KR0160807B1 - High weather resistant compositions and process for preparing the same - Google Patents

Abstract

The present invention improves the chemical resistance and coating processability of silicone-modified polyester resins that have been used as a colorant of high weathering baking paints, minimizes the occurrence of silica materials during curing reactions, and provides weather resistance, water resistance, corrosion resistance, coin scratch and workability, etc. The present invention relates to a high weather resistance silicone-modified polyester resin and a method for producing the same. The high weather resistance silicone modified polyester resin of this invention can be manufactured by copolymerizing with a polyester resin intermediate, a reactive modified body, and a silicone modified body.

Description

High Weatherability Compositions and Methods for Making the Same

The present invention relates to a high weather-resistant silicone-modified polyester resin and a method for producing the same. More specifically, the present invention improves chemical resistance and coating processability of silicone-modified polyester resin which has been used as a colorant of high weathering baking paint, and minimizes generation of silica materials during curing reaction, and weather resistance, water resistance, corrosion resistance, and coin scratch resistance. And high weatherability silicone-modified polyester resins having greatly improved workability and the like, and methods for producing the same.

The coating method of the baking paint includes a post coating method for painting and drying the finished material on the finished work and a precoating coating (PCM) method for processing and molding the dried material. Post coating method is cheap coating equipment cost, there is an advantage in small quantity production, but there is a disadvantage that the production of uniform products and mass production is difficult. On the other hand, the pre-coated coating method is able to mass-produce a uniform quality product in a short time, and is used more because it has the advantage of reducing the loss of paint, the hygiene safety of the worker, and the environmental pollution, but the pre-coated material is coated. Since a separate processing molding process is performed after the coating, in addition to general coating properties such as adhesion, durability, corrosion resistance, and water resistance, workability, fast curing property, stability of paint at high temperatures, and workability due to high speed work are required.

The high weathering paint for pre-coating using the conventional silicone modified polyester resin is coated on corrosion-resistant alloy steel sheets such as molten galvanized steel sheet, galvanyl steel sheet, galvanium steel sheet, aluminum steel sheet, etc., for general building exterior materials, industrial exterior materials, and other industrial materials. Has been used. Silicone-modified polyester resins are widely used as coating materials for high weatherability by combining the excellent weatherability and curability of silicone resins with the processability and workability of polyester resins.

However, the conventional silicone-modified polyester resin used a method of modifying the polyester resin with a silyl group, which is vulnerable to an acidic or alkaline ionic compound, and lacks processability compared to a polyester resin, There is a disadvantage that the drying furnace is contaminated due to the generation of silica during the curing reaction of the paint.

Usually, the compound (hereinafter referred to as silicone intermediate) used for modifying the polyester resin with a silyl group is a multifunctional compound having a molecular weight of 1000 to 3000. In order to modify 20-50% of the polyester resin by this silicone intermediate, the polyester resin should be of a low molecular weight containing a large amount of hydroxyl groups. It is usually reported that the modification reaction rate of the silicone intermediate to the polyester resin is 65% or less, and the unreacted silicon intermediate is scattered to some silica material to contaminate the small part.

In addition, due to the structural properties of the silicone intermediate and the excessive molecular structure adjustment of the polyester resin for modification by the silicone intermediate, the chemical resistance and processability of the ionic compound of the coating film are greatly reduced.

The functional groups of the silicon intermediate are of silanol type and methoxy type. Silicone intermediate suppliers recommend methoxy functional types as precoating paints, but resin designers for coatings prefer intermediates to silanol functional groups due to the generation of silica materials and poor chemical resistance.

However, the silicone intermediate of this silanol functional group has a problem in that the curing ability is excellent but coating film workability is poor.

As a result of recognizing the above problems and making an effort for improvement, the present inventors have not only improved chemical resistance to ionic compounds, remarkably improved coating processability, but also minimized the occurrence of silica material generated during curing of the coating material. It has been developed a high weather resistance silicone modified polyester resin composition with improved weather resistance, water resistance, corrosion resistance, coin scratch and workability, which are important conditions.

The present invention relates to a silicone-modified polyester resin produced by a polyester resin (A), an unsaturated monomer (B) and a silicone modified body (C).

The present invention also relates to a method for producing a silicone-modified polyester resin produced by a polyester resin, an unsaturated monomer and a silicone modified body.

As a method of preparing the silicone-modified polyester resin of the present invention, the following two methods can be used.

The first method synthesizes a possibility-modified polyester resin intermediate (hereinafter referred to as modified polyester) with the polyester resin (A) and an unsaturated monomer (B), and modifies the modified polyester with a silicone modified body (C). It is a method of manufacturing a silicone modified polyester resin.

The second method synthesizes a reactive silicone-modified intermediate (hereinafter referred to as silicone intermediate) from an unsaturated monomer (B) and a silicone-modified product (C), and combines it with the polyester resin (A) to produce a silicone-modified polyester resin. Way.

Referring to the production method of the present invention in more detail as follows.

The production method of the present invention comprises 100 parts by weight of a polyester resin having an average molecular weight of 1,000-10,000, a solid content of 30 to 80% by weight, a hydroxyl value of 0.3-3% by weight, and an acid value of 1-30 mg KOH / G; Unsaturated monomer having the following structure (I), (II) or (III), selected from the group consisting of unsaturated monomers having a glass transition temperature of -50 to 80 ° C and a hydroxyl content of 0.5 to 5% by weight or 3-150 parts by weight of two or more unsaturated monomers; And a silicone intermediate having 2 to 4 functional groups and a molecular weight of 1,000 to 3,000, wherein the silane compound or silicone macromonomer or substituent having an unsaturated functional group of vinyl or methacryl is a methylphenyl group and the functional group is a silanol or methoxy group. It is characterized by copolymerizing 1-50 parts by weight of the silicone modified material selected from the group.

Where

X represents hydrogen or a methyl group,

Y represents C _n H _{2n + 1} , hydrogen or a macromonomer of 5000 in a molecular weight of 50 sow, wherein n represents an integer from 1 to 12;

Where

X represents hydrogen or a methyl group,

n represents an integer of 1 to 10; or

Where

X represents hydrogen or a methyl group,

Z represents phenyl, -CN, -CONH-R ₁ or a macromonomer having a molecular weight of 50 to 5000, wherein R ₁ represents H or -C (CH ₃ ) ₂ CH ₂ C═O.

The polyester resin used in the present invention is prepared by the condensation reaction of a polyol containing a basic acid and glycols as is known, and can be obtained by adjusting the solid content component by producing the acid value and the average molecular weight in accordance with the conditions of the present invention. .

Representative basic acids used in the production of this polyester resin include benzoic acid, para-t-benzoic acid, phthalic acid, phthalic anhydride, isophthalic acid, telephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexadicarboxylic acid, and aroxane. Dimers, azelaic acid, citric acid, dimers made from tall oil fatty acids, trimellitic anhydride, and the like, and unsaturated basic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, succinic anhydride, and the like. Can be.

In addition, representative alcohol monomers that can be used in the production of polyester resins include ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, dimethylhydropropyl Dimethyl-hydroxypropionate, trimethanol propane, triethanol propane and the like.

When the molecular weight of the polyester resin used in the production method of the present invention is less than 1,000, the curing ability and chemical resistance is weak, and when the hydroxyl group is less than 0.3% by weight, the curing ability is poor and the desired coating film hardness cannot be obtained, and the gel fraction is remarkably. Lowers. On the other hand, when the hydroxyl group exceeds 7%, it is not preferable because it becomes a low molecular weight resin.

In the manufacturing method of this invention, an unsaturated monomer (B) is used for the purpose of improving chemical-resistance, curability of a coating film, scratchability, roller workability, and minimizing the crystallinity of resin.

In the resin manufacturing method of this invention, what has a structure of said Formula (I) as an unsaturated monomer is methyl acrylate, butyl methacrylate, lauryl methacrylate, acrylic acid, methyl methacrylate, ethyl acrylate, butyl Acrylate, ethyl methacrylate, polymethylmethacrylvinyl monomers, cadmium resin modified vinyl monomers or glycidyl methacrylate, and the like.

Compounds of the formula (II) that can be used in the present invention include 2-hydroxy methacrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate and the like.

Representatives that can be used in the present invention as the compound of the formula (III) include styrene, acrylonitrile, acrylamide, diacetone acrylamide, polystyrene vinyl monomers, acrylonitrile vinyl monomers and the like.

In the production method of the present invention, the unsaturated monomer is preferably reacted with a reaction initiator upon modification. Representative initiators include isobutylyl peroxide, t-butylperoxy neodecanoate, octanonyl peroxide, and benzoyl perox Seeds, acetylperoxide, di-t-butylperoxide, azoisobutylonitrile, t-butylperoxylaurate and the like.

The unsaturated monomer used in the production method of the present invention preferably has a glass transition temperature (T _g ) in the range of -50 to 80 ° C. The glass transition temperature is lower than -50 ° C because the coating film hardness is weak, and the glass transition temperature is higher than 80 ° C because the paint workability deteriorates rapidly.

The unsaturated monomer used in the resin production method of the present invention is preferably in the range of 0.5 to 5% by weight based on the total hydroxyl monomer content for the uniform curing reaction of the resin of the present invention.

It is preferable that the use ratio of the unsaturated monomer (B) with respect to a polyester resin (A) uses 3-150 weight part with respect to 100 weight part of polyester resin solid content. When the amount of the unsaturated monomer is 3 parts by weight or less, it is difficult to exhibit the denatured property, and when it exceeds 150 parts by weight, the workability of the coating film is inferior.

The silicone modified body (C) for imparting a silyl group in the resin composition of the present invention functions to effectively impart weather resistance to the resin.

In this invention, what can be used as a silicone modified body includes vinyl methoxysilane, vinyl triethoxy silane, vinyl trimethoxy ethoxy silane, and the silicone macromonomer whose terminal group is a methacryloyl group (trade name AK of the Japanese Dong-A synthesis) -5, AK-30), tetraethoxysilane or a polymer thereof (SiO ₂ content 28-45%), the substituent being phenyl, methyl or a mixture thereof, and the functional group being an alcoholic silanol or methoxy group 2- Silicone intermediates having a molecular weight of 1000-3000 having four functional groups (manufacturer; Dow Corning, Barker, Germany, General Electric, USA), and the like.

In the manufacturing method of this invention, it is preferable that the usage-amount of a silicone modified body (C) uses 1-50 weight part with respect to 100 weight part of modified polyester resin solid content. When less than 1 is used, it is difficult to obtain the desired weather resistance, and when it exceeds 50 parts by weight, the workability is remarkably lowered, and the price of the resin is so high that economic efficiency is lost.

In this invention, the silicone modified body used can be used 1 or 2 or more types in mixture.

In order to minimize the occurrence of the silica material, it is preferable to adjust the amount of modification in the range of 1 to 20% of the content of SiO ₂ with respect to the total resin solid content.

It is preferable to adjust the reaction rate of the silicone modified body with respect to a modified polyester resin to 95% or more. This is because the compatibility of the unreacted silicone modified body with the modified polyester resin is poor, so that the coating film may become opaque.

The manufacturing method of the high weather-resistant silicone modified polyester resin of this invention is demonstrated more concretely as follows.

The first manufacturing method of the high weatherability silicone modified polyester resin of this invention is as follows.

First, the modified polyester resin intermediate by polyester resin (A) and unsaturated monomer (B) is manufactured. The following three methods can be used for the manufacturing method of this modified polyester resin intermediate.

First, an unsaturated reactor is introduced into a polyester resin using unsaturated basic acids such as maleic anhydride and fumaric acid, and then copolymerized according to a known method using an unsaturated monomer (B) with an initiator.

At this time, the amount of unsaturated basic acid required to modify the unsaturated monomer in the polyester resin can be calculated by the following formula.

Ma = Fma {Mo-Ea + [Ea (AN / ANO) / ANo]}

Mo: confiscation of the whole raw material

Ma: confiscation of unsaturated organic acids

ANo: Calculated Acid Value of Reaction Initial Polyester Resin

Acid value measured by AN: P% reaction

Ma functions in Fma: P% reaction, usually Fma = 1/3

Ea: equivalent of organic acid

Second, the unsaturated monomer (B) is polymerized with the initiator to prepare a reactive oligomer, and then the reactive oligomer is used together with the polyester raw material in the preparation of the polyester resin (A) to perform a known ester condensation reaction.

When producing the reactive oligomer, the functional group is preferably a hydroxyl group or a carboxyl group or a mixture thereof, the amount of hydroxyl groups is preferably 0.1 to 3% by weight and an acid value of 5 to 100 mg / KOH as the functional group. The molecular weight of the reactive oligomer is preferably in the range of 500 to 10,00 because the modification of the modified body is less when the molecular weight is 500 or less, and when the molecular weight exceeds 10,00, the modification of the polyester resin is difficult.

Third, after the polyester resin is synthesized, one or two or more unsaturated monomers are used together with the initiator to proceed the graft reaction. Special care must be taken to ensure that no unreacted material remains.

The silicone-modified polyester resin of the present invention can be produced by condensation reaction of the hydroxyl functional group of the modified polyester resin prepared as described above with silicon intermediate of silanol or methoxy functional groups in the presence of a titanium catalyst.

At this time, the reactor is attached with a dehydration trap and reacted while refluxing the solvent. If the silicone modified body does not sufficiently react with the modified polyester resin, an opaque dry coating film is formed.

According to the second method of the present invention, as in the method for preparing the oligomer of the unsaturated monomer, the unsaturated monomer is polymerized with a silicone modified body (C) containing an unsaturated group together with an initiator to prepare a reactive silicone modified intermediate, followed by polyester resin ( The resin composition of the present invention can be prepared by administering the reactive silicone-modified intermediate together with the raw material of A) in a reactor to perform condensation copolymerization.

The molecular weight of the silicone-modified polyester resin of the present invention has a number average molecular weight of 2,000 to 20,000 is preferred, the resin solid content is 30 to 80%, the hydroxyl group is 0.3 to 5% range, the acid value is in the range of 1 to 30 mg KOH / g It is preferable.

Hereinafter, the embodiments of the present invention will be described in more detail, but the present invention is not limited to the following examples, and those skilled in the art will be aware of the present invention within the spirit and scope of the present invention based on the detailed description and claims of the present invention. It will be appreciated that various modifications and applications are possible and that such modifications and applications fall within the scope of the present invention.

Example 1

A four-necked 2-liter flask was equipped with a condenser, a decanter, a heating device, a thermometer, and a variable speed agitation device, and 408 parts by weight of neopentyl glycol, 557 parts by weight of isophthalic acid, 30 parts by weight of maleic anhydride, and 61 parts by weight of trimethanol Propane and 82 parts by weight of adipic acid are added and dehydration reaction is carried out at reflux at 230 ° C using xylene as a solvent. When the acid value is 15 mg KOH / g or less, and the Gardner bubble viscosity is u-z at 60% of solid content and 25 ° C, it is cooled to 150 ° C and 378 parts by weight of cocosol (Kocosol ^R pore product) and 8 parts by weight of 2 are used as a diluent. -Ethoxyethyl acetate (aka cellulose solacetate) was added to adjust the solids to 60%.

Example 2

226 parts by weight of 1,6-hexanediol, 208 parts by weight of neopentylglycol, 530 parts by weight of phthalic anhydride, 61 parts by weight of trimethanol propane, and 82 parts by weight of aziraic acid were added to the same device as in Example 1. The reaction is carried out to synthesize a polyester resin having a Gardner bubble viscosity of u to z, a solid content of 60% and an acid value of 12 mg KOH / g.

Example 3

In a 2-liter four-necked flask equipped with a condenser, a heating device, a thermometer, and a variable speed stirrer, 1000 parts by weight of the resin of Example 1 was placed, 30 parts by weight of 2-hydroxyethyl acrylate, 100 parts by weight of butyl acrylate, and 130 parts by weight of methyl. A mixture of methacrylate, 12.8 parts by weight of di-t-butyl peroxide and 171 parts by weight of 2-ethoxyethyl acetate was added dropwise at 150 ° C. for 3 hours, and then reacted at 155 ° C. for 10 hours to obtain a Gardner bubble viscosity. A modified polyester resin of z ₁ to z ₃ and solid content of 60% is prepared.

Example 4

100 parts by weight of xylene and 71 parts by weight of 2-ethoxyethyl acetate were added to the same apparatus as in Example 3, heated to 120 ° C, and then 30 parts by weight of 2-hydroxyacrylate, 130 parts by weight of ethyl acrylate, and 50 parts by weight of Negative methylmethacrylate, 50 parts by weight of styrene, and 12.8 parts by weight of benzoyl peroxide mixture were added dropwise over 3 hours, stirred at the same temperature for 10 hours, and the reaction was carried out with a polymer conversion of 99.5% or more. Terminate

Reagents of the same components as in Example 2 and the above-described reactive oligomer were added together and added dropwise at 150 ° C. over 3 hours, and then reacted at 155 ° C. for 10 hours to give 60% solids and a Gardner bubble viscosity of z _2. A modified polyester resin having ˜z ₄ is prepared.

Example 5

1000 parts by weight of the resin of Example 2 was placed in the same apparatus as in Example 3, 30 parts by weight of 2-hydroxypropyl acrylate, 70 parts by weight of Beoba 10 (Shell, Inc.), 30 parts by weight of butyl acrylate, and 130 parts by weight of methylmeth A mixture of acrylate, 20 parts by weight of benzoyl peroxide and 2-ethoxyethyl acetate was added dropwise at 80 ° C. over 1 hour 30 minutes, and then heated to 110 ° C. for graft reaction for 15 hours. As a result, a resin having a resin solid content of 60% and a Gardner bubble viscosity of w to z ₁ is produced.

Example 6

1000 parts by weight of the resin of Example 3 was placed in the same apparatus as in Example 1, and 257 parts by weight of Z-6018 (Dow Corning agent), 2 parts by weight of tetrabutyl titanate and 171 parts by weight of xylene were added as silicon intermediate. The dehydration condensation reaction is carried out while refluxing at 160 ° C. until the dry coating film becomes transparent. 60% of solid content, resin of Gardner bubble viscosity w-z are synthesize | combined.

Example 7

Into the same device as in Example 1, 257 parts by weight of DC-3074 (Dow Corning agent), 2 parts by weight of tetraisopropyl titanate and 170 parts by weight of xylene as silicon intermediate were added to 1000 parts by weight of the resin of Example 4. Resin was prepared as in Example 6. Solids 60%, Gardner bubble viscosity is made of the resin of z z ~ _3.

Example 8

Resin was prepared in the same manner as in Example 6 using 1000 parts by weight of the modified polyester resin prepared in Example 5. Solids 60%, Gardner bubble viscosity is made of a transparent resin of the y ~ z _2.

Example 9

In preparing the reactive oligomer of Example 4, 50 parts by weight of KBM 503 (new moon product) was added as a silicone modified body, a reactive oligomer was prepared to prepare a modified polyester resin in the same manner as in Example 4, and then In the same manner, a silicone-modified polyester resin having a solid content of 60% and a Gardner bubble viscosity of z ₂ to z ₄ is prepared.

Example 10

Instead of KBM 503 in Example 9, a silicone-modified polyester resin was produced in the same manner using 70 parts by weight of silicone macromonomer AK-5 (manufactured by Nippon Dong-A Synthetic Agent).

Example 11

350 parts by weight of neopentyl glycol, 100 parts by weight of trimethanol propane, 530 parts by weight of isophthalic acid, 30 parts by weight of benzoic acid and 100 parts by weight of adipic acid were added to the same device as Example 1 to reflux with 170 parts by weight of xylene solvent. The dehydration reaction is carried out at 占 폚. When acid value is 11-15 mgKOH / g and viscosity becomes u-y, it cools and adjusts solid content 60 using 150 parts of cocosol 150 as a solvent.

The conventional silicone-modified polyester resin having a solid content of 60% Gardner bubble viscosity y to z ₁ was prepared by the same method as in Preparation Example 6 with respect to 1000 parts by weight of the resin thus prepared.

Example 12

[Production and Comparative Experiment of Paint]

450 parts by weight, 240 parts by weight of titanium dioxide and 0.6 parts by weight of an emulsifier (manufactured by FC 430, 3M) were added to the modified silicone polyester resin of Examples 6 to 10 and the conventional silicone modified resin of Example 11, respectively. The paint was dispersed to a particle size of 7 by a motor mill, followed by 30 parts by weight of hexamethylenemethoxymeramine, 250 parts by weight of 2-ethoxyethyl acetate, 28 parts by weight of 2-butoxyethanol (trade name; butyl cellosolve) and 1.5 parts by weight. A paint is prepared by adding a p-toluenesulfonic acid catalyst.

After the epoxy coating of 3 to 8 microns on a 0.5 mm thick chemically-treated hot-dip galvanized steel sheet, it was coated with a bar coder with paint prepared from the resin composition of Example 6-10 and Comparative Example 11 for 50 seconds at 260 ° C. After baking (PMT 215 ° C.), dry the specimen to 15 microns.

The properties of each paint were tested and shown in Table 1 below.

Each test method and test conditions used a conventional coating film evaluation method, specifically described as follows.

Glossiness was measured for reflectance when the incident and received angle was 60 ℃ with a gloss meter.

Solvent resistance was measured by applying MEK solvent to the gauze, applying a force on the coating film, and then rubbing back and forth to damage the coating film.

Processability (T band) is to bend the painted body 180 ° completely to check whether the coating film is damaged. 1T when 2 sheets are bent at a thickness of 1 sheet, 2T when 2 sheets,. … nT is assumed to be n sheets.

The Ericsen test was performed by extending the coating film by 6 mm with the Eriksen tester, and confirming the presence or absence of the abnormality.

Impact performance was evaluated by placing a specimen at the bottom of the 1/2 diameter sphere with a DuPont impact tester and dropping the weight of 500 g from the height of 50 cm to confirm the abnormality of the coating film.

Coin scratchability was evaluated by measuring the strength and toughness of the coating film by using a coin on the coating film.

Wear resistance was evaluated by calculating the amount of damage to the coating film by rotating it 1000 times with a wear resistance measuring instrument.

Sulfuric acid resistance was spotted by dropping a 5% H ₂ SO ₄ solution on the coating film for 72 hours, and then the damage of the coating film was confirmed.

Alkali resistance was dropped for 5 hours in a drop of 5% NaOH solution on the cutting board, after which the damage to the coating was confirmed.

In the boiling water test, the specimen was placed in boiling water and maintained for 2 hours, and then subjected to abnormality.

Pencil hardness was measured for scratch hardness with a Mitsubishi standard pencil.

The QUV test measured gloss retention and color change (ΔE) after 500 hours using a QUV accelerated weathering tester.

In the salt spray test, the cross-cut specimens were allowed to stand at 35 ° C. for 500 hours in a tester sprayed with a 5% NaCl solution, and then the degree of corrosion was evaluated.

In the following table, each test result is shown as the best (◎), good ((circle)), normal (△), and bad (x).

As described above, the paint made of the silicone-modified polyester resin prepared by the manufacturing method of the present invention is excellent in processability and gloss, and strong against acidic and alkaline chemicals, compared with the paint made of the conventional silicone-modified polyester resin. In addition, the impact, coinstretch and weather resistance were better.

Claims (6)

100 weight part of polyester resin intermediate whose average molecular weight is 1,000-10,000, solid content is 30-80 weight%, a hydroxyl value is 0.3-3 weight%, and an acid value is 1-30 mg KOH / G; Unsaturated monomer having the following structure (I), (II) or (III), selected from the group consisting of unsaturated monomers having a glass transition temperature of -50 to 80 ° C and a hydroxyl content of 0.5 to 5% by weight or 5-100 parts by weight of two or more reactive modified substances; A group consisting of a silicone intermediator having 2 to 4 functional groups and a molecular weight of 1,000 to 3,000, wherein the silane compounding rate or silicone macromonomer or substituent having an unsaturated functional group of vinyl or methacryl is a methylphenyl group and the functional group is a silanol or methoxy group. A method for producing a high weather resistance silicone modified polyester resin, characterized in that for copolymerizing 1-50 parts by weight of the silicone modified material selected from. Wherein X represents hydrogen or a methyl group, Y represents C _n H _{2n + 1} , hydrogen or a macromonomer having a molecular weight of 50 to 5000, where n represents an integer of 1 to 12; Wherein X represents hydrogen or a methyl group, n represents an integer of 1 to 10; or Wherein X represents hydrogen or a methyl group, Z represents phenyl, -CN, -CONH-R ₁ or a markonomer having a molecular weight of 50 to 5000, wherein R ₁ represents H or -C (CH ₃ ) ₂ CH ₂ C = O. The method according to claim 1, wherein the modified polyester resin intermediate is prepared by a polyester resin intermediate and an unsaturated monomer, and then the modified polyester resin intermediate is modified by a silicone modified body. The method of claim 2, wherein the modified polyester resin intermediate is prepared by introducing an unsaturated reactor into the polyester resin using unsaturated basic acid, and then copolymerizing the unsaturated monomer with an initiator. The method of claim 2, wherein the modified polyester resin intermediate is prepared by polymerizing an unsaturated monomer with an initiator to prepare a reactive oligomer, followed by condensation reaction with the polyester resin intermediate. The method of claim 2, wherein the modified polyester resin intermediate is prepared by graft reacting a polyester with one or more unsaturated monomers and an initiator. The method according to claim 1, wherein a reactive silicone intermediate of the silicone modified body of the unsaturated monomer is prepared and then subjected to condensation copolymerization reaction with the polyester resin.