CN110317527B

CN110317527B - Powder coating and preparation method thereof

Info

Publication number: CN110317527B
Application number: CN201910697057.4A
Authority: CN
Inventors: 陈运法; 王好盛; 张婧坤; 薛杨; 张冬海
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2019-07-30
Filing date: 2019-07-30
Publication date: 2020-12-04
Anticipated expiration: 2039-07-30
Also published as: CN110317527A

Abstract

The invention provides a powder coating and a preparation method thereof. The powder coating comprises the following components in parts by weight: 40-60 parts of matrix resin, 3-60 parts of multi-component curing agent, 10-30 parts of filler, 0.5-2 parts of curing accelerator, 1-20 parts of thermosetting fluorocarbon resin, 0.1-10 parts of thermosetting fluorocarbon resin curing agent and 0.01-0.5 part of auxiliary agent; the matrix resin is carboxyl polyester resin, hydroxyl polyester resin, epoxy resin, hydroxyl acrylate resin or epoxy acrylate resin; the multi-component curing agent comprises at least two curing components having different curing rates or compatibilities with the matrix resin. The coating formed by the powder coating provided by the invention has a smooth surface, does not have pinhole shrinkage cavities, has high adhesive force and high water and oil repellency, and has good anti-doodling and anti-sticking effects.

Description

Powder coating and preparation method thereof

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a powder coating and a preparation method thereof.

Background

The powder coating is a novel solid powder coating without solvent, consists of resin, a curing agent, a filler, a pigment, an auxiliary agent and the like, has the characteristics of no solvent, no pollution, environmental protection, energy conservation and the like, and can realize the functional application of the powder coating by adding a functional monomer or the filler.

In outdoor building materials, public facilities and other occasions, the coating surface not only needs certain weather resistance, but also needs certain hydrophobic and oleophobic and self-cleaning performances. The field generally adopts a coating surface micro-nano structure or adds a low surface energy substance to realize the hydrophobic and oleophobic and easy-to-clean effects of the coating. But it is certainly a simpler and more convenient method to add low surface energy substances. The fluorine/silicon anti-doodling auxiliary agent is usually used for reducing the surface tension of a coating, and floats on the surface of the coating under the promotion of surface energy in the drying and curing process of the coating, so that the hydrophobic and oleophobic and easy-to-clean anti-doodling effects of the coating are realized. However, the powder coating is an all-solid component, and compared with a liquid coating, the fluorine/silicon anti-graffiti auxiliary agent in the powder coating is more difficult to float on the surface of a coating and cannot achieve the due effect. In addition, the fluorine/silicon anti-doodling auxiliary agent has too large surface tension difference with the common high molecular resin of the powder coating, so the shrinkage cavity phenomenon is easy to generate.

CN 101712834a discloses a washing-resistant and anti-doodling powder coating using acrylic polyester resin as a matrix, CN 101220243a discloses an anti-doodling powder coating using hydroxyl resin as a matrix, and CN104231906A discloses an anti-doodling powder coating using mixed hydroxyl resin as a matrix. However, the above documents show wash-resistant anti-graffiti, anti-graffiti effect and weather resistance of the coating only by the matrix resin.

Therefore, a powder coating with good anti-sticking effect is to be developed to meet the coating requirements of indoor and outdoor building materials, public facilities and other occasions.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a powder coating and a preparation method thereof. Compared with the powder coating directly added with the anti-doodling auxiliary agent, the powder coating provided by the invention has the advantages that the surface of the coating is smooth, no pinhole shrinkage cavity is formed, and the effects of hydrophobicity, oleophobicity, anti-doodling and anti-sticking are better.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a powder coating, which comprises the following components in parts by weight:

40-60 parts of matrix resin, 3-60 parts of multi-component curing agent, 10-30 parts of filler, 0.5-2 parts of curing accelerator, 1-20 parts of thermosetting fluorocarbon resin, 0.1-10 parts of thermosetting fluorocarbon resin curing agent and 0.01-0.5 part of anti-doodling auxiliary agent;

the matrix resin is carboxyl polyester resin, hydroxyl polyester resin, epoxy resin, hydroxyl acrylate resin or epoxy acrylate resin;

the multi-component curing agent comprises at least two curing components having different curing rates or compatibilities with the matrix resin.

The matrix resin is cured by the multi-component curing agent, and the multi-component curing agent has different curing rates or compatibility with the matrix resin, so that the matrix resin can form a heterogeneous structure in the reaction process. The thermosetting fluorocarbon resin can float up to the surface of the coating more easily in a heterogeneous matrix structure to form a double-layer coating structure, the matrix resin provides adhesive force and basic mechanical property, and the fluorocarbon resin provides good chemical resistance and weather resistance; and the surface tension of the fluorocarbon resin is similar to that of the anti-doodling auxiliary agent, so that the anti-doodling auxiliary agent can be driven to float on the surface of the coating more easily, the hydrophobicity and lipophobicity of the coating are improved, and the anti-doodling and anti-sticking effects of the coating are achieved.

In the present invention, the base resin may be 40 to 60 parts by weight, for example, 40 parts, 42 parts, 43 parts, 45 parts, 46 parts, 48 parts, 50 parts, 52 parts, 53 parts, 55 parts, 56 parts, 58 parts, 60 parts, or the like.

The multi-component curing agent is 3 to 60 parts by weight, for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 13 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 43 parts, 45 parts, 46 parts, 48 parts, 50 parts, 52 parts, 53 parts, 55 parts, 56 parts, 58 parts or 60 parts, etc.

The filler is 10-30 parts by weight, for example, 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 23 parts, 25 parts, 26 parts, 28 parts or 30 parts.

The curing accelerator is used in an amount of 0.5 to 2 parts by weight, and may be, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 parts, 1.3 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, or the like.

The thermosetting fluorocarbon resin is 1-20 parts by weight, and may be, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like.

The thermosetting fluorocarbon resin curing agent is 0.1-10 parts by weight, and may be, for example, 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or the like.

The anti-doodling auxiliary agent is 0.01-0.5 part by weight, for example, 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.06 part, 0.08 part, 0.1 part, 0.12 part, 0.15 part, 0.18 part, 0.2 part, 0.22 part, 0.25 part, 0.28 part, 0.3 part, 0.32 part, 0.35 part, 0.38 part, 0.4 part, 0.42 part, 0.45 part, 0.48 part or 0.5 part.

In the invention, the thermosetting fluorocarbon resin curing agent is used for curing the thermosetting fluorocarbon resin, and the dosage of the thermosetting fluorocarbon resin curing agent can be adjusted according to the dosage of the thermosetting fluorocarbon resin. Preferably, the thermosetting fluorocarbon resin is 10-20 parts by weight, and the thermosetting fluorocarbon resin curing agent is 3-5 parts by weight.

In one embodiment of the present invention, the base resin is a carboxyl polyester resin, the multi-component curing agent is a compound of triglycidyl isocyanurate (TGIC) and hydroxyalkylamide, and the multi-component curing agent is present in an amount of 3 to 6 parts by weight (e.g., 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 parts, 5.5 parts, 5.8 parts, or 6 parts, etc.).

Preferably, the multi-component curing agent consists of triglycidyl isocyanurate and hydroxyalkyl amide in a mass ratio of 1:1.5 to 1.5:1 (e.g., 1:1.5, 1:1.4, 1:1.3, 1:1.2, 1:1.1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1, etc.).

In an embodiment of the present invention, the base resin is a carboxyl polyester resin, the multi-component curing agent is a compound of an epoxy resin and an epoxy acrylate resin, and the weight part of the multi-component curing agent is 35 to 60 parts (for example, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, etc.).

Preferably, the multi-component curing agent consists of an epoxy resin and an epoxy acrylate resin in a mass ratio of 1:1.5 to 1.5:1 (e.g., 1:1.5, 1:1.4, 1:1.3, 1:1.2, 1:1.1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, or 1.5:1, etc.).

In an embodiment of the present invention, the base resin is a hydroxy polyester resin or a hydroxy acrylate resin, the multi-component curing agent is a compound of a blocked polyisocyanate and an amino resin, and the weight part of the multi-component curing agent is 8 to 15 parts (for example, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, etc.).

Preferably, the multi-component curing agent is prepared from the blocked polyisocyanate and the amino resin in a mass ratio of 1-2:1 (e.g., 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, etc.).

As a preferred technical solution of the present invention, the matrix resin is an epoxy resin, the multi-component curing agent is a complex of a carboxyl polyester resin and a carboxyl acrylate resin, and the weight part of the multi-component curing agent is 40 to 60 parts (for example, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts or 60 parts, etc.).

Preferably, the multi-component curing agent consists of a carboxyl polyester resin and a carboxyl acrylate resin in a mass ratio of 1:1.5-1.5:1 (e.g., 1:1.5, 1:1.4, 1:1.3, 1:1.2, 1:1.1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc.).

In an embodiment of the present invention, the base resin is an epoxy acrylate resin, the multi-component curing agent is a compound of dodecanedioic acid and a phenol novolac resin, and the weight part of the multi-component curing agent is 6 to 12 parts (for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, or 12 parts, etc.).

Preferably, the multi-component curing agent consists of dodecanedioic acid and the novolac resin in a mass ratio of 1:2-3 (e.g., 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, or 1:3, etc.).

In the present invention, the components and the amounts of the multi-component curing agent are different depending on the type of the base resin. Wherein, when the matrix resin is epoxy resin, the matrix resin is not suitable for outdoor use and can be used for indoor coating due to poor weather resistance; when the matrix resin is other resin except epoxy resin, the obtained powder coating has good weather resistance and can be used for coating outdoor facilities.

As a preferred technical scheme of the invention, the filler is selected from one or a combination of at least two of titanium dioxide, barium sulfate, silica powder or mica powder.

The filler can regulate the viscosity of the powder coating and reduce the shrinkage rate of the powder coating. Wherein, titanium dioxide is also a white pigment, and when the filler is titanium dioxide, the white pigment does not need to be added in the powder coating.

Preferably, the particle size of the filler is 0.5-10 μm; for example, it may be 0.5. mu.m, 0.6. mu.m, 0.7. mu.m, 0.8. mu.m, 0.9. mu.m, 1. mu.m, 2. mu.m, 3. mu.m, 4. mu.m, 5. mu.m, 6. mu.m, 7. mu.m, 8. mu.m, 9. mu.m, or 10 μm.

Preferably, the curing accelerator is selected from one or a combination of at least two of imidazole, imidazole derivatives, tertiary amines or quaternary ammonium salts.

As a preferred embodiment of the present invention, the thermosetting fluorocarbon resin is FEVE (trifluoroethylene-vinyl ether-vinyl ester copolymer).

Preferably, the hydroxyl value of the FEVE is 50-60mg KOH/g; for example, 50KOH/g, 51KOH/g, 52KOH/g, 53KOH/g, 54KOH/g, 55KOH/g, 56KOH/g, 57KOH/g, 58KOH/g, 59KOH/g, 60KOH/g, etc. may be used.

Preferably, the thermosetting fluorocarbon resin curing agent is blocked polyisocyanate.

Preferably, the anti-doodling auxiliary agent is perfluoropolyether modified acrylic resin.

Preferably, the hydroxyl value of the anti-doodling auxiliary agent is 30-50mg KOH/g; for example, 30KOH/g, 31KOH/g, 32KOH/g, 33KOH/g, 34KOH/g, 35KOH/g, 36KOH/g, 37KOH/g, 38KOH/g, 39KOH/g, 40KOH/g, 42KOH/g, 43KOH/g, 45KOH/g, 46KOH/g, 48KOH/g, or 50KOH/g, etc. may be used.

In a preferred embodiment of the present invention, the powder coating further comprises 0.2 to 1 part (for example, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1 part) of a leveling agent.

Preferably, the leveling agent is a polyacrylate leveling agent.

Preferably, the powder coating further comprises 0.1-0.5 parts (which may be, for example, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, or 0.5 parts, etc.) of a degassing agent.

Preferably, the degassing agent is benzoin.

Preferably, the powder coating further comprises 0.1-0.5 parts (which may be, for example, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, or 0.5 parts, etc.) nano-fumed alumina. The nano gas-phase alumina is an assistant for promoting powder flow, and is a commonly used assistant in powder coating.

Preferably, the powder coating also includes 0.5-2 parts (which may be, for example, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, or 2 parts, etc.) pigment.

The general pigment of the powder coating comprises iron oxide red, ultramarine, titanium pigment, iron yellow, phthalocyanine blue, phthalocyanine green and the like. The kind of the pigment is not particularly limited in the present invention, and those skilled in the art can select the pigment as desired.

In a second aspect, the present invention provides a preparation method of the above powder coating, the preparation method comprising: mixing the components, performing melt extrusion, tabletting and crushing to obtain the powder coating.

As a preferred technical scheme of the invention, the temperature of the melt extrusion is 80-110 ℃; for example, the temperature may be 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃, 108 ℃ or 110 ℃.

Preferably, the pulverization is to a particle size of 20 to 80 μm; for example, it may be 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm or 80 μm.

Preferably, the preparation method comprises the following steps:

(1) mixing thermosetting fluorocarbon resin, an anti-doodling auxiliary agent and a thermosetting fluorocarbon resin curing agent, adding the mixture into a double-screw extruder, carrying out melt extrusion at the temperature of 80-110 ℃, then tabletting, cooling, crushing to the particle size of 20-80 mu m, screening and screening by a 180-mesh screen to obtain a first mixed material;

(2) mixing the rest components, adding into a double-screw extruder, melt-extruding at 80-110 deg.C, tabletting, cooling, pulverizing to particle size of 20-80 μm, sieving, and sieving with 180 mesh net to obtain a second mixed material;

(3) and mixing the first mixed material and the second mixed material to obtain the powder coating.

The thermosetting fluorocarbon resin, the doodling prevention auxiliary agent and the solid fluorocarbon resin curing agent are independently blended and crushed, so that the thermosetting fluorocarbon resin and the doodling prevention auxiliary agent are fully and uniformly mixed, and the doodling prevention auxiliary agent is helped to float upwards along with the thermosetting fluorocarbon resin.

The powder coating provided by the invention can be coated and cured by a conventional method in the field, and exemplarily, the powder coating can be coated by a high-voltage electrostatic method or a fluidized bed method and then heated and cured at 140-200 ℃ for 5-30min, preferably at 160-180 ℃ for 10-20min to form a coating.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, the matrix resin is cured by adopting the multi-component curing agent, so that the matrix resin forms a heterogeneous structure in the reaction process, the thermosetting fluorocarbon resin can float up to the surface of the coating more easily, and the weather resistance of the coating is improved; and the surface tension of the fluorocarbon resin is similar to that of the anti-doodling auxiliary agent, so that the anti-doodling auxiliary agent can be driven to float to the surface of the coating, the utilization rate of the anti-doodling auxiliary agent is improved, and compared with the powder coating with the anti-doodling auxiliary agent directly added, the powder coating provided by the invention has the advantages that the surface of the coating formed by the powder coating is smooth, no pinhole shrinkage exists, the powder coating has high adhesive force, and the effects of hydrophobic and oleophobic, anti-doodling and anti-sticking are better.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples. 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.

The raw materials used in the examples of the invention are as follows:

carboxyl polyester resin: zhanxin CRYCOAT1501, acid number 70 mgKOH/g;

hydroxyl polyester resin: guangzhou product synergistic EL-1200, hydroxyl value 45mg KOH/g;

epoxy resin: ba ling petrochemical CYD-014, epoxy value 0.12;

epoxy acrylate resin: guangzhou product AG-500, epoxy equivalent 500 g/eq;

carboxyl acrylate resin: ESTron G154, acid number 160mg KOH/G;

hydroxy acrylate resin: mitsui chemistry, hydroxyl number 45 mgKOH/g;

amino resin: solid hexamethoxymethyl melamine, chemicals;

phenol novolac resin: daqing luo chemical Amanda 969;

β -hydroxyalkylamides: primid XL 552;

blocked polyisocyanates: degussa B1530;

FEVE: lumiflon LF710, Asahi glass company, with a hydroxyl number of 50mg KOH/g;

perfluoropolyether-modified acrylic resin: a39 of Beijing Hua Tong Rui Chi materials science and technology Co., Ltd, hydroxyl value 40mg KOH/g;

leveling agent: GLP588 by ningbo south sea chemical ltd.

Examples 1 to 6

Examples 1-6 each provide a powder coating, the specific preparation method being as follows:

(1) mixing thermosetting fluorocarbon resin FEVE, perfluoropolyether modified acrylic resin and enclosed polyisocyanate, adding into a double-screw extruder, performing melt extrusion at 100 ℃, tabletting, cooling, crushing to obtain particles with the particle size of 20-80 mu m, screening and screening by a 180-mesh screen to obtain a first mixed material;

(2) mixing carboxyl polyester resin, TGIC, beta-hydroxyalkylamide, titanium dioxide (average particle size of 800nm), a curing accelerator diphenyl imidazoline, a flatting agent, benzoin, nano fumed alumina and pigment, adding into a double-screw extruder, performing melt extrusion at 100 ℃, then performing tabletting, cooling, crushing to obtain particles with the particle size of 20-80 mu m, screening and screening by a 180-mesh screen to obtain a second mixed material;

Comparative example 1

The difference from example 4 is that the components are directly mixed without adding thermosetting fluorocarbon resin and blocked polyisocyanate, melt extruded, and then tableted, cooled, crushed, sieved and screened through a 180 mesh screen.

Comparative example 2

The difference from the example 4 is that no perfluoropolyether modified acrylic resin is added, and other components and the use amount are the same as those in the example 4.

Comparative example 3

The difference from example 4 is that TGIC is replaced by an equal amount of beta-hydroxyalkylamide and the other components and amounts are the same as in example 4.

Comparative example 4

The difference from example 4 is that the β -hydroxyalkylamide is replaced by an equal amount of TGIC and the other components and amounts are the same as in example 4.

Wherein, the kinds and the amounts (parts by weight) of the components in examples 1 to 6 and comparative examples 1 to 4 are shown in the following tables 1 and 2, respectively:

TABLE 1

TABLE 2

The powder coatings provided in examples 1-6 and comparative examples 1-4 were applied to a wood substrate by a high-voltage electrostatic method and cured by heating at 180 ℃ for 20min to form a coating layer. The coating is tested for graffiti resistance, adhesion and weatherability by the following test methods:

anti-graffiti property: testing according to the specification of JGT 304-2011 standard, and respectively testing the performances of the paint film on ink, an oily marker and acrylic acid 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;

wherein the ink meets QB/T2860-2007; the oily marker pen is red and meets QB/T2777-2006; acrylic acid spray painting, black, which conforms to BB/T0047-2007;

anti-sticking property: measuring the 180-degree peel strength of the 3M single-sided marking tape to the coating according to the standard regulation of GB/T2792-2004;

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;

adhesion force: according to the standard test paint film of GB/T9286-1998 for scratching the adhesive force of the hundred grids, a cutting knife is adopted to cut the surface of the coating to form a grid pattern, and the cutting edge of the coating is completely smooth to be 0 level; a little coating falls off at the intersection of the cuts, and the affected cross cutting area is 1 grade less than 5%; the coating falls off at the intersection of the cuts or along the edges of the cuts, and the level 2 is that the affected cross cutting area is more than 5 percent and less than 15 percent;

resistance to weathering (UVB) aging: the weathering resistance (gloss retention after 200h UV ageing, color difference) of the coatings was tested in accordance with ISO 4892-2013.

The results of the above tests are shown in tables 3 and 4 below, respectively:

TABLE 3

TABLE 4

As can be seen from the performance data in tables 3 and 4, the coating prepared from the powder coating provided by the invention has good anti-graffiti, anti-sticking, hydrophobic and oleophobic effects, and higher adhesion and weather resistance.

Compared with example 4, in examples 5 to 6, due to the excessively large difference between the addition amounts of TGIC and β -hydroxyalkylamide, the structure of the matrix resin is more uniform during the reaction process, which is not favorable for the thermosetting fluorocarbon resin to drive the anti-graffiti auxiliary agent to float, and thus the anti-graffiti effect and the weather resistance of the coating formed by the powder coating obtained in examples 5 to 6 are reduced to some extent.

Comparative example 1 does not add thermosetting fluorocarbon resin, is unfavorable for the floating of the anti-doodling auxiliary agent, so the anti-doodling effect and the weather resistance of the coating are poor. Comparative example 2 no anti-graffiti aid was added and the coating had little anti-graffiti effect. Compared with the prior art, only the curing agent with a single component is used in the comparative examples 3 and 4, the matrix resin cannot form a heterogeneous structure in the curing process, and the thermosetting fluorocarbon resin is not favorable for driving the anti-doodling auxiliary agent to float upwards, so that the anti-doodling effect and the weather resistance of the coating are poor.

Examples 7 to 9

Examples 7-9 each provide a powder coating, the specific preparation of which is as follows:

(2) mixing carboxyl polyester resin, epoxy acrylate resin, titanium dioxide (average particle size of 800nm), a curing accelerator diphenyl imidazoline, a flatting agent, benzoin, nano fumed alumina and pigment, adding into a double-screw extruder, carrying out melt extrusion at 100 ℃, then tabletting, cooling, crushing to obtain particles with the particle size of 20-80 mu m, screening and passing through a 180-mesh screen to obtain a second mixed material;

Comparative example 5

The difference from example 7 is that the components are mixed directly without adding thermosetting fluorocarbon resin and blocked polyisocyanate, melt extruded, then tableted, cooled, crushed, sieved and screened through a 180 mesh screen.

Comparative example 6

The difference from example 7 is that the epoxy resin is replaced with an equal amount of epoxy acrylate resin, and the other components and amounts are the same as in example 7.

Comparative example 7

The difference from example 7 is that the epoxy acrylate resin was replaced with the same amount of epoxy resin, and the other components and amounts were the same as in example 7.

Wherein, the kinds and amounts (parts by weight) of each component in examples 7 to 9 and comparative examples 5 to 7 are shown in the following table 5:

TABLE 5

The powder coatings provided in examples 7 to 9 and comparative examples 5 to 7 were applied to a wood substrate by a high-voltage electrostatic method and cured by heating at 160 ℃ for 15min to form a coating layer. The coating was tested for adhesion and the results are shown in table 6 below:

TABLE 6

As can be seen from the performance data in Table 6, the coating prepared from the powder coating provided by the invention has good anti-graffiti, anti-sticking, hydrophobic and oleophobic effects and high adhesion. Comparative example 5 no thermosetting fluorocarbon resin was added, which is not conducive to the floating of the anti-graffiti auxiliary agent; comparative examples 6-7 only used the curing agent of single component, and matrix resin can't form heterogeneous structure in the course of curing, is unfavorable for thermosetting fluorocarbon resin to drive the anti-graffiti auxiliary agent come-up, therefore the anti-graffiti effect of coating is relatively poor.

Examples 10 to 12

Examples 10-12 each provide a powder coating, the specific preparation of which is as follows:

(1) mixing thermosetting fluorocarbon resin FEVE, perfluoropolyether modified acrylic resin and blocked polyisocyanate A, adding into a double-screw extruder, performing melt extrusion at 100 ℃, then performing tabletting, cooling, crushing to obtain particles with the particle size of 20-80 mu m, screening and screening by a 180-mesh screen to obtain a first mixed material;

(2) mixing hydroxyl polyester resin, blocked polyisocyanate B, amino resin, barium sulfate (with the average particle size of 5 microns), curing accelerator diphenyl imidazoline, a flatting agent, benzoin, nano fumed alumina and pigment, adding the mixture into a double-screw extruder, carrying out melt extrusion at 100 ℃, then tabletting, cooling, crushing to obtain particles with the particle size of 20-80 microns, screening and passing through a 180-mesh screen to obtain a second mixed material;

It should be noted that the blocked polyisocyanate A and the blocked polyisocyanate B in examples 10 to 12 are actually the same blocked polyisocyanate, and they are given names by man for convenience of explanation of the components and preparation method of the powder coating.

Comparative example 8

The difference from example 10 is that the components are mixed directly without adding thermosetting fluorocarbon resin and blocked polyisocyanate, melt extruded, and then tableted, cooled, crushed, sieved and screened through a 180 mesh screen.

Comparative example 9

The difference from example 10 is that blocked polyisocyanate B was replaced with the same amount of amino resin and the other components and amounts were the same as in example 10.

Comparative example 10

The difference from example 10 is that the amino resin is replaced by the same amount of blocked polyisocyanate B and the other components and amounts are the same as in example 10.

The kinds and amounts (parts by weight) of the respective components in examples 10 to 12 and comparative examples 8 to 10 are shown in Table 7 below:

TABLE 7

The powder coatings provided in examples 10 to 12 and comparative examples 8 to 10 were applied to a wood substrate by a high-voltage electrostatic method and cured by heating at 160 ℃ for 10min to form a coating layer. The coatings were tested for graffiti resistance, adhesion, and weatherability and the results are shown in table 8 below:

TABLE 8

As can be seen from the performance data in Table 8, the coating prepared from the powder coating provided by the invention has good anti-graffiti, anti-sticking, hydrophobic and oleophobic effects, and high adhesion and weather resistance. Compared with the prior art, the method has the advantages that no thermosetting fluorocarbon resin is added, so that the doodling prevention auxiliary agent is not beneficial to floating; comparative examples 9 to 10 only use the curing agent of single component, matrix resin can't form heterogeneous structure in the course of curing, is unfavorable for thermosetting fluorocarbon resin to drive the floating of anti-graffiti auxiliary agent, therefore the anti-graffiti effect and weatherability of the coating are all relatively poor.

Examples 13 to 15

Examples 13-15 each provide a powder coating, the specific preparation of which is as follows:

(2) mixing hydroxyl acrylate resin, blocked polyisocyanate B, amino resin, barium sulfate (with the average particle size of 5 microns), curing accelerator diphenyl imidazoline, a flatting agent, benzoin, nano-fumed alumina and pigment, adding the mixture into a double-screw extruder, carrying out melt extrusion at 100 ℃, then tabletting, cooling, crushing to obtain particles with the particle size of 20-80 microns, screening and passing through a 180-mesh screen to obtain a second mixed material;

Comparative example 11

The difference from example 13 is that the components are mixed directly without adding thermosetting fluorocarbon resin and blocked polyisocyanate, melt extruded, then tableted, cooled, crushed, sieved and screened through a 180 mesh screen.

Comparative example 12

The difference from example 13 is that blocked polyisocyanate B was replaced with the same amount of amino resin and the other components and amounts were the same as in example 13.

Comparative example 13

The difference from example 13 is that the amino resin is replaced by the same amount of blocked polyisocyanate B and the other components and amounts are the same as in example 13.

The kinds and amounts (parts by weight) of the respective components in examples 13 to 15 and comparative examples 11 to 13 are shown in Table 9 below:

TABLE 9

The powder coatings provided in examples 13-15 and comparative examples 11-13 were applied to a wood substrate by a high-pressure electrostatic method and cured by heating at 160 ℃ for 10min to form a coating layer. The coatings were tested for graffiti resistance, adhesion, and weatherability and the results are shown in table 10 below:

watch 10

As can be seen from the performance data in Table 10, the coating prepared from the powder coating provided by the invention has good anti-graffiti, anti-sticking, hydrophobic and oleophobic effects, and high adhesion and weather resistance. Comparative example 11 no thermosetting fluorocarbon resin was added, which is not conducive to the floating of the anti-graffiti auxiliary; comparative examples 12 to 13 only use the curing agent of single component, the matrix resin can't form heterogeneous structure in the course of curing, is unfavorable for thermosetting fluorocarbon resin to drive the floating of the anti-graffiti auxiliary agent, therefore the anti-graffiti effect and weatherability of the coating are all relatively poor.

Examples 16 to 18

Examples 16-18 each provide a powder coating, the specific method of preparation being as follows:

(2) mixing epoxy resin, carboxyl polyester resin, carboxyl acrylate resin, barium sulfate (with the average particle size of 5 microns), a curing accelerator diphenyl imidazoline, a flatting agent, benzoin, nano gas-phase aluminum oxide and pigment, adding the mixture into a double-screw extruder, carrying out melt extrusion at 100 ℃, then tabletting, cooling, crushing to the particle size of 20-80 microns, screening and passing through a 180-mesh screen to obtain a second mixed material;

Comparative example 14

The difference from example 16 is that the components are mixed directly without adding thermosetting fluorocarbon resin and blocked polyisocyanate, melt extruded, then tableted, cooled, crushed, sieved and screened through a 180 mesh screen.

Comparative example 15

The difference from example 16 is that the carboxyl polyester resin was replaced with the same amount of carboxyl acrylate resin, and the other components and amounts were the same as in example 16.

Comparative example 16

The difference from example 16 is that the carboxyl acrylate resin was replaced with the same amount of carboxyl polyester resin, and the other components and amounts were the same as in example 16.

The kinds and amounts (parts by weight) of the respective components in examples 16 to 18 and comparative examples 14 to 16 are shown in Table 11 below:

TABLE 11

The powder coatings provided in examples 16-18 and comparative examples 14-16 were applied to a wood substrate by a high-pressure electrostatic method and cured by heating at 180 ℃ for 20min to form a coating layer. The coating was tested for graffiti resistance, adhesion and the results are shown in table 12 below:

TABLE 12

As can be seen from the performance data in Table 12, the coating prepared from the powder coating provided by the invention has good anti-graffiti, anti-sticking, hydrophobic and oleophobic effects, and high adhesion. Comparative example 14 no thermosetting fluorocarbon resin was added, which is not conducive to the floating of the anti-graffiti adjuvant; comparative examples 15 to 16 only use the curing agent of single component, matrix resin can't form heterogeneous structure in the course of curing, is unfavorable for thermosetting fluorocarbon resin to drive the floating of anti-graffiti auxiliary agent, therefore the anti-graffiti effect of the coating is relatively poor.

Examples 19 to 21

Examples 19-21 each provide a powder coating, the specific preparation of which is as follows:

(2) mixing epoxy acrylate resin, dodecanedioic acid, linear phenolic resin, barium sulfate (with the average particle size of 5 microns), a curing accelerator diphenyl imidazoline, a flatting agent, benzoin, nano fumed alumina and a pigment, adding the mixture into a double-screw extruder, carrying out melt extrusion at 100 ℃, then tabletting, cooling, crushing to the particle size of 20-80 microns, screening and screening through a 180-mesh screen to obtain a second mixed material;

Comparative example 17

The difference from example 19 is that the components are mixed directly without adding thermosetting fluorocarbon resin and blocked polyisocyanate, melt extruded, then tableted, cooled, crushed, sieved and screened through a 180 mesh screen.

Comparative example 18

The difference from example 19 is that dodecanedioic acid is replaced by a phenol novolac resin according to the ratio of dodecanedioic acid to phenol novolac resin in example 19, and the other components and the amounts are the same as in example 19.

Comparative example 19

The difference from example 19 is that the ratio of dodecanedioic acid to the phenol novolac resin in example 19 was changed to dodecanedioic acid, and the other components and amounts were the same as in example 19.

Wherein, the kinds and amounts (parts by weight) of the respective components in examples 19 to 21 and comparative examples 17 to 19 are shown in the following Table 13:

watch 13

The powder coatings provided in examples 19 to 21 and comparative examples 17 to 19 were applied to a wood substrate by a high-voltage electrostatic method and cured by heating at 180 ℃ for 20min to form a coating layer. The coatings were tested for graffiti resistance, adhesion, and weatherability and the results are shown in table 14 below:

TABLE 14

As can be seen from the performance data in Table 14, the coating prepared from the powder coating provided by the invention has good anti-graffiti, anti-sticking, hydrophobic and oleophobic effects, and high adhesion and weather resistance. Compared with the prior art, the method has the advantages that no thermosetting fluorocarbon resin is added, so that the doodling prevention auxiliary agent is not beneficial to floating; in the comparative examples 18 to 19, only the curing agent with a single component is used, the matrix resin cannot form a heterogeneous structure in the curing process, and the thermosetting fluorocarbon resin is not favorable for driving the anti-doodling auxiliary agent to float, so that the anti-doodling effect and the weather resistance of the coating are poor.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. The anti-doodling powder coating is characterized by comprising the following components in parts by weight:

40-60 parts of matrix resin, 3-60 parts of multi-component curing agent, 10-30 parts of filler, 0.5-2 parts of curing accelerator, 10-20 parts of thermosetting fluorocarbon resin, 3-5 parts of thermosetting fluorocarbon resin curing agent and 0.01-0.5 part of anti-doodling auxiliary agent;

2. The powder coating of claim 1, wherein the matrix resin is a carboxyl polyester resin, the multi-component curing agent is a compound of an epoxy resin and an epoxy acrylate resin, and the multi-component curing agent is 35 to 60 parts by weight.

3. The powder coating according to claim 2, wherein the multi-component curing agent consists of an epoxy resin and an epoxy acrylate resin in a mass ratio of 1:1.5 to 1.5: 1.

4. The powder coating of claim 1, wherein the matrix resin is a carboxyl polyester resin, the multi-component curing agent is a combination of triglycidyl isocyanurate and a hydroxyalkylamide, and the multi-component curing agent is present in an amount of 3 to 6 parts by weight.

5. The powder coating according to claim 4, wherein the multi-component curing agent consists of triglycidyl isocyanurate and hydroxyalkylamide in a mass ratio of 1:1.5 to 1.5: 1.

6. The powder coating of claim 1, wherein the matrix resin is a hydroxy polyester resin or a hydroxy acrylate resin, the multi-component curing agent is a compound of a blocked polyisocyanate and an amino resin, and the weight part of the multi-component curing agent is 8-15 parts.

7. The powder coating according to claim 6, wherein the multi-component curing agent is prepared from a blocked polyisocyanate and an amino resin in a mass ratio of 1-2: 1.

8. The powder coating of claim 1, wherein the matrix resin is an epoxy resin, the multi-component curing agent is a complex of a carboxyl polyester resin and a carboxyl acrylate resin, and the weight part of the multi-component curing agent is 40-60 parts.

9. The powder coating according to claim 8, wherein the multi-component curing agent consists of a carboxyl polyester resin and a carboxyl acrylate resin in a mass ratio of 1:1.5-1.5: 1.

10. The powder coating of claim 1, wherein the matrix resin is an epoxy acrylate resin, the multi-component curing agent is a complex of dodecanedioic acid and a novolac resin, and the multi-component curing agent is present in an amount of 6 to 12 parts by weight.

11. The powder coating of claim 10, wherein the multi-component curing agent consists of dodecanedioic acid and a novolac resin in a mass ratio of 1: 2-3.

12. The powder coating according to claim 1, wherein the filler is selected from one or a combination of at least two of titanium dioxide, barium sulfate, silica micropowder or mica powder.

13. The powder coating according to claim 1, wherein the filler has a particle size of 0.5-10 μm.

14. The powder coating according to claim 1, wherein the curing accelerator is selected from one or a combination of at least two of imidazole, imidazole derivatives, tertiary amines or quaternary ammonium salts.

15. The powder coating of claim 1, wherein the thermosetting fluorocarbon resin is a trifluoroethylene-vinyl ether-vinyl ester copolymer.

16. The powder coating of claim 1, wherein the thermosetting fluorocarbon resin curing agent is a blocked polyisocyanate.

17. The powder coating of claim 1, wherein the anti-graffiti aid is a perfluoropolyether-modified acrylic resin.

18. The powder coating according to claim 1, further comprising 0.2 to 1 part of a leveling agent.

19. The powder coating of claim 18, wherein the leveling agent is a polyacrylate leveling agent.

20. The powder coating of claim 1, further comprising 0.1-0.5 parts of a degassing agent.

21. The powder coating of claim 20, wherein the degassing agent is benzoin.

22. The powder coating of claim 1, further comprising 0.1-0.5 parts nano-fumed alumina.

23. The powder coating of claim 1, further comprising 0.5-2 parts pigment.

24. A process for preparing a powder coating according to any one of claims 1 to 23, wherein the process comprises: mixing the components, performing melt extrusion, tabletting and crushing to obtain the powder coating.

25. The method of claim 24, wherein the melt extrusion temperature is 80-110 ℃.

26. The method of claim 24, wherein the pulverization is carried out to a particle size of 20 to 80 μm.

27. The method of manufacturing of claim 24, comprising the steps of: