellowing: Yellowing degree after normal firing at 150'C X 1 hour

10. Adhesion: Cross-cut after OVER-BAKING (150 "C X 1 hour).

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Curing condition 145 ℃, 25 minutes 145 ℃, 25 minutes 145 ℃, 25 minutes 145 ℃, 25 minutes 145 ℃, 25 minutes 145 ℃, 25 minutes 145 ° C x 25 minutes Flow 35 μm 33 μm 37 μm 38 μm 24 μm 27 μm 27 μm Acid resistance Good Good Good Good Good Good Good Water resistance Good Good Good Good BLISTER Good BLISTER Chipping resistance Good Good Good Good Good Good Good Adhesion Good Good Good Good Good Good Good Yellowing 0.7 0.6 0.7 0.8 1.5 1.3 1.5 Zhejiang Good Good Good Good Separation Incremental Separation Workability Good Good Good Good DUST DUST Good Exterior 16-17 16-17 16 16-17 16 16 16 Weather Resistance (4,000 hr) Good Good Good Good CRACK discoloration discoloration discoloration cold-crackability 30 times Episode 28 Episode 29 30 times Episode 28 25 times 24 times

From the results of Table 1, according to the present invention, the paint of the present invention prepared by further comprising a CAB-modified acrylic resin in the composition used in the manufacture of a conventional non-dispersible resin is not only excellent in flowability, It can be seen that it does not cause a problem.

As described in detail above, in the preparation of the non-aqueous dispersion resin, an acrylic resin modified with cellulose acetate butylate (CAB) may be further added to prevent aggregation of the resin particles, thereby improving storage and flowability.

Claims (8)

( Crystalline) a three-dimensional repulsion layer in which at least two compounds selected from an epoxy copolymer, reactive methane, 1,2-hydroxy stearic acid, and an oil acid react with a monoisocyanate to apply some urethane bonds; Two or more adsorption layers selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl copolymer, acrylic acid, methacrylic acid and fatty acid; And a first step of preparing a dispersion stabilizer by addition reaction of the remaining amount of the solvent , and the dispersion stabilizer prepared above. Acrylic monomers; Polymerization initiator; In the method for producing a non-aqueous dispersion resin for automotive topcoat comprising a second step of preparing a non-water dispersion resin by mixing an ethylenically unsaturated monomer containing at least two or more hydroxyl groups in the molecule, In the preparation of the non-aqueous dispersion resin of the second step, 5 to 20 weight of the acrylic resin modified with cellulose acetate butyrate obtained by reacting the cellulose acetate butyrate modified acrylic monomer with an acrylic monomer and a polymerization initiator in a solvent. Method for producing a non-aqueous dispersion resin for automotive top coat, characterized in that it further comprises%. (delete) (Correction) The method according to claim 1, wherein the cellulose acetate butyrate modified acrylic monomer is obtained by reacting cellulose acetate butyrate with at least one member selected from isocyanate group-containing acrylic monomers represented by the following formulas (1) to (3). Method for producing a non-aqueous dispersion resin. Formula 1

Formula 2

Formula 3

In Formulas 1, 2 and 3, R is hydrogen or a methyl group. (Correction) The method according to claim 1, wherein the three-dimensional repulsive layer is contained in 30 to 60% by weight of the total composition of the dispersion stabilizer. (Correction) The method according to claim 1, wherein the adsorption layer is contained in an amount of 10 to 30% by weight in the total composition of the dispersion stabilizer. The non-aqueous dispersion resin according to claim 1, wherein the non-aqueous dispersion resin contains 3.0 to 30% by weight of dispersion stabilizer, 52 to 80.5% by weight of acrylic monomer, 0.3 to 8.0% by weight of polymerization initiator, and 5 to 4 ethylenically unsaturated monomers containing at least two hydroxyl groups in the molecule. 20% by weight and cellulose acetate butyrate modified acrylic resin 5 to 20% by weight of the method for producing a non-dispersible resin for automotive topcoat, characterized in that it comprises. (delete) The ethylenically unsaturated monomer according to claim 1 or 6, wherein the ethylenically unsaturated monomer containing at least two hydroxyl groups in the molecule contains 2,3-dihydroxy propylmethacrylate, 2,3-dihydroxypropyl acrylate, carboxyl group. An addition product of polyhydric alcohols with an epoxy group-containing ethylenically unsaturated monomer, selected from macromers, cellulose methacrylates, and cellulose acrylates obtained by reacting a hydroxyl group-containing copolymer derived from a carboxyl group-containing chain transfer agent with an epoxy group-containing ethylenically unsaturated monomer A method for producing a non-aqueous dispersion resin for automotive top coat, characterized in that at least one.