KR101503871B1 - Solvent borne resin for paint and method for preparing the same, and paint composition comprising the same for forming paint coating with excellent chipping resistance and appearance - Google Patents

Abstract

The present invention relates to an oil-soluble resin for paints, a process for producing the same, and a coating composition containing the same, and more particularly, to an oil-soluble resin for paints which is economical because it can be produced without using an expensive raw material component, And particularly to an oil-based resin which is suitable for use as a coating material and which is particularly suitable for use as an intermediate coating material for an automotive coating system, a method for producing the same, and a coating composition containing the same.

Description

TECHNICAL FIELD The present invention relates to an oil-soluble resin for paints, a process for producing the oil-soluble resin, and a coating composition containing the same and having excellent chipping resistance and appearance. BACKGROUND OF THE INVENTION 1. Field of the Invention EXCELLENT CHIPPING RESISTANCE AND APPEARANCE}

The present invention relates to an oil-soluble resin for paints, a process for producing the same, and a coating composition containing the same, and more particularly, to an oil-soluble resin for paints which is economical because it can be produced without using an expensive raw material component, And particularly to an oil-based resin which is suitable for use as a coating material and which is particularly suitable for use as an intermediate coating material for an automotive coating system, a method for producing the same, and a coating composition containing the same.

United States Patent Publication No. 2011-0244157 discloses a branched polyester resin obtained by polymerizing a double bond of an unsaturated polyester prepolymer containing a hard segment, a polyol segment and an unsaturated carboxylic acid, and a coating composition comprising the same. . However, this coating composition has problems such as storage stability and yellowing.

U.S. Patent No. 4,816,528 discloses an oil-resistant intermediate resin that blends an epoxy-modified polyester grafted resin with a block isocyanate, and a coating composition comprising the same. However, this coating composition has a problem in UV transmittance and high manufacturing cost.

Japanese Unexamined Patent Application Publication No. 2002-180000 discloses an intermediate resin for mixing polycaprolactone diol and block isocyanate and a coating composition comprising the same. Here, the block isocyanate has a buret form rather than an isonurate form in order to overcome the problem of deteriorating appearance. However, this coating composition also has a problem of high manufacturing cost.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in an effort to solve the problems of the prior art, and it is an object of the present invention to provide a coating film which can be produced without using an expensive raw material component, And particularly to an oil-based resin which is very suitable for use as an intermediate coating for an automotive coating system, a method for producing the same, and a coating composition containing the same.

In order to solve the above technical problems, the present invention provides a resin composition comprising (A) oligomers of bifunctional monomers; And (B) a trifunctional or higher polyfunctional monomer condensed at the terminal of the oligomer (A).

According to another aspect of the present invention, there is provided a process for preparing an oligomer comprising: (1) preparing an oligomer of bifunctional monomers; And (2) condensing the oligomer with a monomer mixture comprising a trifunctional or higher functional polyfunctional monomer.

According to another aspect of the present invention, there is provided a coating composition comprising an oil-soluble polyester resin of the present invention, a curing agent, a pigment, and an organic solvent.

INDUSTRIAL APPLICABILITY The oil-soluble resin and coating composition containing the same according to the present invention can be produced without using an expensive raw material component, and are economical and can form a coating film having remarkably excellent chipping resistance and appearance at the time of curing, It is very suitable for the intermediate use of paint systems.

Figure 1 is a schematic view of a typical automotive paint system.
Figure 2 is an illustration of the schematic structure of the oil-soluble resin according to the present invention.
Fig. 3 is a chipping resistance rating standard (left to right in order from first grade to sixth grade).

Hereinafter, the present invention will be described in detail.

1. Usability Polyester resin

The usable polyester resin of the present invention comprises (A) an oligomer of bifunctional monomers; And (B) a multifunctional monomer having three or more functional groups condensed at the terminal of the oligomer (A).

The oligomer (A) of the bifunctional monomers may preferably be prepared by a condensation reaction of a bifunctional acid group-containing monomer and a bifunctional alcohol group-containing monomer. The polyester resin of the present invention has a structure in which at least part of a linear polyester main chain structure is secured through the oligomer (A) of such bifunctional monomers and a multifunctional monomer having three or more functional groups described later is condensed and reacted at the terminal of the main chain .

The bifunctional acid group-containing monomer may preferably be a C ₂ -C ₃₀ aliphatic, alicyclic, aromatic or acid anhydride monomer having two carboxylic acid groups, and more specifically, succinic acid, glutaric acid, There may be mentioned acid anhydrides such as adipic acid, azelaic acid, sebacic acid, fumaric acid, diglycolic acid, dimethylsuccinic acid, dimethylglutaric acid, cyclic diacids, phthalic acid, naphthalic acid, dimethylterephthalic acid, isophthalic acid, terephthalic acid, succinic anhydride, , Dodecylsuccinic anhydride, octylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and tetrahydrophthalic anhydride.

The bifunctional alcohol group-containing monomer may preferably be a C ₂ -C ₃₀ aliphatic, alicyclic or aromatic monomer having two alcohol groups, and more specifically, ethylene glycol, propylene glycol, butylene glycol, And may be at least one selected from the group consisting of tylene glycol, hexylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, butylethylpropanediol, trimethylpropanediol, diethylene glycol and cyclohexanediol.

The number average molecular weight (Mn) of the oligomer (A) of the bifunctional monomers is preferably 150 to 20,000. When the number-average molecular weight of the oligomer (A) is less than 150, there may be a problem that the dipping resistance, chemical resistance and crack resistance of the final coating film are lowered. When the number average molecular weight is more than 20,000, gelation occurs during oligomer synthesis, And the like.

The trifunctional or more multifunctional monomer (B) which is condensed with the oligomer (A) of the bifunctional monomers and is connected to the terminal thereof is preferably an acid group-containing monomer having three or more functional groups, an alcohol group-containing monomer having three or more functional groups, ≪ / RTI >

The acid group-containing monomer having three or more functional groups may be a C ₂ -C ₃₀ aliphatic, alicyclic, aromatic or acid anhydride monomer having preferably at least three carboxylic acid groups, and more specifically, citric acid, trimellitic acid, Trimellitic anhydride, pyromellitic dianhydride, melitic acid, pyromellitic dianhydride (PMDA), 3,3 ', 4,4-oxydiphthalic dianhydride (ODPA), 3,3' , 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride (6FDA), benzoquinone tetracarboxylic dianhydride and ethylene tetracarboxylic dianhydride And a carboxylic acid dianhydride.

The alcohol group-containing monomer having three or more functional groups may be a C ₂ -C ₃₀ aliphatic, alicyclic or aromatic monomer having preferably at least three alcohol groups, and more specifically, glycerin, trimethylol ethane, trimethylol propane, Xanthol, erythritol, xylitol, mannitol, pentaerythritol, and inositol.

In addition to the oligomer (A) and the trifunctional or higher functional polyfunctional monomer (B), the usable polyester resin of the present invention may further contain (C) an acid group-containing monomer having at least one functional group, an alcohol group- Or both. ≪ RTI ID = 0.0 > The additional constituent unit may be condensed to the terminal of the oligomer (A), which is the main chain, or may be condensed and connected to a trifunctional or more multifunctional monomer (B) condensed at the terminal of the oligomer (A) May be condensed and connected to another further monomer (C) condensed and connected to the trifunctional or higher multifunctional monomer (B).

As the optional additional constitutional unit, the above-mentioned monofunctional or higher functional group-containing monomer may be preferably a C ₁ -C ₃₀ aliphatic, alicyclic, aromatic or acid anhydride monomer having at least one carboxylic acid group, and more specifically, But are not limited to, formic acid, acetic acid, benzoic acid, naphthenic acid, rosin acid, castor oil fatty acid, coconut oil fatty acid, tolol fatty acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, There may be mentioned acid addition salts with organic acids such as formic acid, behenic acid, cerotic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, fumaric acid, diglycolic acid, citric acid, dimethylsuccinic acid, dimethylglutaric acid, cyclic diacid, phthalic acid, But are not limited to, dimethyl terephthalic acid, isophthalic acid, terephthalic acid, succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, octylic anhydride, phthalic anhydride, hexahydrophthalic anhydride, (PMDA), 3,3 ', 4,4-oxydiphenylmethane diisocyanate, trimellitic acid, trimellitic acid anhydride, pyromellitic dianhydride, mellitic acid, pyromellitic acid dianhydride (6FDA), 4,4'-benzoquinone tetracarboxylic acid dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride Quinone tetracarboxylic acid dianhydride, and ethylene tetracarboxylic acid dianhydride.

As the optional additional constitutional unit, the monofunctional or higher alcohol group-containing monomer may be a C ₁ -C ₃₀ aliphatic, alicyclic or aromatic monomer having preferably at least one alcohol group, and more specifically, methanol, ethanol, But are not limited to, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, hexadecanol, cyclohexanol, benzyl alcohol, tertiary amyl alcohol, ethylene glycol, propylglycol, butylene glycol, pentyleneglycol, Butanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, butylethylpropanediol, trimethylpropanediol, diethylene glycol, cyclohexanediol, glycerin, trimethylolethane, trimethylolpropane, erythritol, xylitol, mannitol, pentaerythritol and ≪ / RTI > and inositol.

There is no particular limitation on the content ratio of the oligomer (A), the multifunctional monomer (B) having three or more functional groups, which are essential constituent units of the usable polyester resin of the present invention, in the resin, 30: 70 to 90: 10, but is not limited thereto. When the structural unit (C) is further included, for example, the weight ratio of (A): (C) may be 70:30 to 95: 5, but the present invention is not limited thereto.

The acid value (based on solid content) of the oil-soluble polyester resin of the present invention is preferably 0 to 30 mg KOH / g, and the acid value is preferably 50 to 200 mg KOH / g. If the acid value of the resin exceeds 30 mg KOH / g, the discoloration resistance, crack resistance and hardness of the coating film may be lowered. If the hydroxyl value of the resin is less than 50 mg KOH / g, the smoothness and hardness of the coating film may be lowered and problems such as gelation may occur. When the water value is more than 200 mg KOH / g, the hardness, chemical resistance, There may be a problem with flowing down.

The usable polyester resin of the present invention can be produced by a conventional polymerization method of a polyester monomer by a condensation reaction. According to a preferred embodiment of the present invention, an oligomer of the bifunctional monomers is prepared, but not necessarily limited thereto, by condensation reaction of the oligomer with a monomer mixture containing the trifunctional or higher polyfunctional monomer, An ester resin can be produced. Accordingly, in accordance with another aspect of the present invention, there is provided a process for preparing oligomers comprising: (1) preparing oligomers of bifunctional monomers; And (2) condensing the oligomer with a monomer mixture comprising a trifunctional or higher functional polyfunctional monomer.

In the step (1) of the process for producing an oil-soluble polyester resin according to the present invention, the oligomer of the bifunctional monomers is preferably the oligomer of the bifunctional acid group-containing monomer and the bifunctional alcohol group- , And this condensation reaction can be preferably carried out while removing the condensed water under elevated conditions (for example, 80 to 250 ° C) in the presence of an acid catalyst or a base catalyst. The condensation reaction in the step (1) can be terminated when the acid value of the reaction mixture reaches an appropriate level (for example, 3 to 7 mg KOH / g).

In the step (2) of the process for producing the oil-soluble polyester resin according to the present invention, the trifunctional or higher functional polyfunctional monomer may be at least one selected from the group consisting of trifunctional or higher acid group-containing monomers, trifunctional or higher alcohol group-containing monomers, Can be preferably used. As a result of the step (1), the oligomer and the monomer mixture reacting in the step (2) may be composed solely of the trifunctional or higher polyfunctional monomers, and may include the monofunctional or higher acid group-containing monomer, the monofunctional or higher- Or both. The condensation reaction in the step (2) may preferably be carried out while removing the condensed water under elevated temperature conditions (for example, 80 to 250 ° C), and the acid value of the reaction mixture may be adjusted to an appropriate level (for example, 8 to 12 mg KOH / g) Quot ;, it can be terminated.

2. Paint composition

The above-described oil-soluble polyester resin of the present invention is very suitable as a binder component for paints, particularly as a binder component for intermediate paints of automotive coating systems, because it can form a coating film having excellent resistance to chipping and appearance during curing. Accordingly, according to another aspect of the present invention, there is provided a coating composition comprising an oil-soluble polyester resin, a curing agent, a pigment, and an organic solvent of the present invention, more preferably a vehicle-use intermediate coating composition.

In the coating composition of the present invention, the content of the usable polyester resin is preferably 15 to 50% by weight, more preferably 20 to 40% by weight, based on the total weight of the composition. When the content of the resin in the coating composition is less than 15% by weight, general physical properties of the coating composition may be deteriorated. When the content of the resin exceeds 50% by weight, the appearance of the coating film, workability, hardness and the like may be deteriorated.

As the curing agent contained in the coating composition of the present invention, it is preferable to use a melamine curing agent. As the melamine curing agent, for example, one containing at least one of methylated melamine resin, butylated melamine resin or hybrid (methylated + butylated) melamine resin can be preferably used, and its solid content is 30 to 70 wt% %, And the curing temperature is preferably 130 to 160 ° C. In the coating composition of the present invention, the content of the curing agent is preferably 10 to 30% by weight, more preferably 15 to 30% by weight, based on the total weight of the composition. If the content of the curing agent in the coating composition is less than 10% by weight, a problem may arise in the hardness of the coating film. If the content of the curing agent is more than 30% by weight, chipping resistance and impact resistance may occur.

The organic and inorganic pigments that can be used for automotive coatings can be used in the coating composition of the present invention. Specifically, TiO ₂ white pigment, carbon black based FW285, Raven Ultra 5000, Raven 3500, Blanc Fixe Micro, Hostaperm Violet RL-S, Heliogen Green L8730, Manstral Blue FNX, Sicopal Yellow L1100, Paliotan Yellow L1945, Irgazin DPP BO, Hostaperm Red E3B, and the like, but the present invention is not limited thereto. In the coating composition of the present invention, the content of the pigment is preferably 1 to 40% by weight, and more preferably 5 to 30% by weight, based on the total weight of the composition. If the content of the pigment in the coating composition is less than 1% by weight, defects such as low hiding power may occur. If the content exceeds 40% by weight, the leveling of the coating may be lowered and the clear feeling may be deteriorated. There may be a decrease in the amount of

As the organic solvent to be contained in the coating composition of the present invention, any organic solvent which can be used for an automotive coating material may be used. Specifically, aromatic hydrocarbon type solvents such as xylene; Esters such as methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate and butyl cellosolve acetate; And alcoholic solvents such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tertiary butanol. In the coating composition of the present invention, the content of the organic solvent is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total weight of the composition. If the content of the organic solvent in the coating composition is less than 5% by weight, pinholes may be formed on the surface of the coating film. If the content of the organic solvent is more than 50% by weight, the solids content of the coating composition may deteriorate.

In addition to the above-mentioned components, the coating composition of the present invention may further include one or more components that are usually added to the coating composition for controlling the appearance of the coating film and other physical properties. For example, the coating composition of the present invention may further include a buffering agent for improving the chipping resistance, the sandmark hiding power, and the like. In this case, the content may be 0.1 to 10 wt%, more preferably 0.5 to 5 wt%, based on the total weight of the composition, but if the amount of the buffer is excessively large, the appearance of the coating film may be deteriorated. In addition, the coating composition of the present invention may further include an antifogging agent, a smoothing agent, an antifoaming agent, a dispersing agent, and the like in order to control the appearance and physical properties of the coating film. If necessary, an aromatic and a fluorinated hydrocarbon- The viscosity of the paint may also be adjusted. These other additives may be added in the amounts normally used.

When the coating composition according to the present invention is used as an intermediate weight for automobiles, the undercoat which can be used together with it is an electrodeposition paint used for automobile painting. The coating composition according to the present invention is applicable to almost all electrodeposition paints using epoxy as a main resin. Examples of the basecoat paint which can be used in combination with the coating composition according to the present invention include basecoat paint for use as a base coat, which is produced by using carboxyl group-containing acrylic acid, a hydroxyl group-containing acrylic resin, a melamine curing agent or a polyester resin, a metal pigment, It is possible to use an automotive paint or a water-soluble automotive paint using a polyurethane dispersant, an acrylic urethane dispersion, an acrylic emulsion or the like as a single or hybrid type main resin and selectively using melamine as a curing agent. As the clear coating for topical use, one-component automotive top clear coatings using a block isocyanate curing agent together with an epoxy or carboxyl group-containing acrylic acid, a hydroxyl group or a siloxane group-containing thermosetting acrylic resin, or a two-component type transparent coating using an isocyanate curing agent Transparent paints for automotive use can be used.

Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples are intended to assist the understanding of the present invention, and the scope of the present invention is not limited thereto.

[ Example ]

Synthetic example  One: Oligomer  (A)

In a four-necked flask equipped with a thermometer, a condenser and a packed column, 205 g of neopentylcyclole, 126 g of adipic acid and 0.3 g of butyl chlorotintehydroxide were charged under a nitrogen atmosphere, and a packed column top ) The temperature was raised to 220 ° C while maintaining the temperature below 102 ° C, and the reaction was maintained while removing the condensed water until the acid value reached 3-7 mg KOH / g. As a result, a yellow transparent oligomer component was obtained (solid content: 100%, viscosity: 8 poise (150 DEG C), acid value: 5 mg KOH / g).

Synthetic example  2: Oligomer  (A)

A transparent yellow oligomer component (solid content: 100%, viscosity: 16 poise) was obtained in the same manner as in Synthesis Example 1, using 115 g of neopentylcyclole, 126 g of adipic acid and 0.3 g of butyl chlorotintehydroxide as starting materials (150 DEG C), acid value: 5 mg KOH / g).

Synthetic example  3: Oligomer  (A)

A transparent yellow oligomer component was obtained in the same manner as in Synthesis Example 1, using 222 g of hexanediol, 120 g of adipic acid and 0.3 g of butyl chlorotintihydroxide as starting materials (solid content: 100%, viscosity: 5 poise (150 C), acid value: 5 mg KOH / g).

Example  1: Production of polyester resin

In a four-necked flask equipped with a thermometer, a condenser and a packed column, 300 g of the oligomer of Synthesis Example 1, 67 g of trimethylol propane, 146 g of phthalic anhydride and 57 g of hexahydrophthalic anhydride were charged under a nitrogen atmosphere, column top). The temperature was raised to 220 ° C while maintaining the temperature below 102 ° C, and the reaction was maintained while condensation water was removed until the acid value reached 8 to 12 mg KOH / g. When the target acid value was reached, 228 g of xylene was added after cooling to 120 캜. As a result, a transparent yellow polyester resin component was obtained (solid content: 70.5%, Gardner viscosity: Y (25 占 폚), acid value: 10 mg KOH / g).

Example  2: Production of polyester resin

A yellow transparent polyester resin component was obtained in the same manner as in Example 1, using 210 g of the oligomer of Synthesis Example 2, 90 g of neopentylcyclole, 67 g of trimethylolpropane, 146 g of phthalic anhydride and 57 g of hexahydrophthalic anhydride as starting materials (Solid content: 70.5%, Gardner viscosity: Z- (25 ° C), acid value: 10 mg KOH / g).

Example  3: Production of polyester resin

A yellow transparent polyester resin component (solid content: 70.5%) was obtained in the same manner as in Example 1 except that 313 g of the oligomer of Synthesis Example 3, 64 g of trimethylolpropane, 140 g of phthalic anhydride and 54 g of hexahydrophthalic anhydride were used as starting materials. , Gardner viscosity: X (25 캜), acid value: 10 mg KOH / g).

Comparative Example  One: Oligomer  Production of unused polyester resin

The same procedure as in Example 1 was carried out except that 205 g of neopentylcyclole, 67 g of trimethylolpropane, 126 g of adipic acid, 146 g of phthalic anhydride, 57 g of hexahydrophthalic anhydride and 0.3 g of butyltin dihydroxide were used as starting materials, (Solid content: 70.5%, Gardner viscosity: Y (25 占 폚), acid value: 10 mg KOH / g).

Example  4 to 6 and Comparative Example  2: Manufacture of coating compositions for automobiles

The intermediate coating composition for automobiles containing the respective polyester resins prepared in Examples 1 to 3 and Comparative Example 1 as a binder component was prepared with the composition shown in Table 1 and the physical properties were evaluated.

Paint coating was carried out under the following conditions by using an electrostatic coating Bell: flow rate of 170 ~ 250cc / min, external voltage -60kV, shaping air 0.5 ~ 1kg / cm 2, Bell rpm 40000 ~ 55000, Head target distance (HTD) 200 ~ 250mm. Immediately after coating, the coating was pre-dried for 3 to 10 minutes to stabilize the coating. Thereafter, after baking at 140 DEG C for 20 minutes, gloss, adhesion, hardness and smoothness of the coating film were evaluated by the intermediate coating alone. The evaluation results are shown in Table 2 below.

[Ingredients Used]

Melamine curing agent: Cymel 1161 (made by Cytec)

Leveling agent: DISPARLON L-1984N (manufactured by King industries)

Defoamer: DISPARLON OX-60 (manufactured by Kusumoto)

Dispersant: EFKA-4061 (made by BASF)

Xylene: Made by SK Corporation

Coco sol # 150: made by SK Corporation

Butanol: Hanwha Petrochemical

Pigment 1: BFM (manufactured by Sachtleben Chemie GmbH)

Pigment 2: CR-97 (manufactured by ISHIHARA SANGYO KAISHA, LTD.)

[Property evaluation method]

- gloss: measure the horizontal coating with a polisher (BYK micro gloss)

- Adhesiveness: Check whether film is attached after crosscut (2 * 2mm, 100ea)

[Good: Maintain the attached state without falling off the coating film; Medium: 1 or 2 drops; Defective: more than 3 drops]

- Hardness: measured by pencil hardness method

[Measurement of hardness which does not damage the coating film with each pencil of 3B, 2B, B, HB, F, H, 2H and 3H]

- Smoothness: Measurement of smoothness of coating film by Wave scan Dual, confirmed by long wave value

- Chipping resistance: Specimen temperature -20 ℃, 45 ° chip mounting (MS 653-01)

[Chipping Rating Standard (MS 653-01): Figure 3]

Claims (15)

As constituent units of the resin, (A) oligomers of bifunctional monomers; And (B) a multifunctional monomer having three or more functional groups condensed at the terminal of the oligomer (A). The resin according to claim 1, wherein the oligomer (A) of the bifunctional monomers is prepared by a condensation reaction of a bifunctional acid group-containing monomer and a bifunctional alcohol group-containing monomer. The method according to claim 2, wherein the bifunctional acid group-containing monomer is a C ₂ -C ₃₀ aliphatic, alicyclic, aromatic, or acid anhydride monomer having two carboxylic acid groups and the bifunctional alcohol group- Is an aliphatic, cycloaliphatic, or aromatic monomer having from _{2 to 30} carbon atoms. 3. The method of claim 2,
Wherein the bifunctional acid group-containing monomer is at least one selected from the group consisting of succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, diglycolic acid, dimethyl succinic acid, dimethylglutaric acid, cyclic diacids, phthalic acid, Selected from the group consisting of dimethyl terephthalic acid, isophthalic acid, terephthalic acid, succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, octylic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and tetrahydrophthalic anhydride Lt; / RTI >
Wherein the bifunctional alcohol group-containing monomer is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, butylethylpropanediol, Ethylene glycol, and cyclohexanediol. ≪ RTI ID = 0.0 > 11. < / RTI > The resin according to claim 1, wherein the oligomer (A) of the bifunctional monomers has a number average molecular weight (Mn) of 150 to 20,000. The resin according to claim 1, wherein the trifunctional or more polyfunctional monomer (B) is an acid group-containing monomer having three or more functional groups, an alcohol group-containing monomer having three or more functional groups, or a mixture thereof. The method of claim 6, wherein the trifunctional or higher acid group-containing monomer is a C ₂ -C ₃₀ aliphatic, alicyclic, aromatic, or acid anhydride monomer having three or more carboxylic acid groups and the trifunctional or higher alcohol group- A C ₂ -C ₃₀ aliphatic, alicyclic or aromatic monomer having at least three alcohol groups. The method according to claim 6,
Wherein the acid group-containing monomer having three or more functional groups is at least one selected from the group consisting of citric acid, trimellitic acid, trimesic acid, trimellitic acid anhydride, pyromellitic dianhydride, mellitic acid, pyromellitic acid dianhydride (PMDA) 4-oxydiphthalic acid dianhydride (ODPA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride 6FDA), benzoquinone tetracarboxylic acid dianhydride, and ethylene tetracarboxylic acid dianhydride,
Wherein the trifunctional or higher alcohol group-containing monomer is at least one selected from the group consisting of glycerin, trimethylol ethane, trimethylol propane, erythritol, xylitol, mannitol, pentaerythritol and inositol. The resin according to claim 1, further comprising (C) an acid group-containing monomer having at least one or more functional groups, an alcohol group-containing monomer having at least one functional group, or both as constituent units of the resin. The method of claim 9, wherein the at least one acid group-containing monomer is a C ₁ -C ₃₀ aliphatic, alicyclic, aromatic, or acid anhydride monomer having at least one carboxylic acid group and the at least one alcohol group- A C ₁ -C ₃₀ aliphatic, alicyclic or aromatic monomer having at least one alcohol group. 10. The method of claim 9,
Wherein the acid group-containing monomers having one or more functional groups are selected from the group consisting of formic acid, acetic acid, benzoic acid, naphthenic acid, rosin acid, castor oil fatty acid, coconut oil fatty acid, tolol fatty acid, caprylic acid, capric acid, lauric acid, But are not limited to, citric acid, citric acid, tartaric acid, citric acid, tartaric acid, citric acid, tartaric acid, citric acid, tartaric acid, tartaric acid, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetra acetic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, terephthalic anhydride, Pyromellitic dianhydride, melitic acid, pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4'-tetramethyluronic anhydride, trimellitic anhydride, trimellitic anhydride, pyromellitic dianhydride, 4-oxydiphthalic acid dianhydride (ODPA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride 6FDA), benzoquinone tetracarboxylic acid dianhydride, and ethylene tetracarboxylic acid dianhydride,
Wherein the monofunctional or higher alcohol group-containing monomer is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, hexadecanol, cyclohexanol, benzyl alcohol, tertiary amyl alcohol, , Butylene glycol, pentylene glycol, hexylene diglycol, butanediol, pentanediol, hexanediol, neopentyl glycol, butylethylpropanediol, trimethylpropanediol, diethylene glycol, cyclohexanediol, glycerin, trimethylolethane, trimethyl Wherein the resin is at least one selected from the group consisting of propane, erythritol, xylitol, mannitol, pentaerythritol, and inositol. The resin according to claim 1, wherein the acid value (on a solid basis) is 0 to 30 mg KOH / g and the water value is 50 to 200 mg KOH / g. (1) preparing an oligomer of bifunctional monomers; And (2) condensing the oligomer with a monomer mixture containing a trifunctional or higher polyfunctional monomer. A coating composition comprising the oil-soluble polyester resin of any one of claims 1 to 12, a curing agent, a pigment, and an organic solvent. 15. The composition according to claim 14, which is a vehicle-use intermediate paint.

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