CN116096777B - A polyester resin for metal powder coating and its preparation method and application - Google Patents
A polyester resin for metal powder coating and its preparation method and application Download PDFInfo
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- CN116096777B CN116096777B CN202280004573.4A CN202280004573A CN116096777B CN 116096777 B CN116096777 B CN 116096777B CN 202280004573 A CN202280004573 A CN 202280004573A CN 116096777 B CN116096777 B CN 116096777B
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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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
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- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- 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
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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
- C08G63/78—Preparation processes
- C08G63/81—Preparation processes using solvents
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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
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Abstract
本发明提供一种金属粉末涂料用聚酯树脂及其制备方法和应用，所述金属粉末涂料用聚酯树脂制备原料包括：多元醇、卤代双酚A、对苯二甲酸、苯酐、酸解剂和叔碳酸缩水甘油酯。本发明的金属粉末涂料用聚酯树脂由于引入了具有卤素侧基的卤代双酚A而增强了聚酯树脂的极性，极性的增强有利于提高树脂的表面张力。金属粉末涂料在高温固化过程中，金属颜料在树脂表面张力的拉动力下可以减轻重力沉降的影响，将金属颜料稳固在涂层表面，使涂层表现出更佳的金属效果。The present invention provides a polyester resin for metal powder coating, a preparation method and application thereof, wherein the raw materials for preparing the polyester resin for metal powder coating include: polyol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, an acidolysis agent and tert-butyl glycidyl carbonate. The polyester resin for metal powder coating of the present invention enhances the polarity of the polyester resin due to the introduction of halogenated bisphenol A with halogen side groups, and the enhancement of polarity is beneficial to improving the surface tension of the resin. During the high-temperature curing process of the metal powder coating, the metal pigment can reduce the influence of gravity sedimentation under the pulling force of the resin surface tension, stabilize the metal pigment on the coating surface, and make the coating show a better metal effect.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a polyester resin for a metal powder coating, and a preparation method and application thereof.
Background
With the importance of environmental protection, as an environment-friendly, high-efficiency and economical powder coating, the variety is continuously increased and the application field is gradually expanded with the rapid development of technology in recent years. In the aspect of decoration, besides the common powder coating varieties with different gloss and flat surfaces, the varieties and the amounts of orange lines, wrinkles, sand lines, patterns, hammers and metal powder coatings are also increased, and the powder coatings gradually penetrate into various fields of solvent type coating application. Among the above-mentioned varieties, metal powder coating materials are known by industry as a high-grade product in the field of powder coating materials, and the product can be further subdivided into metal powder coating materials such as metal sparkling, metal plating, metal pattern, hammer tone, metal luster texture and the like.
At present, a high-performance metal powder coating in the market is mostly prepared by a thermal bonding method, and because the bonding method is high in requirements on bonding equipment and technology, more researches are conducted on the bonding equipment and technology. The research reports on metal powder coating are basically concentrated on bonding equipment and technology, and the research on matched polyester is basically not reported. Because of the lack of matched polyester resin in the market at present, the advanced powder manufacturer utilizes stronger formulation research and development design capability, and simultaneously prepares the metal powder coating by matching with advanced bonding equipment and strict process control, but the problem of unstable product batch is still difficult to solve. For most small and medium enterprises with weak capital and technical capability, the research and development production of related metal powder are difficult. In order to promote the development of metal powder coating, research on the aspects of strengthening manufacturing equipment, process, raw materials and the like by linking up the upstream and downstream is needed. In terms of matched resin, the research on special polyester for metal powder coating is relatively lacking at present, and in order to meet the demand of the market on rapid increase of the dosage of the metal powder coating, it is necessary to provide a polyester resin suitable for the metal powder coating, so as to reduce the dependence on equipment and process control, thereby promoting rapid development of the metal powder coating.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the first aspect of the invention provides a polyester resin for metal powder coating, and bonding metal powder coating prepared by using the polyester resin has outstanding metal effect and beautiful appearance.
The second aspect of the invention provides a preparation method of the polyester resin for the metal powder coating.
In a third aspect, the present invention provides a metal powder coating comprising the polyester resin for a metal powder coating.
According to a first aspect of the present invention, there is provided a polyester resin for metal powder coating, which is prepared from a polyhydric alcohol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, an acidolysis agent and glycidyl versatate.
In some embodiments of the invention, the polyester resin for the metal powder coating is prepared from, by mass, 20-35% of polyol, 3-20% of halogenated bisphenol A, 30-55% of terephthalic acid, 2-10% of phthalic anhydride, 5-15% of acidolysis agent and 1-5% of glycidyl versatate.
In some preferred embodiments of the present invention, the halogenated bisphenol a has the structural formula of formula I:
Wherein each R is independently selected from H and/or halogen, and at least one R is H and at least one R is halogen.
Preferably, the halogenated bisphenol a comprises a dihalo bisphenol a having the structural formula Ia:
Wherein R 1 is halogen;
further preferred, the halogenated bisphenol a has the structural formula Ib:
in some preferred embodiments of the present invention, the halogenated bisphenol A is used in an amount of 5wt% to 20wt%, preferably 5wt% to 15wt%, based on mass fraction.
In some more preferred embodiments of the present invention, the polyol comprises at least one of neopentyl glycol, ethylene glycol, 2-methyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 1, 6-hexanediol, 1, 4-cyclohexane diol, or trimethylolpropane, preferably a combination of neopentyl glycol and other polyols. It is further preferred that the ratio of neopentyl glycol to other polyols is greater than 5:1, and it is still further preferred that the ratio of neopentyl glycol to other polyols is greater than 6:1.
In some more preferred embodiments of the present invention, the polyol is used in an amount of 25wt% to 35wt%, preferably 28wt% to 33wt%, by mass.
In some more preferred embodiments of the present invention, the terephthalic acid is used in an amount of 30wt% to 50wt%, preferably 35wt% to 50wt%, and more preferably 35wt% to 45wt% in terms of mass fraction.
In some more preferred embodiments of the present invention, the phthalic anhydride acid is used in an amount of 3wt% to 10wt%, preferably 4wt% to 10wt%, and more preferably 5wt% to 10wt% in terms of mass fraction.
In some more preferred embodiments of the present invention, the acidolysis agent comprises at least one of isophthalic acid, succinic acid, adipic acid or 1, 4-cyclohexanedicarboxylic acid, and preferably, the acidolysis agent is used in an amount of 7wt% to 15wt%, and preferably, 7wt% to 12wt%.
In some more preferred embodiments of the present invention, the amount of the tertiary glycidyl ester is 1.5wt% to 5wt%, preferably 2wt% to 5wt%, and more preferably 3wt% to 5wt% in terms of mass fraction.
In some more preferred embodiments of the present invention, the raw materials for preparing the polyester resin for the metal powder coating further include an esterification catalyst, a curing accelerator, and an antioxidant. The polyester resin for the metal powder coating is prepared from the raw materials of polyhydric alcohol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent and tertiary glycidyl ester serving as a blocking agent, wherein the tertiary glycidyl ester is used as a skeleton structure component of the polyester resin, the esterification catalyst is used for adjusting the esterification polycondensation reaction rate and the reaction degree, and the curing accelerator and the antioxidant are respectively used for improving certain performances of the polyester resin.
In some more preferred embodiments of the present invention, the esterification catalyst comprises at least one of monobutyl tin oxide, dibutyl tin oxide, or stannous oxalate. Preferably, the dosage of the esterification catalyst is 0.05% -0.15% of the total mass of the materials.
In some more preferred embodiments of the present invention, the curing accelerator comprises at least one of benzyl triethyl ammonium chloride, triphenyl, and phosphorus bromide, triphenylphosphine or tert-butylamine, and the amount of the curing accelerator is 0.01% -0.1% of the total mass of the material.
In some more preferred embodiments of the invention, the antioxidants include a primary antioxidant that includes antioxidant 1076 and/or antioxidant 1010 and a secondary antioxidant that includes antioxidant 168 and/or antioxidant 626. Preferably, the mass ratio of the primary antioxidant to the secondary antioxidant is 1:2-2:1, and more preferably 1:1.
In some more preferred embodiments of the present invention, the polyester resin for metal powder coating has an acid value of 30mgKOH/g to 35mgKOH/g, a melt viscosity of 200 ℃ of 350 mp.s to 9000mp.s, a glass transition temperature Tg of 60 ℃ to 70 ℃, and a reactivity of 180 ℃ of 120s to 360s. Preferably, the melt viscosity of the polyester resin for the metal powder coating is 200 ℃ to 800 mp.s, the glass transition temperature Tg is 62 ℃ to 70 ℃, and the reactivity of the polyester resin for the metal powder coating is 180 ℃ to 360s. Further preferably, the polyester resin for metal powder coating has a melt viscosity of 5000mp.s to 7000mp.s at 200 ℃, a glass transition temperature Tg of 62 ℃ to 68 ℃ and a reactivity of 240s to 330s at 180 ℃.
According to a second aspect of the present invention, there is provided a method for producing a polyester resin for a metal powder coating, comprising the steps of:
s1, heating and melting polyalcohol and halogenated bisphenol A in an inert atmosphere, and adding terephthalic acid to perform esterification polycondensation reaction until the materials are clear and transparent;
S2, after cooling, adding phthalic anhydride to react until the material is clear and transparent, continuously cooling, adding acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45mgKOH/g to 52mgKOH/g;
s3, cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the material is 35mgKOH/g to 42 mgKOH/g;
and S4, continuously cooling, and adding tertiary glycidyl ester to carry out end capping reaction to obtain the polyester resin for the metal powder coating.
In some embodiments of the invention, in S1, the temperature of the esterification polycondensation reaction is 240 ℃ to 245 ℃.
In some preferred embodiments of the invention, in S2, the temperature is reduced to 230-236 ℃, phthalic anhydride is added for reaction until the material is clear and transparent, the temperature is continuously reduced to 228-233 ℃, an acidolysis agent is added for reaction until the material is clear and transparent, and the acid value is controlled to be 45-52 mgKOH/g.
In some more preferred embodiments of the present invention, in S3, the temperature of the vacuum polycondensation reaction is 225 ℃ to 230 ℃ and the vacuum degree is-0.085 MPa to-0.1 MPa, preferably-0.095 MPa.
The preparation method of the polyester resin for the metal powder coating comprises the following steps:
S1, heating and melting polyol, halogenated bisphenol A and an esterification catalyst in an inert atmosphere, and adding terephthalic acid to perform esterification polycondensation reaction until the materials are clear and transparent;
S2, after cooling, adding phthalic anhydride to react until the material is clear and transparent, continuously cooling, adding acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45mgKOH/g to 52mgKOH/g;
s3, cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the material is 35mgKOH/g to 42 mgKOH/g;
and S4, continuously cooling, adding tertiary glycidyl ester to carry out end capping reaction, cooling, adding a curing agent and an antioxidant when the acid value of the material is 30mgKOH/g to 35mgKOH/g, and stirring to obtain the polyester resin for the metal powder coating.
According to a third aspect of the present invention, there is provided a metal powder coating comprising the polyester resin for a metal powder coating.
The beneficial effects of the invention are as follows:
1. The polyester resin for the metal powder coating has the advantages that the polarity of the polyester resin is enhanced due to the introduction of the halogenated bisphenol A with the halogen side group, and the enhancement of the polarity is beneficial to the improvement of the surface tension of the resin. In the high-temperature curing process of the metal powder coating, the metal pigment can lighten the influence of gravity sedimentation under the tensile force of the resin surface tension, and the metal pigment is firmly fixed on the surface of the coating, so that the coating shows better metal effect.
2. According to the invention, the tertiary glycidyl ester is introduced into the main chain of the polyester resin as the end-capping agent, and the tertiary carbon group suspended in the tertiary glycidyl ester structure can increase the wettability to the metal pigment, so that the metal pigment is better coated in the resin, and the peeling risk of the metal pigment after bonding and bonding the resin is reduced.
3. The preparation method of the polyester resin for the metal powder coating enables raw materials to be fully polymerized into a main chain, brings further optimization performance for the resin, and is characterized in that (a) phthalic anhydride has obviously higher reactivity than terephthalic acid, the phthalic anhydride is fed and added in a second step, so that incomplete reaction with terephthalic acid caused by competing polymerization reaction of terephthalic acid can be avoided, the complete reaction of halogenated bisphenol A can be ensured, and (b) tertiary glycidyl ester is taken as a monofunctional group, the polymerization degree of the main chain can be influenced by the addition of the tertiary glycidyl ester in the early stage of synthesis, meanwhile, the Tg of polyester can be obviously reduced by a larger side group in the structure.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a graph showing the distribution of silver powder in a metal powder coating of a polyester resin according to example 1 of the present invention.
FIG. 2 is a graph showing the distribution of silver powder in the metal powder paint coating of the polyester resin of comparative example 1 of the present invention.
FIG. 3 is a graph showing the distribution of silver powder in the metal powder paint coating of the polyester resin of comparative example 2 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Examples 1 to 5
S1, heating polyalcohol, halogenated bisphenol A and an esterification catalyst to be melted under the protection of inert gas according to the formula composition of the table 1, then adding terephthalic acid, and gradually heating to 240-245 ℃ for esterification polycondensation reaction until the materials are clear and transparent;
s2, cooling to below 236 ℃, adding phthalic anhydride, and continuing the reaction until the materials are clear and transparent;
s3, cooling to below 233 ℃, adding an acidolysis agent, continuing to react until the material is clear and transparent, and controlling the acid value within the range of 45mgKOH/g to 52 mgKOH/g;
S4, cooling to below 228 ℃ to carry out vacuum polycondensation reaction, and releasing vacuum when the acid value of the reaction material is 35mgKOH/g to 42 mgKOH/g.
S5, cooling to below 210 ℃, adding tertiary glycidyl ester for end capping reaction, and when the acid value of the detected material reaches 30-35 mgKOH/g, cooling, adding a curing accelerator and an antioxidant, stirring and dispersing uniformly, and discharging to obtain the polyester resin for the metal powder coating.
Comparative example 1
This comparative example produced a polyester resin, which differs from example 5 in that the tertiary glycidyl ester was adjusted to the first charge, in the following steps:
s1, heating polyol, halogenated bisphenol A, tertiary glycidyl ester and an esterification catalyst to be melted under the protection of inert gas according to the formula composition of a table 1, then adding terephthalic acid, gradually heating to a heat preservation temperature for esterification polycondensation reaction until materials are clear and transparent;
s2, cooling to below 236 ℃, adding phthalic anhydride, and continuing the reaction until the materials are clear and transparent;
S3, cooling to below 233 ℃, adding an acidolysis agent, continuing to react until the material is clear and transparent, and controlling the acid value within the range of 42mgKOH/g to 46 mgKOH/g;
S4, cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the reaction material is 30mgKOH/g to 35 mgKOH/g.
S5, cooling to below 210 ℃, adding the curing accelerator and the antioxidant, stirring and dispersing uniformly, and discharging to obtain the polyester resin.
Comparative example 2
The comparative example prepared a polyester resin, which was prepared by the following steps:
1) Heating the polyalcohol and the esterification catalyst to be melted under the protection of inert gas according to the formula composition of the table 1, then adding terephthalic acid, gradually heating to the heat preservation temperature for esterification polycondensation reaction until the materials are clear and transparent;
2) Cooling to below 235 ℃, adding acidolysis agent to continue the reaction until the material is clear and transparent, and controlling the acid value within the range of 42mgKOH/g to 46 mgKOH/g;
3) Cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the reaction material is 30mgKOH/g to 35 mgKOH/g.
4) Cooling, adding a curing accelerator and an antioxidant, stirring, dispersing uniformly, and discharging to obtain the polyester resin.
TABLE 1 polyester resin formulation
Test examples
Performance tests were performed on the polyester resins produced in examples 1 to 5 and comparative examples 1 to 2, in which:
Acid number was tested according to GB/T6743-2008;
melt viscosity ICI cone plate viscosity at 200℃as determined according to ASTM D4287-88;
glass transition temperature (Tg) tested according to GB/T19466.2;
surface tension is tested according to GB/T22237-2008;
Reactivity refers to the time required for the resin to react with the curing agent to gel, as determined according to GB/T16995-1997 at 180 ℃.
The test results are shown in table 2:
TABLE 2 Properties of polyester resin
Further, the polyester resins prepared according to the methods of examples 1-5 and comparative examples 1-2 are respectively prepared on metal powder coatings, the preparation of the metal powder coatings can be divided into two sections according to the process flow, namely 1) the preparation of the powder coating base powder, namely weighing each component according to the base powder formula of the table 3, and obtaining the required powder coating base powder after premixing, melt extrusion, cooling tabletting, crushing and crushing sieving, and 2) the bonding processing, namely putting the powder base powder, silver powder and bonding auxiliary agent into a bonding pot according to the metal powder coating formula of the table 3, stirring at high speed, heating, and bonding. After bonding, rapidly placing the materials into a cold mixing pot for low-speed stirring and cooling, and sieving to obtain the metal powder coating. The bonded metal powder coating was electrostatically sprayed on the pretreated cold-rolled steel sheet, cured at 200 ℃ for 10min to obtain a coating template, and the coating properties and metal effects thereof were measured, and the test results were as shown in table 4 below.
TABLE 3 composition of metallic powder coatings
The effect of the metal powder is mainly to meet the apparent metal effect, and the judging method is basically a visual method, which is also a commonly adopted method in the industry. The leveling property is mainly to observe the evenness of a coating film and see whether orange peel and other phenomena exist or not, and the leveling property is generally compared with a PCI standard board, wherein 1-9 shows that the evenness is poor to good. The uniformity of the metal powder is mainly to see whether the metal powder is uniformly distributed on the surface of the sample plate, and whether the metal powder is excessive in some areas and less in some areas is known as bloom in the industry. If the bonding effect is poor, the free metal pigment is easily adsorbed on the periphery of the template due to electrostatic adsorption, so that four sides are shiny, namely the frame effect in the industry. If the metal pigment is settled in the curing process, the metal effect of the coating can be directly affected, the coating with the metal effect can be obtained only if the metal pigment floats on the surface of the coating, and the distribution of the metal pigment on the surface of the coating can be observed microscopically through a scanning electron microscope. The scanning patterns of the coating electron microscope of example 1, comparative example 1 and comparative example 2 correspond to those shown in fig. 1, fig. 2 and fig. 3, respectively.
TABLE 4 Properties of Metal powder coating
| Appearance leveling | Uniformity of metal powder | Silver powder floating condition | Frame effect | |
| Example 1 | 5-6 | Uniformity of | Float upwards | Without any means for |
| Example 2 | 7-8 | Uniformity of | Float upwards | Without any means for |
| Example 3 | 4-5 | Uniformity of | Float upwards | Without any means for |
| Example 4 | 6-7 | Uniformity of | Float upwards | Without any means for |
| Example 5 | 6-7 | Uniformity of | Float upwards | Without any means for |
| Comparative example 1 | 6-7 | Uniformity of | Slightly sink down | Without any means for |
| Comparative example 2 | 6-7 | Hair waving | Obvious sinking | Obvious and obvious |
As can be seen from the comparison results of Table 4, when the polyester prepared by the formulation and the process of the invention is used for preparing metal powder coating, the metal pigment and the base powder are fully bonded together, the metal pigment and the base powder basically have no peeling phenomenon, and the coating has no bloom and frame effect. As can be seen from the observation of the distribution of the silver powder in the coating by a scanning electron microscope (figures 1-3), the silver powder in the coating prepared by the polyester provided by the invention floats upwards and is uniformly distributed on the surface of the coating, the silver powder in the coating of the comparative example 1 prepared by the formula provided by the invention and the conventional process only slightly sinks, and the silver powder in the coating of the comparative example 2 prepared by the conventional formula obviously sinks. In addition, the polyester of the invention can meet the preparation of metal powder coatings with different levels of level.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2022/126222 WO2024082179A1 (en) | 2022-10-19 | 2022-10-19 | Polyester resin for metal powder coating, preparation method therefor, and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN116096777A CN116096777A (en) | 2023-05-09 |
| CN116096777B true CN116096777B (en) | 2024-12-10 |
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| CN202280004573.4A Active CN116096777B (en) | 2022-10-19 | 2022-10-19 | A polyester resin for metal powder coating and its preparation method and application |
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| CN119119443B (en) * | 2024-11-16 | 2025-04-01 | 雅涂科技(张家港)有限公司 | A three-dimensional polyester resin synthesis process and its application |
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| CN104311806A (en) * | 2014-10-20 | 2015-01-28 | 浙江天松新材料股份有限公司 | Polyester resin for high-leveling transparent powder coating, and preparation method of polyester resin |
| CN106046336A (en) * | 2016-07-15 | 2016-10-26 | 广州擎天材料科技有限公司 | A kind of water-soluble polyester resin with hydroxy acid end cap and preparation method thereof |
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| US6710137B2 (en) * | 2001-02-06 | 2004-03-23 | Dainippon Ink And Chemicals, Inc. | Resin composition for powder coating, powder coating, and article coated therewith |
| US7071286B2 (en) * | 2003-12-02 | 2006-07-04 | E. I. Dupont De Nemours And Company | Coating compositions with high solids content for vehicle coating |
| JP4634131B2 (en) * | 2004-12-16 | 2011-02-16 | 関西ペイント株式会社 | Amino resin aqueous dispersion composition and thermosetting aqueous coating composition |
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| CN107254240B (en) * | 2017-04-20 | 2019-05-28 | 浙江传化天松新材料有限公司 | A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof |
| CN107540826A (en) * | 2017-07-31 | 2018-01-05 | 安徽优科新材料科技有限公司 | Novel high-grade bicycle use saturated polyester and preparation method thereof |
| WO2021022389A1 (en) * | 2019-08-02 | 2021-02-11 | 擎天材料科技有限公司 | Polyester resin composition, powder coating and workpiece |
| CN110408013A (en) * | 2019-08-30 | 2019-11-05 | 广东工业大学 | A kind of polyester resin for powder coating and preparation method thereof |
| CN112625224A (en) * | 2020-12-28 | 2021-04-09 | 常州市碳索新材料科技有限公司 | Polyester resin for heat dissipation powder coating and preparation method thereof |
| CN113999376B (en) * | 2021-11-24 | 2023-06-13 | 新中法高分子材料股份有限公司 | High Tg high impact resistance polyester resin for dual-curable powder coating and preparation method and application thereof |
| CN115124701B (en) * | 2022-08-10 | 2023-12-22 | 浙江超浪新材料有限公司 | Difunctional polyester resin, powder coating and application |
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| CN104311806A (en) * | 2014-10-20 | 2015-01-28 | 浙江天松新材料股份有限公司 | Polyester resin for high-leveling transparent powder coating, and preparation method of polyester resin |
| CN106046336A (en) * | 2016-07-15 | 2016-10-26 | 广州擎天材料科技有限公司 | A kind of water-soluble polyester resin with hydroxy acid end cap and preparation method thereof |
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