CN113336925A - Saturated polyester resin and preparation method thereof - Google Patents
Saturated polyester resin and preparation method thereof Download PDFInfo
- Publication number
- CN113336925A CN113336925A CN202110618920.XA CN202110618920A CN113336925A CN 113336925 A CN113336925 A CN 113336925A CN 202110618920 A CN202110618920 A CN 202110618920A CN 113336925 A CN113336925 A CN 113336925A
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- Prior art keywords
- polyester resin
- saturated polyester
- acid
- lactide
- solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
Abstract
A saturated polyester resin and a preparation method thereof. The invention discloses a saturated polyester resin which comprises the following components in percentage by mass: 5-50% of a polyol; 5-50% of polybasic acid and/or polybasic acid anhydride; 5-80% lactide; 0-1% of a color reducing agent; 0-1% of a catalyst; 0-5% of a reflux solvent; 0-41% of a diluent solvent. The saturated polyester resin can be used for preparing elastic hand-feeling paint with good hand feeling and excellent wear resistance.
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to a saturated polyester resin and a preparation method thereof.
Background
The elastic hand feeling coating can be sprayed on the plastic or plastic surfaces of small electronic products and electric products to improve the touch feeling of the surfaces of the products. The elastic hand feeling coating is generally divided into a primer and a finish, and the finish plays a role in improving touch feeling. The predominant system employed for topcoats is the polyurethane system, in which the hydroxyl resin portion is generally saturated polyester. The saturated polyester has good flexibility, can provide elasticity and hand feeling for a system, but has poor wear resistance. In the case where abrasion resistance is required, other types of resins such as acrylic resins and polycarbonate diol resins must be supplemented. Although the resin compounding can effectively improve the wear resistance of the resin, the compatibility and the stability of the system are easily influenced.
There is a need to solve the above-mentioned technical problems by providing a saturated polyester resin that provides both an elastic hand feel and abrasion resistance.
Disclosure of Invention
In order to solve the above problems, the present invention provides a saturated polyester resin and a method for preparing the same. The saturated polyester resin effectively improves the wear resistance of the resin under the condition of keeping the original elasticity and hand feeling. The preparation method of the saturated polyester resin is simple and easy to popularize.
The invention solves the technical problems by the following technical scheme:
the invention provides a saturated polyester resin which comprises the following components in percentage by mass: 5-50% of a polyol;
5-50% of polybasic acid and/or polybasic acid anhydride;
5-80% lactide;
0-1% of a color reducing agent;
0-1% of a catalyst;
0-5% of a reflux solvent;
0-41% of a diluent solvent.
Preferably, the saturated polyester resin comprises the following components in percentage by mass:
15-17% of a polyol;
14-16% of polybasic acid and/or polybasic acid anhydride;
35-40% lactide;
0.1-0.4% of a color reducing agent;
1-3% of a reflux solvent;
25-30% of a diluent solvent.
More preferably, the saturated polyester resin comprises the following components in percentage by mass:
16% of a polyol;
15% of a polybasic acid and/or a polybasic acid anhydride;
38.7% lactide;
0.3% of a color reducing agent;
2% of a reflux solvent;
28% of a diluent solvent.
In the present invention, the polyols are conventional in the art;
preferably, the polyhydric alcohol is one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-butanediol, 2, 4-trimethyl-1, 3-pentanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, glycerol, trimethylolethane, trimethylolpropane and pentaerythritol.
In the present invention, the polybasic acids and/or polybasic anhydrides are conventional in the art;
preferably, the polybasic acid and/or polybasic acid anhydride is one or more of phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid and trimellitic anhydride.
In the invention, the lactide is one or more of L-lactide, D-lactide, DL-lactide and Meso-lactide;
preferably, the lactide is L-lactide.
In the present invention, the color reducing agent is conventional in the art;
preferably, the color reducing agent is one or more of phosphoric acid, hypophosphorous acid and triphenyl phosphite.
In the present invention, the catalyst is conventional in the art;
preferably, the catalyst is one or more of a titanium catalyst, a tin catalyst and an antimony catalyst;
more preferably, the catalyst is one or more of monobutyltin oxide, dibutyltin dilaurate, stannous octoate, tetraisopropyl titanate, tetrabutyl titanate and antimony acetate.
In the present invention, the refluxing solvent is conventional in the art;
preferably, the refluxing solvent is xylene and/or D40 solvent oil.
In the present invention, the diluting solvent is conventional in the art;
preferably, the diluting solvent is one or more of toluene, xylene, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, diacetone alcohol, methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone and cyclohexanone.
The invention also provides a preparation method of the saturated polyester resin, which comprises the following steps:
s1, putting the polyol, the polybasic acid and/or the polybasic acid anhydride, the lactide, the color reducing agent and the catalyst into a reactor, introducing nitrogen, and enabling the flow rate to be 0.1-15 m3And h, stirring, heating until water is discharged, keeping the temperature for 0.1-3 h at the water discharge temperature, then heating for 0.1-10 h to the maximum reaction temperature of 200-250 ℃, adding a reflux solvent, keeping the temperature at the maximum reaction temperature until the solid acid value is less than 25mgKOH/g, and the Gauss viscosity is 25 ℃: z to Z8;
s2, cooling to 80-190 ℃, adding a diluting solvent, and uniformly stirring.
Preferably, in S1, the flow rate of nitrogen is 5m3And h, preserving the heat of the effluent for 1h at the temperature of the effluent, heating the effluent to 225 ℃ in 4h, adding a reflux solvent, preserving the heat at 225 ℃ until the solid acid value is 6-20 mgKOH/g and the Grignard viscosity is 25 ℃: Z3-Z5;
preferably, in S2, the temperature is reduced to 120 ℃, and the diluting solvent is added and stirred uniformly.
The starting materials of the present invention are all commercially available.
The invention has the advantages and beneficial effects that: the saturated polyester resin provided by the invention has good hand feeling and excellent wear resistance. The preparation method of the saturated polyester resin is simple and easy to popularize.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The starting materials used in the following examples and comparative examples are commercially available.
Example 1
The embodiment provides a saturated polyester resin, which comprises the following components: 11kg of 1, 6-hexanediol; 5kg of trimethylolpropane; 38.7kg of L-lactide; 15kg of isophthalic acid; hypophosphorous acid 0.2 kg; 0.1kg of triphenyl phosphite; 2kg of dimethylbenzene; 28kg of butyl acetate.
The preparation method of the saturated polyester resin of the embodiment comprises the following steps:
s1, putting 1, 6-hexanediol, trimethylolpropane, L-lactide, isophthalic acid, hypophosphorous acid and triphenyl phosphite into a reactor, introducing nitrogen, and controlling the flow rate to be 5m3And/h, starting stirring, heating to effluent, keeping the temperature for 1h at the effluent temperature, then heating to 225 ℃ for 5h, adding dimethylbenzene, keeping the temperature at 225 ℃ until the solid acid value is less than 20mgKOH/g, and the Grignard viscosity is 25 ℃: Z3-Z5;
s2, cooling to 120 ℃, adding butyl acetate, and stirring uniformly.
Example 2
The embodiment provides a saturated polyester resin, which comprises the following components: 20kg of 1, 4-cyclohexanedimethanol; 2kg of trimethylolpropane; 1kg of glycerol; 6.2kg of 1, 4-butanediol; 30kg of L-lactide; 17.4kg of hexahydrophthalic anhydride; 4kg of adipic acid; hypophosphorous acid 0.2 kg; 2kg of dimethylbenzene; 17.2kg of butyl acetate.
The preparation method of the saturated polyester resin of the embodiment comprises the following steps:
s1, putting 1, 4-cyclohexanedimethanol, trimethylolpropane, glycerol, 1, 4-butanediol, L-lactide, hexahydrophthalic anhydride, adipic acid and hypophosphorous acid into a reactor, introducing nitrogen, and introducing 6m of flow3And/h, starting stirring, heating to effluent, keeping the temperature for 1h at the effluent temperature, then heating to 220 ℃ for 4h, adding dimethylbenzene, keeping the temperature at 220 ℃ until the solid acid value is less than 12mgKOH/g, and the Grignard viscosity is 25 ℃: Z6-Z8;
s2, cooling to 120 ℃, adding butyl acetate, and stirring uniformly.
Example 3
The embodiment provides a saturated polyester resin, which comprises the following components: 19.5kg of 1, 6-hexanediol; 4kg of trimethylolethane; 22.8kg of L-lactide; 11.5kg of phthalic anhydride; 12kg of adipic acid; hypophosphorous acid 0.1 kg; 0.1kg of triphenyl phosphite; 2kg of dimethylbenzene; propylene glycol methyl ether acetate 28 kg.
The preparation method of the saturated polyester resin of the embodiment comprises the following steps:
s1, putting 1, 6-hexanediol, trimethylolethane, L-lactide, phthalic anhydride, adipic acid, hypophosphorous acid and triphenyl phosphite into a reactor, introducing nitrogen, and introducing 3m of nitrogen3And/h, starting stirring, heating to effluent, keeping the temperature for 1h at the effluent temperature, then heating to 230 ℃ after 6h, adding dimethylbenzene, keeping the temperature at 230 ℃ until the solid acid value is less than 15mgKOH/g, and the Grignard viscosity is 25 ℃: Z2-Z4;
s2, cooling to 140 ℃, adding propylene glycol methyl ether acetate, and stirring uniformly.
Example 4
The embodiment provides a saturated polyester resin, which comprises the following components: 15kg of 1, 4-butanediol; 29.7kg of diethylene glycol; 2kg of trimethylolpropane; 10kg of L-lactide; 13kg of methyl hexahydrophthalic anhydride; 30kg of adipic acid; 0.3kg of triphenyl phosphite.
The preparation method of the saturated polyester resin of the embodiment comprises the following steps:
putting 1, 4-butanediol, diethylene glycol, trimethylolpropane, L-lactide, methyl hexahydrophthalic anhydride and triphenyl phosphite into a reactor, introducing nitrogen gas, and controlling the flow at 5m3And/h, starting stirring, heating to effluent, keeping the temperature for 1h at the effluent temperature, then heating to 225 ℃ for 5h, and keeping the temperature at 225 ℃ until the solid acid value is less than 15mgKOH/g and the Grignard viscosity is 25 ℃: Z5-Z7;
s2, cooling to 90 ℃, and stirring uniformly.
Comparative example 1
This comparative example provides a saturated polyester resin having a designation of ESC-2200 manufactured by Dongsheng chemical (Shanghai) Co., Ltd, which comprises, in mass percent: 18.5% of 1, 4-butanediol, 13.4% of diethylene glycol, 9.3% of ethylene glycol and 58.8% of adipic acid.
The solid content is more than 99.0 percent; gaster viscosity 25 ℃: y to Z1, and the solid acid value is less than 12 mgKOH/g.
The resins of the above examples 1,2, 3, 4 and 1 are added with a curing agent Bayer N75, a matting agent OK520, a leveling agent Tego450, a drier DBTDL, a solvent and other auxiliary agents, dispersed at high speed to obtain an elastic hand feeling coating, and then sprayed on a plastic substrate coated with a primer. And testing the surface performance of the paint film after curing.
The properties of the coatings prepared from the products of example 1, example 2, example 3, example 4, and comparative example 1 were examined as shown in table 1 below:
TABLE 1 coating Properties prepared from the resins of examples 1-4 and comparative example 1
In the RCA wear-resistant test, 175 grams of force is applied to an RCA wear-resistant mill, the surface of a paint film is rubbed, and the times of the scratch of the paint film are recorded, and more times are preferred.
The effect shows that the elastic hand feeling coating prepared from the saturated polyester resin greatly improves the wear resistance of a paint film under the condition of keeping the hand feeling of the paint film unchanged.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The saturated polyester resin is characterized by comprising the following components in percentage by mass:
5-50% of a polyol;
5-50% of polybasic acid and/or polybasic acid anhydride;
5-80% lactide;
0-1% of a color reducing agent;
0-1% of a catalyst;
0-5% of a reflux solvent;
0-41% of a diluent solvent.
2. The saturated polyester resin according to claim 1, comprising the following components in percentage by mass:
15-17% of a polyol;
14-16% of polybasic acid and/or polybasic acid anhydride;
35-40% lactide;
0.1-0.4% of a color reducing agent;
1-3% of a reflux solvent;
25-30% of a diluent solvent.
3. The saturated polyester resin according to claim 2, wherein the saturated polyester resin comprises the following components in percentage by mass:
16% of a polyol;
15% of a polybasic acid and/or a polybasic acid anhydride;
38.7% lactide;
0.3% of a color reducing agent;
2% of a reflux solvent;
28% of a diluent solvent.
4. The saturated polyester resin according to any one of claims 1 to 3, wherein the polyhydric alcohol is one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-butanediol, 2, 4-trimethyl-1, 3-pentanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, glycerol, trimethylolethane, trimethylolpropane and pentaerythritol;
and/or the polybasic acid and/or polybasic acid anhydride is one or more of phthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid and trimellitic anhydride;
and/or the lactide is one or more of L-lactide, D-lactide, DL-lactide and Meso-lactide;
and/or the color reducing agent is one or more of phosphoric acid, hypophosphorous acid and triphenyl phosphite.
5. The saturated polyester resin according to any one of claims 1 to 3, wherein the catalyst is one or more of a titanium-based catalyst, a tin-based catalyst and an antimony-based catalyst.
6. The saturated polyester resin of claim 5, wherein the catalyst is one or more of monobutyltin oxide, dibutyltin dilaurate, stannous octoate, tetraisopropyl titanate, tetrabutyl titanate, and antimony acetate.
7. The saturated polyester resin according to any one of claims 1 to 3, wherein the refluxing solvent is xylene and/or D40 solvent oil;
and/or the diluting solvent is one or more of toluene, xylene, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, diacetone alcohol, methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone and cyclohexanone.
8. The method for preparing a saturated polyester resin according to any one of claims 1 to 7, comprising the steps of:
s1, putting the polyol, the polybasic acid and/or the polybasic acid anhydride, the lactide, the color reducing agent and the catalyst into a reactor, introducing nitrogen, and enabling the flow rate to be 0.1-15 m3And/h, stirring, heating until water is discharged, keeping the temperature for 0.1-3 h at the water discharge temperature, then heating for 0.1-10 h to the highest reaction temperature of 200-250 ℃, adding a reflux solvent, keeping the temperature at the highest reaction temperature until the solid acid value is less than 25mgKOH/g and the Gauss viscosity is 25 ℃: z to Z8;
s2, cooling to 80-170 ℃, adding a diluting solvent, and uniformly stirring.
9. The method for preparing saturated polyester resin according to claim 8, wherein the flow rate of nitrogen gas in S1 is 5m3And h, preserving the heat of the effluent for 1h, heating the effluent to 225 ℃ in 5h, adding a reflux solvent, preserving the heat at 225 ℃ until the solid acid value is 6-20 mgKOH/g and the Grignard viscosity is 25 ℃: Z3-Z5.
10. The method for preparing saturated polyester resin according to claim 8, wherein in S2, the temperature is reduced to 120 ℃, and the diluent solvent is added and stirred uniformly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110618920.XA CN113336925A (en) | 2021-06-03 | 2021-06-03 | Saturated polyester resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110618920.XA CN113336925A (en) | 2021-06-03 | 2021-06-03 | Saturated polyester resin and preparation method thereof |
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| CN113336925A true CN113336925A (en) | 2021-09-03 |
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| CN202110618920.XA Pending CN113336925A (en) | 2021-06-03 | 2021-06-03 | Saturated polyester resin and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114933695A (en) * | 2022-03-09 | 2022-08-23 | 东胜化学(上海)有限公司 | Alkyd resin and preparation method thereof |
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| WO1998029470A1 (en) * | 1996-12-30 | 1998-07-09 | Daicel Chemical Industries, Ltd. | Polyester elastomers, processes for preparing the same, and compositions of the same |
| US20030083191A1 (en) * | 2001-02-23 | 2003-05-01 | Takahiro Nakajima | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
| CN102174201A (en) * | 2011-01-31 | 2011-09-07 | 华润包装材料有限公司 | Modified copolyester material for manufacturing high-gloss thick-wall products, and preparation method thereof |
| CN102695991A (en) * | 2010-01-08 | 2012-09-26 | Sk化学株式会社 | Polyester resin and toner including same |
| CN103492453A (en) * | 2011-04-06 | 2014-01-01 | Sk化学株式会社 | Polyester binder resin for coating, and coating composition containing same |
| US20140205786A1 (en) * | 2012-03-30 | 2014-07-24 | E I Du Pont De Nemours And Company | Polyesters and articles made therefrom |
-
2021
- 2021-06-03 CN CN202110618920.XA patent/CN113336925A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998029470A1 (en) * | 1996-12-30 | 1998-07-09 | Daicel Chemical Industries, Ltd. | Polyester elastomers, processes for preparing the same, and compositions of the same |
| US20030083191A1 (en) * | 2001-02-23 | 2003-05-01 | Takahiro Nakajima | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
| CN102695991A (en) * | 2010-01-08 | 2012-09-26 | Sk化学株式会社 | Polyester resin and toner including same |
| US20120276479A1 (en) * | 2010-01-08 | 2012-11-01 | Young Man Yoo | Polyester resin and toner including same |
| CN102174201A (en) * | 2011-01-31 | 2011-09-07 | 华润包装材料有限公司 | Modified copolyester material for manufacturing high-gloss thick-wall products, and preparation method thereof |
| CN103492453A (en) * | 2011-04-06 | 2014-01-01 | Sk化学株式会社 | Polyester binder resin for coating, and coating composition containing same |
| US20140205786A1 (en) * | 2012-03-30 | 2014-07-24 | E I Du Pont De Nemours And Company | Polyesters and articles made therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114933695A (en) * | 2022-03-09 | 2022-08-23 | 东胜化学(上海)有限公司 | Alkyd resin and preparation method thereof |
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