CN110343445B - Powder coating composition and preparation method and application thereof - Google Patents
Powder coating composition and preparation method and application thereof Download PDFInfo
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- CN110343445B CN110343445B CN201910647235.2A CN201910647235A CN110343445B CN 110343445 B CN110343445 B CN 110343445B CN 201910647235 A CN201910647235 A CN 201910647235A CN 110343445 B CN110343445 B CN 110343445B
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- 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
- C09D5/033—Powdery paints characterised by the additives
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The invention provides a powder coating composition and a preparation method and application thereof, wherein the preparation raw materials of the powder coating composition comprise the following components: 51-90 parts of epoxy resin, 40-60 parts of carboxyl-terminated polyester resin, 0.5-10 parts of hyperbranched polymer, 0.2-5 parts of low-surface-energy auxiliary agent and 0.1-10 parts of isocyanate curing agent. The powder coating composition is prepared by dispersing, mixing, extruding, tabletting and crushing the components. The powder coating composition provided by the invention realizes low-temperature rapid curing, is highly suitable for coating the surfaces of thermosensitive substrates such as wood, glass, paper and plastics, and the cured paint film has high hardness, good flexibility, high crosslinking density, excellent anti-graffiti property and excellent stain resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a powder coating composition, and a preparation method and application thereof.
Background
The powder coating is a solid powdery synthetic resin coating composed of resin, a curing agent, an inorganic filler, a pigment, an auxiliary agent and the like, and is different from a common solvent-based coating and a water-based coating, and a dispersion medium of the powder coating is not an organic solvent or water but air. The powder coating can form a film with 100 percent, has no solvent pollution, can not cause water pollution, is a real environment-friendly coating, has the characteristics of low energy consumption and recyclability, and is widely applied to the fields of building materials, home appliances, furniture, engineering machinery, electronics and electricity, industrial corrosion prevention and the like. With the continuous development of powder coatings, people also have new requirements on the performance of a coating film, the coating not only needs to realize the protection function of a base material in the aspects of mechanical performance and the like, but also needs to meet the requirements on the external ornamental effect, and particularly in the fields of buildings, public facilities and household appliances, the coating has the performances of stain resistance and doodling resistance after film forming, so that the base material can keep attractive appearance on one hand, the cleaning difficulty can be reduced on the other hand, and the cleaning cost can be saved. Therefore, the development of powder coatings with stain-resistant and anti-graffiti properties is of great significance.
CN103194140B discloses a self-cleaning super-weather-resistant powder coating and a preparation method thereof, wherein the powder coating comprises a carboxyl-terminated polyester particle system and a fluorocarbon resin particle system with a weight ratio of 4: 1-1: 4, the carboxyl-terminated polyester particle system and the fluorocarbon resin particle system respectively comprise corresponding matrix resin, a curing agent, an auxiliary agent and pigment filler, and the fluorocarbon resin particle system further comprises TiO2The nano particles endow the coating with good oxidation resistance. The powder coating can be cured at 200 ℃, the formed coating film has good base material adhesion, high aging resistance and high stability, and the fluorocarbon resin system enables the coating film to have excellent weather resistance and self-cleaning performance.
CN101712834A discloses an anti-doodling powder coating and a preparation method thereof, wherein the powder coating comprises 150-250 parts of acrylic resin, 30-40 parts of acrylic curing agent, 20-100 parts of titanium dioxide and 1-20 parts of auxiliary agent, wherein the acrylic resin is glycidyl acrylic resin, and the acrylic curing agent is saturated aliphatic diacid; the powder coating has the characteristics of simple formula, convenience in coating and curing, excellent chemical resistance, quick erasing and the like, and is suitable for coating white boards, public facilities and the like.
CN104231906A discloses an anti-doodling powder coating, which comprises matrix resin, a curing agent, pigment fillers and auxiliaries, wherein the matrix resin is a composition of low-hydroxyl polyester resin and high-hydroxyl polyester resin, and the curing agent is closed isocyanate; the powder coating has the advantages of low production cost, high leveling property, high surface hardness, pollution resistance and the like.
CN109354996A discloses a powder coating and its use, the components of the powder coating include polyurethane resin, cyanate ester, nano barium spar and BYK defoaming micronized wax; wherein the weight average molecular weight of the polyurethane resin is 3000-6000; the powder coating is cured at 200 ℃, and the formed paint film has graffiti resistance, easy cleaning and scratch resistance, and can maintain the surface effect of the coating for a long time.
However, in the prior art, most of the powder coatings with stain resistance and anti-graffiti performance take polyurethane, polyester or acrylic acid as matrix resin, and need to be cured into films at a high temperature of 200 ℃ by baking, and the severe curing conditions greatly limit the selection range of substrates. With the expansion of the application field of the powder coating to the fields of interior decoration, furniture and the like, the heat-sensitive base materials represented by wood and plastic cannot bear the high-temperature curing conditions of the powder coating in the prior art, and the mechanical property and the surface property of a paint film cannot be realized.
Based on the above, it is important to develop a low-temperature curable powder coating suitable for heat-sensitive substrates, which has anti-graffiti and anti-staining properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a powder coating composition and a preparation method and application thereof, wherein the powder coating composition adopts epoxy resin as matrix resin, matches carboxyl-terminated polyester resin and a curing agent to realize low-temperature rapid curing and high crosslinking density of a coating, and enables the coating to have anti-staining and anti-doodling performances through the synergistic cooperation of a highly branched polymer and a low surface energy auxiliary agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a powder coating composition prepared from raw materials comprising:
the powder coating composition provided by the invention takes the epoxy resin as the matrix resin, on one hand, because epoxy groups and side hydroxyl groups in epoxy resin molecules have reactivity and can be reacted and cured with various cross-linking agents, the curing temperature is low, and the epoxy resin can be completely cured at 140-160 ℃, so that the powder coating composition is highly suitable for coating on heat-sensitive substrates such as wood, paper, glass, RPVC, POM and the like; on the other hand, the epoxy resin can be connected with the functional resin or the auxiliary agent through chemical bonds, and a coating film formed by curing has mechanical properties, resistance and appearance effects. Carboxyl in carboxyl-terminated polyester resin molecules can be esterified and crosslinked with side hydroxyl in epoxy resin on one hand, and epoxy groups can be promoted to open rings and generate further crosslinking reaction on the other hand; more importantly, the carboxyl-terminated polyester resin contains a rigid chain mainly comprising a benzene ring, which is beneficial to improving the hardness and the impact property of a paint film, and the polyester resin has good fullness and glossiness after film forming, thereby effectively making up the defect of the appearance of the epoxy resin paint film. the-NCO functional group of the isocyanate curing agent can react with-OH in epoxy resin, carboxyl-terminated polyester resin, highly branched polymer and low surface energy auxiliary agent to form a compact and stable crosslinking network.
In order to obtain a coating film with stain resistance and anti-graffiti performance, the invention creatively combines a low surface energy auxiliary agent and a highly branched polymer, wherein the special cluster structure of the highly branched polymer can promote the fluidity of the powder coating composition in a molten state and is beneficial to obtaining the coating film surface with good leveling property; the hyperbranched molecular structure of the highly branched polymer can be combined with the low surface energy auxiliary agent, so that the low surface energy auxiliary agent can effectively float to the surface of the coating film under the drive of the highly branched polymer, thereby reducing the surface energy of the coating film and realizing the anti-stain and anti-graffiti performances of the coating film; in addition, the hyperbranched polymer drives the low-surface-energy auxiliary agent to rise to the surface of the coating, so that the reduction of the effective concentration of the low-surface-energy auxiliary agent caused by the fact that the low-surface-energy auxiliary agent is solidified in the coating is avoided, and the consumption of the low-surface-energy auxiliary agent is reduced by reducing the loss of the low-surface-energy auxiliary agent. The dosage of the highly branched polymer is controlled within the range defined by the invention, if the addition amount is too low, the floating of the low-surface-energy auxiliary agent cannot be effectively promoted, and a low-surface-energy coating film cannot be obtained; if the amount of the additive is too high, the continuity of the coating film is deteriorated, and the mechanical properties of the coating film are impaired.
In the present invention, the epoxy resin may be used in an amount of 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, 63 parts by weight, 65 parts by weight, 67 parts by weight, 70 parts by weight, 72 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 85 parts by weight, 87 parts by weight, or 89 parts by weight, and specific points therebetween are not limited for the sake of brevity and brevity, the present invention is not exhaustive of the specific points included in the ranges.
The carboxyl-terminated polyester resin may be used in an amount of 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 53 parts by weight, 55 parts by weight, 57 parts by weight, or 59 parts by weight, and specific values therebetween, which are not exhaustive for the purpose of brevity and clarity, are not intended to be exhaustive.
The highly branched polymer may be used in an amount of 0.6, 0.8, 1, 3, 5, 7, or 9 parts by weight, with specific values therebetween, not being exhaustive of the specific values included in the ranges, limited to space and for the sake of brevity.
The low surface energy adjuvant may be used in an amount of 0.3 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.7 parts by weight, 2 parts by weight, 2.3 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 4 parts by weight, or 4.5 parts by weight, and specific points therebetween are not intended to limit the disclosure and for brevity, and the invention is not intended to be exhaustive of the specific points included in the range.
The isocyanate-based curing agent may be used in an amount of 0.3 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, or 9 parts by weight, and specific values therebetween, which are not exhaustive for the purpose of brevity and clarity, are not intended to limit the invention to the specific values included in the recited ranges.
Preferably, the epoxy resin comprises the following components:
40-60 parts by weight of bisphenol epoxy resin
10-20 parts by weight of novolac epoxy resin
1-10 parts of aliphatic epoxy resin.
Preferably, the bisphenol type epoxy resin is selected from any one of or a combination of at least two of bisphenol a type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, or tetrabrominated bisphenol a type epoxy resin.
Preferably, the novolac epoxy resin is a novolac epoxy resin.
The epoxy resin is a composition of a plurality of epoxy resins, wherein the functionality of the novolac epoxy resin is more than 2, and the novolac epoxy resin has more reactive sites, so that the crosslinking density of the powder coating composition is improved; the aliphatic epoxy resin is added to introduce alkyl flexible chain segments into the powder coating so as to improve the flexibility of the coating film. The three epoxy resins are combined in the weight parts defined by the invention to obtain a paint film with high crosslinking density and balanced hardness and flexibility; if the content of the novolac epoxy resin exceeds the range defined by the invention, the crosslinking density cannot be effectively improved if the content of the novolac epoxy resin is too low, and the paint film is likely to be hard and brittle if the content of the novolac epoxy resin is too high; too low a content of aliphatic epoxy resin affects the flexibility of the paint film, and too high a content results in insufficient hardness of the paint film.
The epoxy resin of the present invention may be any commercially available product, and therefore, the molecular weight and epoxy equivalent of the epoxy resin are not particularly limited. For example, bisphenol type epoxy resin (e.g., bisphenol A type epoxy resin) may be selected from Anhui Meijia E12(604) or Baoling CYD-014, phenolic epoxy resin may be selected from Ciba-Geigy, Switzerland CTAB Aradur7255 or Dow DER672U, and aliphatic epoxy resin may be selected from Dow DER732 or DER 736.
In the present invention, the bisphenol type epoxy resin may be used in an amount of 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 53 parts by weight, 55 parts by weight, 57 parts by weight or 59 parts by weight, and specific points therebetween, which are not exhaustive for the purpose of brevity and clarity.
The novolac epoxy resin may be used in an amount of 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, or 19 parts by weight, and specific values therebetween, which are not exhaustive for the purpose of brevity and clarity.
The aliphatic epoxy resin may be used in an amount of 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and specific values therebetween are not exhaustive for the purpose of brevity and clarity.
Preferably, the carboxyl-terminated polyester resin is a mixture of a high acid value polyester resin and a low acid value polyester resin.
Preferably, the mass ratio of the high acid value polyester resin to the low acid value polyester resin is 1 (4-9), such as 1:4.5, 1:5, 1:6, 1:7, 1:8 or 1: 8.5.
Preferably, the acid value of the high acid value polyester resin is 70-90 mg KOH/g, such as 72mg KOH/g, 74mg KOH/g, 75mg KOH/g, 77mg KOH/g, 80mg KOH/g, 82mg KOH/g, 84mg KOH/g, 85mg KOH/g, 87mg KOH/g, 89mg KOH/g, and the like.
Preferably, the acid value of the low acid value polyester resin is 10-40 mg KOH/g, such as 12mg KOH/g, 15mg KOH/g, 17mg KOH/g, 20mg KOH/g, 23mg KOH/g, 25mg KOH/g, 27mg KOH/g, 30mg KOH/g, 33mg KOH/g, 35mg KOH/g, 37mg KOH/g, 39mg KOH/g, and the like.
The carboxyl-terminated polyester resin is used as a curing agent to provide carboxyl for a crosslinking reaction with a matrix epoxy resin, and rigid chain segments such as benzene rings in the molecular structure of the carboxyl-terminated polyester resin endow the powder coating composition with glossiness, fullness and hardness after film forming. The carboxyl-terminated polyester resin is a combination of high-acid-value polyester resin and low-acid-value polyester resin, wherein a large number of carboxyl groups in the high-acid-value polyester resin are subjected to crosslinking reaction with epoxy groups in epoxy resin, more residual hydroxyl groups in the low-acid-value polyester resin are subjected to reaction with-NCO in an isocyanate curing agent, and the two crosslinking reactions are simultaneously performed, so that an interpenetrating compact three-dimensional network structure is formed after the powder coating composition is formed into a film, and a paint film is endowed with high crosslinking density, high hardness and anti-doodling performance. If the mass ratio of the high acid value polyester resin to the low acid value polyester resin is out of the range defined in the present invention, too little high acid value polyester resin will affect the crosslinking density with the epoxy resin, and too much high acid value polyester resin will affect the yellowing resistance and flexibility of the powder coating composition after film formation.
Preferably, the low surface energy additive is used in an amount of 0.2 to 3 parts by weight.
Preferably, the low surface energy adjuvant is a silicone adjuvant and/or a fluorine adjuvant.
Preferably, the organic silicon auxiliary agent is any one or a combination of at least two of organic silicon modified hydroxyl acrylate, hydroxyl silicone oil or organic silicon modified hydroxyl polyester resin.
Preferably, the fluorine assistant is fluorine modified hydroxyl acrylate.
Preferably, the highly branched polymer is a dendritic polymer or a hyperbranched polymer, further preferably a hyperbranched polymer.
Preferably, the hyperbranched polymer is a hydroxyl-terminated hyperbranched polyester.
Preferably, the hydroxyl-terminated hyperbranched polyester has a number average molecular weight of 500 to 3000g/mol, such as 550g/mol, 600g/mol, 800g/mol, 1000g/mol, 1200g/mol, 1500g/mol, 1800g/mol, 2000g/mol, 2300g/mol, 2500g/mol, 2700g/mol or 2900g/mol, and the like.
Preferably, the hydroxyl value of the hydroxyl-terminated hyperbranched polyester is 500-600 mg KOH/g, such as 505mg KOH/g, 510mg KOH/g, 520mg KOH/g, 540mg KOH/g, 550mg KOH/g, 570mg KOH/g, 580mg KOH/g, 590mg KOH/g, and the like.
Preferably, the hydroxyl-terminated hyperbranched polyester has a hydroxyl group number of moles of 4 to 25mol, such as 5mol, 7mol, 9mol, 10mol, 12mol, 15mol, 18mol, 20mol, 21mol, or 22 mol.
The hyperbranched polymer in the powder coating composition has a unique cluster structure, and a cavity is formed in the hyperbranched structure of the molecular structure, so that the hyperbranched structure can be combined with the low-surface-energy auxiliary agent and wraps the low-surface-energy auxiliary agent in the branched structure to form a composite structure. The highly branched polymer can promote the fluidity of a matrix in a molten state in a powder coating composition, simultaneously drives the low-surface-energy auxiliary agent to float to the surface of a paint film, and further reacts with the isocyanate curing agent for curing, so that the low surface energy of a surface coating is realized, and the coating has the characteristics of stain resistance and graffiti resistance.
Preferably, the isocyanate curing agent is an internally blocked polyisocyanate.
Preferably, the powder coating composition further comprises 0.1-2 parts by weight (e.g., 0.2 part by weight, 0.4 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight, or 1.9 parts by weight) of a nano filler.
Preferably, the nano filler is selected from any one or a combination of at least two of nano alumina, nano titanium dioxide, nano silica, nano magnesium oxide or nano zinc oxide.
Preferably, the particle size of the nanofiller is 30 to 200nm, such as 40nm, 60nm, 80nm, 100nm, 120nm, 140nm, 150nm, 170nm or 190nm, and more preferably 50 to 120 nm.
The nano filler can promote the infrared absorption rate of the powder coating composition in the curing process, and is favorable for realizing the quick low-temperature curing of a paint film.
Preferably, the powder coating composition further comprises 0.5-2 parts by weight (e.g., 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight, or 1.9 parts by weight) of a curing accelerator.
Preferably, the curing accelerator is selected from any one of imidazole, imidazole derivatives, tertiary amine salts, quaternary ammonium salts, tetraalkylammonium carboxylates or dibutyltin dilaurate, or a combination of at least two thereof.
Preferably, the powder coating composition further comprises 5 to 30 parts by weight (e.g., 7 parts by weight, 9 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 29 parts by weight, etc.) of a pigment and a filler.
Preferably, the pigment and/or filler is a pigment and/or filler.
Preferably, the pigment is selected from any one or a combination of at least two of titanium dioxide, iron oxide red, ultramarine, iron yellow, phthalocyanine blue or phthalocyanine green.
Preferably, the filler is selected from any one of barium sulfate, wax powder, silicon micropowder or mica powder or a combination of at least two of the above.
Preferably, the powder coating composition further comprises 0.2 to 1 part by weight (e.g., 0.3 part by weight, 0.5 part by weight, 0.7 part by weight, 0.8 part by weight, or 0.9 part by weight) of a leveling agent.
Preferably, the leveling agent is a polyacrylate leveling agent.
Preferably, the powder coating composition further comprises 0.1-0.5 parts by weight (e.g. 0.2 parts by weight, 0.3 parts by weight, or 0.4 parts by weight) of degassing agent.
Preferably, the degassing agent is benzoin.
Preferably, the powder coating composition further comprises 0.2-2 parts by weight (e.g., 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 1.3 parts by weight, 1.5 parts by weight, 1.7 parts by weight, or 1.9 parts by weight) of a wetting dispersant.
Preferably, the powder coating composition has a particle size of 20 to 80 μm, such as 22 μm, 25 μm, 28 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, or 79 μm.
Preferably, the raw materials for preparing the powder coating composition comprise the following components:
the carboxyl-terminated polyester resin is a mixture of high-acid-value polyester resin and low-acid-value polyester resin, and the mass ratio of the high-acid-value polyester resin to the low-acid-value polyester resin is 1 (4-9).
In another aspect, the present invention provides a process for the preparation of a powder coating composition as described above, comprising the steps of:
(1) mixing and dispersing a highly branched polymer and a low surface energy auxiliary agent to obtain a mixture;
(2) mixing and extruding the mixture obtained in the step (1) with epoxy resin, carboxyl-terminated polyester resin and isocyanate curing agent to obtain a prefabricated material;
(3) and (3) tabletting the prefabricated material obtained in the step (2) and crushing to obtain the powder coating composition.
Preferably, the dispersing in step (1) is performed by a high-speed disperser.
Preferably, the dispersing speed of the high-speed disperser is 500-2000 revolutions, such as 600 revolutions, 800 revolutions, 1000 revolutions, 1200 revolutions, 1400 revolutions, 1500 revolutions, 1700 revolutions, 1900 revolutions, or the like.
Preferably, the dispersing time in the step (1) is 2-10 min, such as 3min, 4min, 5min, 6min, 7min, 8min or 9 min.
Preferably, the extruding of step (2) is performed by an extruder.
Preferably, the temperature of the extrusion in step (2) is 80-110 ℃, such as 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃, 108 ℃ or 110 ℃, etc.
Preferably, the pulverization in step (3) is to a particle size of 20 to 80 μm, for example, 22 μm, 25 μm, 28 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm or 79 μm.
Preferably, the preparation method specifically comprises the following steps:
(1) mixing the hyperbranched polymer and the low-surface-energy auxiliary agent, and dispersing for 2-10 min at the speed of 500-2000 revolutions by using a high-speed dispersion machine to obtain a mixture;
(2) mixing and crushing the mixture obtained in the step (1) with epoxy resin, carboxyl-terminated polyester resin, an isocyanate curing agent, a nano filler, a curing accelerator, a pigment filler, a leveling agent, a degassing agent and a wetting dispersant, and extruding the mixture by using an extruder at the temperature of 80-110 ℃ to obtain a prefabricated material;
(3) and (3) tabletting the prefabricated material obtained in the step (2), cooling, crushing to obtain particles with the particle size of 20-80 mu m, and screening to obtain the powder coating composition.
When the powder coating composition is prepared, the low-surface-energy auxiliary agent and the highly branched polymer are fully mixed and uniformly dispersed, and then the mixture is blended with other components, crushed and extruded; the preparation sequence is to combine the low surface energy auxiliary agent and the highly branched polymer firstly, and the highly branched polymer can promote the low surface energy auxiliary agent to float to the surface of a coating film more efficiently during film formation.
In another aspect, the present invention provides a heat-sensitive substrate coating comprising a heat-sensitive substrate and a coating film on the surface thereof, wherein the powder coating composition is used as a raw material of the coating film.
In another aspect, the present invention provides a method for preparing a heat-sensitive substrate coating as described above, comprising the steps of:
and coating the powder coating composition on a heat-sensitive substrate by adopting a high-voltage electrostatic method or a fluidized bed method, and curing by a medium-wave infrared furnace to obtain the heat-sensitive substrate coating.
Preferably, the curing power is 5-30 kW/m2For example 6kW/m2、8kW/m2、10kW/m2、12kW/m2、14kW/m2、15kW/m2、17kW/m2、20kW/m2、23kW/m2、25kW/m2、27kW/m2Or 29kW/m2And the like.
Preferably, the curing time is 3-10 min, such as 4min, 5min, 6min, 7min, 8min or 9min, and more preferably 3-5 min.
Compared with the prior art, the invention has the following beneficial effects:
the powder coating composition provided by the invention can be rapidly cured to form a film at a low temperature by designing the components and mutually matching the components in a specific ratio, the curing degree of a cured paint film is more than 98%, the solvent-resistant wiping frequency is more than 200 times, the contact angle with water is not less than 100 degrees, the anti-doodling performance is level 1, and the anti-sticking property is less than 0.1N/mm. The powder coating composition is highly suitable for coating the surfaces of thermosensitive substrates such as wood, glass, paper, plastics and the like, and a cured paint film has high hardness, good flexibility, high crosslinking density, excellent scrawling resistance and excellent stain resistance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Examples 1 to 8
A powder coating composition was prepared from the raw materials shown in Table 1, the units of the components being "parts by weight".
TABLE 1
Wherein, the bisphenol A type epoxy resin is E12(604) with Anhui Meijia, and the epoxy equivalent is 830; the epoxy equivalent weight of the novolac epoxy resin is 225(Aralaite ECN 9669); the aliphatic epoxy resin is aliphatic glycidyl ether epoxy resin, and the epoxy equivalent is 330 (Dow DER 732); the acid value of the high acid value polyester resin was 70mg KOH/g (Crylcoat 1501); the acid value of the low acid value polyester resin was 35mg KOH/g (Crylcoat 04432); the number average molecular weight of the hydroxyl-terminated hyperbranched polyester is 1100g/mol, and the hydroxyl value is 580mg KOH/g (SeHBP H102); the low surface energy auxiliary agent is organosilicon modified hydroxyl acrylate (WE-9610D); the isocyanate curing agent is internally blocked polyisocyanate (VESTAGON 1321); the average grain diameter of the nano-alumina is 80 nm; the flatting agent is acrylate flatting agent (Ningbo south sea chemical GLP 588); the degassing agent is benzoin; the wetting dispersant is GLP 701.
The preparation method comprises the following steps:
(1) mixing the highly branched polymer and the low surface energy auxiliary agent, and dispersing for 5min at the speed of 1000 revolutions by using a high-speed dispersion machine to obtain a mixture;
(2) mixing and crushing the mixture obtained in the step (1) and other components, and extruding the mixture at the temperature of 100 ℃ by using an extruder to obtain a prefabricated material;
(3) and (3) tabletting the prefabricated material obtained in the step (2), cooling, crushing to obtain particles with the particle size of 20-80 mu m, and screening to obtain the powder coating composition.
Example 9
This example differs from example 4 in that the low surface energy adjuvant is a fluorine modified hydroxy acrylate (warriol a 89).
Comparative example 1
This comparative example differs from example 4 in that no hydroxyl-terminated hyperbranched polyester is added.
Comparative example 2
The comparative example differs from example 4 in that no hydroxyl-terminated hyperbranched polyester is added and the amount of the low surface energy additive added is 10 parts by weight.
Comparative example 3
This comparative example is different from example 4 in that the high acid value polyester resin was not added and the low acid value polyester resin was added in an amount of 35 parts by weight.
Comparative example 4
This comparative example differs from example 4 in that no low surface energy adjuvant is added.
Comparative example 5
This comparative example differs from example 4 in that the amount of the hydroxyl-terminated hyperbranched polyester added was 11 parts by weight.
Comparative example 6
This comparative example differs from example 4 in that the hydroxyl-terminated hyperbranched polyester is added in an amount of 0.3 part by weight.
Application example
A coating of powder paint is prepared by the following steps:
the powder coating compositions provided in examples 1 to 9 and comparative examples 1 to 6 were applied to a surface-cleaned substrate by a high-voltage electrostatic method, and then placed in a medium-wave infrared oven (TRIAB, Sweden) with a curing power of 10kW/m2Curing, the mixtureAfter 4min, the coating was removed to give an average dry film thickness of 80 μm.
The base materials are selected according to different test items, heat-sensitive base materials such as wood, glass and the like can be used for evaluating the appearance performance (leveling property and glossiness) of the paint film, and the base materials are selected according to corresponding test standards for evaluating the mechanical properties such as solvent wiping resistance, adhesive force, hardness and the like of the paint film.
And (3) testing the performance of the paint film:
(1) coating surface temperature: monitoring the surface temperature of the coating in the curing process in real time by using a thermal infrared imager, wherein the higher the temperature is, the higher the infrared absorption rate of the powder coating is;
(2) coating curing degree: the degree of cure of the coating is a and the total heat released when the uncured powder coating is fully cured is Δ H0(J/g), the remaining heat of reaction at incomplete curing is Δ HR(J/g) wherein Δ H0(J/g)、ΔHR(J/g) were all obtained by DSC test, and the degree of cure a ═ (. DELTA.H)0-ΔHR)/ΔH0；
(3) Anti-graffiti property: testing according to the specification of JGT 304-2011 standard, and respectively testing the anti-graffiti performance of the paint film on ink, an oily marking pen and acrylic acid spray paint; grade 1 indicates that the cleaning agent can be removed by dry lint-free cotton cloth, grade 2 indicates that the cleaning agent can be removed by 1% neutral water-based weak cleaning agent, grade 3 indicates that the cleaning agent can be removed by orange-based cleaning agent, grade 4 indicates that the cleaning agent can be removed by absolute ethyl alcohol, and the 'unremovable' indicates that the four cleaning materials can not be removed or that the coating is discolored or damaged due to light loss after cleaning;
(4) contact angle: the contact angle of the surface of the paint film is tested by using a contact angle measuring instrument (KRUSS DSA100), and the contact angle of a water drop and the contact angle of an oil drop (olive oil) are respectively tested, wherein the larger the contact angle is, the better the anti-contamination property of the paint film is represented;
(5) hardness: testing the pencil hardness of the paint film according to the specification of GB/T6739-2006 standard;
(6) solvent resistance: testing is carried out according to an instrument wiping method specified by GB/T23989-2009 standard, wherein the wiping reagent is butanone;
(7) anti-sticking property: the 180-degree peel strength test is carried out according to the standard specification of GB/T2792-2004;
(8) flexibility: the test was performed according to the standard regulation of GB/T1731-1993;
(9) adhesion force: the paint films were tested for cross-hatch adhesion according to the standard GB/T9286-1998.
The powder coating compositions provided in examples 1 to 9 were tested for their properties after film formation according to the method described above, and the results are shown in table 2:
TABLE 2
The powder coating compositions provided in comparative examples 1 to 6 were tested for their properties after film formation according to the method described above, and the results are shown in table 3:
TABLE 3
As can be seen from the data in Table 2, the powder coating composition provided by the invention has high infrared absorption rate and high curing speed when being cured into a film, and the obtained paint film has higher hardness, flexibility, adhesion and solvent resistance, and excellent graffiti resistance and stain resistance. Compared with example 4, the single type of bisphenol A epoxy resin in example 7 and the single type of low acid value polyester resin in example 8 both reduce the crosslinking density of the paint film, thereby reducing the hardness, solvent resistance and flexibility of the paint film.
Comparing the data in tables 2 and 3, it can be seen that when the powder coating composition does not contain the hyperbranched polymer (comparative example 1), the curing degree, surface temperature, hardness, flexibility, adhesion, solvent resistance, anti-graffiti property and anti-stain property of the paint film are all significantly reduced, which indicates that the hyperbranched polymer not only promotes the low surface energy auxiliary agent to float up to the surface of the paint film and contributes to the reduction of the surface energy of the paint film, but also is used as one of the crosslinking components to react with the curing agent, so that the crosslinking density of the powder coating after film formation is increased, thereby contributing to the improvement of the hardness and the solvent resistance.
When the amount of the low surface energy aid is increased without the highly branched polymer in the powder coating composition (comparative example 2), the graffiti resistance and contact angle of the paint film are improved, but the solvent resistance and mechanical properties are still poor, which indicates that the graffiti resistance and stain resistance of the paint film of the present invention are the result of the synergistic combination of the highly branched polymer and the low surface energy aid, and a single increase in the amount of the low surface energy aid contributes to the reduction of the surface energy of the paint film, but has no significant benefit on the overall index of the paint film, such as resistance, mechanical properties, etc.
When the amount of the carboxyl-terminated polyester resin in the powder coating composition is lower than the range defined by the invention (comparative example 3), the curing degree, hardness, flexibility, adhesive force, solvent resistance, graffiti resistance and stain resistance of a paint film are all obviously reduced, which shows that a large number of crosslinking reaction sites provided by the carboxyl-terminated polyester resin are key factors for improving the crosslinking density of the paint film, and the too low content of the carboxyl-terminated polyester resin directly causes the reduction of the crosslinking density of the paint film, thereby affecting the mechanical property and solvent resistance of the paint film; the reduction in hardness further affects the graffiti and stain resistance of the paint film.
When the powder coating composition does not contain a low surface energy adjuvant (comparative example 4), the surface energy of the paint film is high and the graffiti resistance and stain resistance are poor.
When the amount of highly branched polymer in the powder coating composition is below the range defined in the present invention, too high an amount (comparative example 5) results in a hard and brittle paint film with poor flexibility; if the dosage is too low (comparative example 6), the functions of promoting the floating of the low-surface-energy assistant and increasing the crosslinking density are not obvious, and the mechanical property and the anti-graffiti and anti-fouling performance of a paint film cannot be effectively improved.
The applicant states that the present invention is illustrated by the above examples of the powder coating composition of the present invention and the method of preparation and use thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (46)
1. The anti-stain and anti-graffiti powder coating composition is characterized by being prepared from the following raw materials:
the highly branched polymer is hydroxyl-terminated hyperbranched polyester.
2. A powder coating composition as recited in claim 1, wherein the epoxy resin comprises the following ingredients:
40-60 parts by weight of bisphenol epoxy resin
10-20 parts by weight of novolac epoxy resin
1-10 parts of aliphatic epoxy resin.
3. A powder coating composition according to claim 2, wherein the bisphenol-type epoxy resin is selected from any one of or a combination of at least two of bisphenol a-type epoxy resin, bisphenol S-type epoxy resin, bisphenol F-type epoxy resin, hydrogenated bisphenol a-type epoxy resin, or tetrabrominated bisphenol a-type epoxy resin.
4. The powder coating composition of claim 2, wherein the novolac epoxy resin is a novolac epoxy resin.
5. A powder coating composition as recited in claim 1, wherein the carboxyl-terminated polyester resin is a mixture of a high acid number polyester resin and a low acid number polyester resin.
6. The powder coating composition of claim 5, wherein the mass ratio of the high acid value polyester resin to the low acid value polyester resin is 1 (4-9).
7. The powder coating composition of claim 5, wherein the high acid number polyester resin has an acid number of 70 to 90mg KOH/g.
8. The powder coating composition of claim 5, wherein the low acid number polyester resin has an acid number of 10 to 40mg KOH/g.
9. The powder coating composition of claim 1, wherein the low surface energy adjuvant is used in an amount of 0.2 to 3 parts by weight.
10. The powder coating composition of claim 1, wherein the low surface energy adjuvant is a silicone adjuvant and/or a fluorine adjuvant.
11. A powder coating composition as recited in claim 10, wherein the silicone adjuvant is any one of or a combination of at least two of silicone-modified hydroxy acrylate, hydroxy silicone oil, or silicone-modified hydroxy polyester resin.
12. A powder coating composition as recited in claim 10, wherein the fluorine coagent is a fluorine-modified hydroxy acrylate.
13. The powder coating composition of claim 1, wherein the hydroxyl-terminated hyperbranched polyester has a number average molecular weight of 500 to 3000 g/mol.
14. The powder coating composition of claim 1, wherein the hydroxyl terminated hyperbranched polyester has a hydroxyl number of 500 to 600mg KOH/g.
15. The powder coating composition of claim 1, wherein the hydroxyl-terminated hyperbranched polyester has a hydroxyl number of moles of 4 to 25 mol.
16. The powder coating composition of claim 1, wherein the isocyanate-based curing agent is an internally blocked polyisocyanate.
17. The powder coating composition of claim 1, further comprising 0.1 to 2 parts by weight of a nanofiller.
18. A powder coating composition as claimed in claim 17, wherein the nanofiller is selected from any one of or a combination of at least two of nano alumina, nano titania, nano silica, nano magnesia or nano zinc oxide.
19. The powder coating composition of claim 17, wherein the nanofiller has a particle size of 30 to 200 nm.
20. The powder coating composition of claim 19, wherein the nanofiller has a particle size of 50 to 120 nm.
21. The powder coating composition of claim 1, further comprising 0.5 to 2 parts by weight of a curing accelerator.
22. A powder coating composition as recited in claim 21, wherein the cure accelerator is selected from any one of, or a combination of at least two of, imidazole derivatives, tertiary amine salts, quaternary ammonium salts, tetraalkylammonium carboxylates, or dibutyltin dilaurate.
23. The powder coating composition of claim 1, wherein the raw materials for preparing the powder coating composition further comprise 5-30 parts by weight of pigment and filler.
24. A powder coating composition as recited in claim 23, wherein the pigment and filler are pigments and/or fillers.
25. A powder coating composition as claimed in claim 24, wherein the pigment is selected from any one or a combination of at least two of titanium dioxide, red iron oxide, ultramarine, iron yellow, phthalocyanine blue or phthalocyanine green.
26. A powder coating composition as claimed in claim 24, wherein the filler is selected from any one of barium sulphate, wax powder, silica fume or mica powder or a combination of at least two thereof.
27. The powder coating composition of claim 1, further comprising 0.2 to 1 part by weight of a leveling agent.
28. A powder coating composition as recited in claim 27, wherein the leveling agent is a polyacrylate leveling agent.
29. The powder coating composition of claim 1, further comprising 0.1 to 0.5 parts by weight of a degassing agent.
30. A powder coating composition as recited in claim 29, wherein the air release agent is benzoin.
31. The powder coating composition of claim 1, further comprising 0.2 to 2 parts by weight of a wetting dispersant.
32. The powder coating composition of claim 1, wherein the particle size of the powder coating composition is 20 to 80 μm.
33. A powder coating composition as claimed in any one of claims 1 to 32, wherein the powder coating composition is prepared from raw materials comprising:
the carboxyl-terminated polyester resin is a mixture of high-acid-value polyester resin and low-acid-value polyester resin, and the mass ratio of the high-acid-value polyester resin to the low-acid-value polyester resin is 1 (4-9); the highly branched polymer is hydroxyl-terminated hyperbranched polyester.
34. A process for preparing a powder coating composition as claimed in any one of claims 1 to 33, comprising the steps of:
(1) mixing and dispersing a highly branched polymer and a low surface energy auxiliary agent to obtain a mixture;
(2) mixing and extruding the mixture obtained in the step (1) with epoxy resin, carboxyl-terminated polyester resin and isocyanate curing agent to obtain a prefabricated material;
(3) and (3) tabletting the prefabricated material obtained in the step (2) and crushing to obtain the powder coating composition.
35. The method according to claim 34, wherein the dispersion in the step (1) is carried out by a high-speed disperser.
36. The method according to claim 35, wherein the dispersing speed of the high-speed disperser is 500 to 2000 revolutions.
37. The method according to claim 34, wherein the dispersing time in step (1) is 2-10 min.
38. The method of claim 34, wherein the extruding of step (2) is performed by an extruder.
39. The method according to claim 34, wherein the temperature of the extrusion in the step (2) is 80 to 110 ℃.
40. The method according to claim 34, wherein the pulverization in the step (3) is carried out to a particle size of 20 to 80 μm.
41. The preparation method according to any one of claims 34 to 40, comprising the following steps:
(1) mixing the hyperbranched polymer and the low-surface-energy auxiliary agent, and dispersing for 2-10 min at the speed of 500-2000 revolutions by using a high-speed dispersion machine to obtain a mixture;
(2) mixing and crushing the mixture obtained in the step (1) with epoxy resin, carboxyl-terminated polyester resin, an isocyanate curing agent, a nano filler, a curing accelerator, a pigment filler, a leveling agent, a degassing agent and a wetting dispersant, and extruding the mixture by using an extruder at the temperature of 80-110 ℃ to obtain a prefabricated material;
(3) and (3) tabletting the prefabricated material obtained in the step (2), cooling, crushing to obtain particles with the particle size of 20-80 mu m, and screening to obtain the powder coating composition.
42. A heat-sensitive substrate coating comprising a heat-sensitive substrate and a coating film on the surface thereof, wherein the powder coating composition according to any one of claims 1 to 33 is used as a raw material for the coating film.
43. A method of preparing a heat-sensitive substrate coating according to claim 42, comprising the steps of:
and coating the powder coating composition on a heat-sensitive substrate by adopting a high-voltage electrostatic method or a fluidized bed method, and curing by a medium-wave infrared furnace to obtain the heat-sensitive substrate coating.
44. The preparation method of claim 43, wherein the curing power is 5-30 kW/m2。
45. The method according to claim 43, wherein the curing time is 3 to 10 min.
46. The method of claim 43, wherein the curing time is 3-5 min.
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| CN110964409A (en) * | 2019-11-28 | 2020-04-07 | 老虎表面技术新材料（清远）有限公司 | Low-temperature curing bamboo board powder coating and bamboo board coating applied by same |
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| CN114806377A (en) * | 2021-02-01 | 2022-07-29 | 天津盛达新材料有限公司 | Self-cleaning powder coating and preparation method and application thereof |
| CN113789105B (en) * | 2021-09-16 | 2022-06-14 | 安徽华辉塑业科技股份有限公司 | Antistatic coating for wooden furniture and preparation method thereof |
| CN113881315A (en) * | 2021-10-28 | 2022-01-04 | 江苏卓奇新材料科技有限公司 | Hyperbranched modified epoxy powder coating and preparation method thereof |
| CN114058250A (en) * | 2021-11-23 | 2022-02-18 | 擎天材料科技有限公司 | Coiled material powder coating and preparation method and application thereof |
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| CN114574078B (en) * | 2022-03-09 | 2023-06-06 | 黄山佳杰新材料科技有限公司 | High-temperature-resistant and anti-doodling polyester powder coating composition and application thereof |
| CN114621451B (en) * | 2022-03-31 | 2023-05-23 | 兰州金睿合新材料科技有限责任公司 | Pure polyester resin modified epoxy resin and preparation method and application thereof |
| CN115340668B (en) * | 2022-09-23 | 2024-03-26 | 黄山嘉恒科技有限公司 | Wear-resistant and high-temperature-resistant polyester resin for powder coating and preparation method thereof |
| CN115948105A (en) * | 2022-12-28 | 2023-04-11 | 广东西敦千江粉漆科学研究有限公司 | Anti-doodling powder coating composition and preparation method thereof |
| CN116769383B (en) * | 2023-08-21 | 2024-02-13 | 宁德时代新能源科技股份有限公司 | Epoxy resin powder coating material, battery case, secondary battery, and electric device |
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| CN104231906A (en) * | 2013-06-24 | 2014-12-24 | 江苏长松科技发展有限公司 | Anti-graffiti powder coating |
| CN105440880B (en) * | 2014-08-26 | 2017-12-08 | 宁波大达化学有限公司 | A kind of marine steel pile tube protection epoxy coating and preparation method thereof |
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