CN107151468B - Acrylic resin powder composition, coating and application - Google Patents
Acrylic resin powder composition, coating and application Download PDFInfo
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- CN107151468B CN107151468B CN201610122437.1A CN201610122437A CN107151468B CN 107151468 B CN107151468 B CN 107151468B CN 201610122437 A CN201610122437 A CN 201610122437A CN 107151468 B CN107151468 B CN 107151468B
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic compounds
- D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid
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Abstract
The present invention relates to an acrylic resin powder composition comprising: the curing agent comprises glycidyl acrylate resin, a curing agent, a leveling agent and a nano functional filler, wherein the mass of the nano functional filler is 0.1-1 part by mass based on 100 parts by mass of the glycidyl acrylate resin. The invention also provides an acrylic resin coating, which comprises a product obtained by melt extrusion, crushing, sieving, spraying and curing of the acrylic resin powder composition. The obtained acrylic resin coating has the characteristics of high hardness, high glossiness and high wear resistance, does not discharge volatile organic compounds, and is environment-friendly.
Description
Technical Field
The invention relates to an acrylic resin powder composition, in particular to a nano modified acrylic resin powder composition.
Background
The powder composition coating belongs to an environment-friendly material due to no Volatile Organic Compound (VOC) emission, and is rapidly developed along with the improvement of the living standard of people and the enhancement of environmental awareness. The wood as a natural renewable material is widely applied to furniture, woodware, tools, decoration materials and other aspects. Compared with metal base materials, wood contains more moisture and volatile matters, and is volatile at higher curing temperature, so that pinholes and other defects are formed on the surface of the coating, and the coating is damaged. One of the solutions is to make a coating with a grain structure such as sand grains or orange peel, and then to cure at a low temperature or reduce the curing time to avoid volatilization of water and other volatile matters in the wood, thereby solving the problem of surface pinholes. Some foreign people research the application of the powder composition coating on woodware, but the coating of the powder composition coating is difficult to achieve high gloss and high hardness.
Disclosure of Invention
In accordance with the deficiencies of the prior art, the present invention provides an acrylic resin powder composition with which coatings prepared can be applied to the coating of wood or paper surfaces. The coating has the characteristics of high hardness, high glossiness and high wear resistance, does not discharge volatile organic compounds, and is environment-friendly.
According to one aspect of the invention, the acrylic resin coating composition comprises glycidyl acrylate resin, a curing agent, a leveling agent and a nano functional filler, wherein the nano functional filler accounts for 0.1-1 part by mass based on 100 parts by mass of the glycidyl acrylate resin.
According to the invention, the glycidyl acrylate resin can be selected from glycidyl acrylate resin materials commonly used in the field, according to a specific embodiment of the invention, the glass transition temperature of the glycidyl acrylate resin is 20-70 ℃, the epoxy value of the glycidyl acrylate resin is 200-800, preferably 200-600, and the glycidyl acrylate resin is glycidyl methacrylate type acrylic resin, specifically a copolymer of at least one of glycidyl methacrylate, glycidyl methacrylate and methyl methacrylate, butyl acrylate, methyl acrylate and hydroxyethyl methacrylate.
According to another embodiment of the present invention, the curing agent is selected from at least one of polycarboxylic acids and/or anhydrides thereof, and the polycarboxylic acid may be selected from at least one of adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid.
According to an embodiment of the present invention, the curing agent is 20 to 40 parts by mass based on 100 parts by mass of the glycidyl acrylate resin.
According to another embodiment of the invention, the leveling agent is preferably polybutyl acrylate, and more preferably linear polybutyl acrylate having a molecular weight of 6000 to 8000.
According to an embodiment of the present invention, the leveling agent is 1 to 3 parts by mass based on 100 parts by mass of the glycidyl acrylate resin.
According to the invention, the hardness, the adhesive force and the impact strength of the coating can be improved by adding the nano functional filler. According to an embodiment of the present invention, the nano-functional filler is at least one selected from the group consisting of nano titanium dioxide, nano calcium carbonate, nano silica, nano alumina, nano zinc oxide and cage-like silsesquioxane, and from the viewpoint of further improving strength and gloss, it is preferable to use cage-like silsesquioxane and a composition comprising the same, and the nano-functional filler particles have an average particle diameter of 10 to 200 nm.
According to the invention, an excessive amount of the nano-functional filler can cause the reduction of compatibility and influence the glossiness of the coating. According to an embodiment of the present invention, the amount of the nano-functional filler is 0.1 to 1 part, preferably 0.1 to 0.5 part, and more preferably 0.2 to 0.5 part.
According to the invention, the powder composition also comprises a curing accelerator and/or benzoin, and the effects of the curing accelerator and the benzoin comprise further accelerating curing, generating synergistic action with a curing agent, improving the curing speed, reducing the curing reaction temperature, improving the curing degree and improving the hardness of a paint film. The benzoin can eliminate bubbles in the molten powder coating, eliminate the defects of film coating pinholes and the like, and improve the glossiness of a paint film. For example, the curing accelerator is at least one selected from the group consisting of quaternary ammonium salt curing accelerators, imidazole curing accelerators and tertiary amine curing accelerators.
According to another embodiment of the present invention, the quaternary ammonium salt-based curing accelerator is at least one selected from the group consisting of cetyltributylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium bromide and cetyltrimethylammonium bromide.
According to another embodiment of the present invention, the imidazole-based curing accelerator is at least one selected from the group consisting of imidazole, 2-methylimidazole, and 2-methyl-4-ethylimidazole.
According to another specific embodiment of the present invention, the tertiary amine-based curing accelerator is selected from at least one of N, N-dimethylcyclohexylamine and N, N-diethylcyclohexylamine.
According to another embodiment of the present invention, the curing accelerator is 0.1 to 2 parts by mass based on 100 parts by mass of the glycidyl acrylate resin.
According to another embodiment of the present invention, the benzoin is 0.5 to 2 parts by mass, preferably 0.5 to 1 part by mass, based on 100 parts by mass of the glycidyl acrylate resin.
According to another aspect of the present invention, there is also provided an acrylic resin coating layer, including: and (3) after the acrylic resin powder composition is subjected to melt extrusion, crushing and sieving, and finally spraying and curing to obtain a product.
According to the present invention, the melt-kneading extrusion can be carried out using equipment commonly used in the art, for example, an extruder, preferably with a melt temperature of 110 ℃, and the number of times of extrusion is based on the uniform mixing, preferably 4 times of extrusion.
According to the invention, said comminution screening can be carried out using methods or equipment customary to the person skilled in the art, for example comminution screening machines, preferably with a screen mesh size of 200 mesh.
According to the invention, the spray curing can be carried out using methods or equipment customary to the person skilled in the art, preferably using electrostatic spraying.
According to the present invention, the curing process is suitably a low temperature curing. According to an embodiment of the invention, the curing temperature is 140-160 ℃, and the curing time is 20-40 minutes.
The coating prepared from the powder composition has the advantages of simple preparation method, less used components, cost saving, lower curing temperature and shorter time, and the powder composition and the coating can be applied to the coating on the surface of wood or paper. The coating has the characteristics of high hardness, high glossiness and high wear resistance, does not discharge volatile organic compounds, and is environment-friendly.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but do not limit the present invention.
(1) Measuring the hardness by using a QHQ type coating pencil hardness tester;
(2) the gloss was measured using a gloss meter (model: AG-4446) manufactured by BYK Additives & Instruments, Germany.
Example 1
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid, 1 part of hexadecyltributylammonium chloride, 2 parts of polybutyl acrylate, 1 part of benzoin and 0.2 part of nano titanium oxide, then carrying out melt mixing extrusion on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 150 ℃ for 30 minutes to obtain the acrylic resin coating. The coating had a gloss of 94 ° at 60 ° and a hardness of 4H.
Example 2
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid, 1 part of 2-methylimidazole, 2 parts of polybutyl acrylate, 1 part of benzoin and 0.5 part of nano titanium oxide, then melting, mixing and extruding on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 150 ℃ for 30 minutes to obtain the acrylic resin coating. The coating had a gloss of 95 ° at 60 ° and a hardness of 5H.
Example 3
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid, 1 part of 2-methylimidazole, 2 parts of polybutyl acrylate, 1 part of benzoin and 0.2 part of cage-type silsesquioxane, then carrying out melt mixing extrusion on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 150 ℃ for 25 minutes to obtain the acrylic resin coating. The coating had a gloss of 98 ° at 60 ° and a hardness of 5H.
Example 4
Uniformly mixing 100 parts of glycidyl methacrylate, 35 parts of tetradecanedioic acid, 1.5 parts of 2-methylimidazole, 2 parts of polybutyl acrylate, 1 part of benzoin and 0.5 part of cage-type silsesquioxane, then melting, mixing and extruding on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 140 ℃ for 25 minutes to obtain the acrylic resin coating. The coating had a gloss of 96 ° at 60 ° and a hardness of 6H.
Example 5
100 parts of glycidyl methacrylate, 35 parts of tetradecanedioic acid, 1.5 parts of hexadecyltributylammonium chloride, 2 parts of polybutyl acrylate, 0.5 part of benzoin, and 0.5 part of cage-type silsesquioxane are uniformly mixed, then the mixture is melted, mixed and extruded on an extruder, the melting temperature is 110 ℃, the extrusion is repeated for 4 times, and then the mixture is cooled, tableted, crushed, ground and sieved to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 140 ℃ for 20 minutes to obtain the acrylic resin coating. The coating had a gloss of 97 ° at 60 ° and a hardness of 7H.
Example 6
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid, 1 part of hexadecyltributylammonium chloride, 2 parts of polybutyl acrylate and 1 part of nano titanium oxide, then carrying out melt mixing extrusion on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, and crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 150 ℃ for 30 minutes to obtain the acrylic resin coating. The coating had a gloss of 93 ° at 60 ° and a hardness of 4H.
Example 7
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid, 2 parts of polybutyl acrylate and 1 part of nano titanium oxide, then melting, mixing and extruding on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling, tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 150 ℃ for 30 minutes to obtain the acrylic resin coating. The coating had a gloss of 93 ° at 60 ° and a hardness of 3H.
Comparative example 1
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid, 0.5 part of hexadecyltributylammonium chloride, 2 parts of polybutyl acrylate and 1 part of benzoin, then carrying out melt mixing extrusion on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 160 ℃ for 30 minutes to obtain the acrylic resin coating. The coating had a gloss of 95 ° at 60 ° and a hardness of 3H.
Comparative example 2
Uniformly mixing 100 parts of glycidyl methacrylate, 35 parts of tetradecanedioic acid, 1.5 parts of hexadecyltributylammonium chloride, 2 parts of polybutyl acrylate, 0.5 part of benzoin and 20 parts of nano-alumina, then melting, mixing and extruding on an extruder, wherein the melting temperature is 110 ℃, repeatedly extruding for 4 times, then cooling, tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 160 ℃ for 30 minutes to obtain the acrylic resin coating. The coating had a gloss of 85 ° at 60 ° and a hardness of 4H.
Comparative example 3
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid, 1 part of 2-methylimidazole, 2 parts of polybutyl acrylate, 1 part of benzoin and 2 parts of cage-type silsesquioxane, then carrying out melt mixing extrusion on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 150 ℃ for 25 minutes to obtain the acrylic resin coating. The coating had a gloss of 95 ° at 60 ° and a hardness of 5H.
Comparative example 4
Uniformly mixing 100 parts of glycidyl methacrylate, 30 parts of dodecanedioic acid and 2 parts of polybutyl acrylate, then melting, mixing and extruding on an extruder at the melting temperature of 110 ℃, repeatedly extruding for 4 times, then cooling and tabletting, crushing, grinding and screening to obtain the acrylic resin mixture.
Curing the acrylic resin mixture at 150 ℃ for 30 minutes to obtain the acrylic resin coating. The coating had a gloss of 93 ° at 60 ° and a hardness of 2H.
Compared with the comparative example, the coating prepared by using the acrylic resin powder composition of the present invention uses less nano-functional filler, and has high hardness while having high gloss.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. An acrylic resin powder composition comprises glycidyl acrylate resin, a curing agent, a leveling agent and a nano functional filler, wherein the nano functional filler is 0.1-0.5 part by mass based on 100 parts by mass of the glycidyl acrylate resin, and the nano functional filler is cage-like silsesquioxane or a composition containing the cage-like silsesquioxane.
2. The powder composition according to claim 1, wherein the amount of the nano-functional filler is 0.2 to 0.5 parts by mass based on 100 parts by mass of the glycidyl acrylate resin.
3. The powder composition according to claim 1, wherein the curing agent is 20 to 40 parts by mass based on 100 parts by mass of the glycidyl acrylate resin; and/or the leveling agent is 1-3 parts by mass.
4. The powder composition according to any one of claims 1 to 3, wherein the glycidyl acrylate resin is a glycidyl methacrylate type acrylic resin; and/or the curing agent is a polycarboxylic acid and/or an anhydride thereof; and/or the leveling agent is an acrylate leveling agent.
5. The powder composition of claim 4, wherein the polycarboxylic acid is selected from at least one of adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid; and/or the acrylate leveling agent is polybutyl acrylate.
6. Powder composition according to any of claims 1 to 3, further comprising a curing accelerator and/or benzoin.
7. The powder composition according to claim 6, wherein the curing accelerator is 0.1 to 2 parts by mass based on 100 parts by mass of the glycidyl acrylate-based resin; and/or 0.5 to 2 parts by mass of benzoin based on 100 parts by mass of the glycidyl acrylate resin; and/or the curing accelerator is at least one selected from quaternary ammonium salt curing accelerators, imidazole curing accelerators and tertiary amine curing accelerators.
8. An acrylic resin coating comprising a product obtained by melt-kneading and extruding the powder composition according to any one of claims 1 to 7, pulverizing and sieving, and finally spray-curing.
9. The coating of claim 8, wherein the curing temperature is 140 to 160 ℃ and the curing time is 20 to 40 minutes.
10. Coating according to claim 8 or 9, wherein the coating hardness is 4-7H.
11. Use of a powder composition according to any one of claims 1-7 or a coating according to any one of claims 8-10 for surface coating of wood or paper.
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| CN201610122437.1A CN107151468B (en) | 2016-03-04 | 2016-03-04 | Acrylic resin powder composition, coating and application |
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| CN201610122437.1A CN107151468B (en) | 2016-03-04 | 2016-03-04 | Acrylic resin powder composition, coating and application |
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| CN108504254A (en) * | 2018-05-11 | 2018-09-07 | 佛山市上利丰装饰材料有限公司 | The preparation method of powdery paints for plastic wood sheet surface |
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| CN1478836A (en) * | 2003-07-10 | 2004-03-03 | 广州电器科学研究院 | Thermo setting low temperature solidify whether resistant low light powder paint |
| CN101358097A (en) * | 2008-09-19 | 2009-02-04 | 河北科技大学 | Nano composite powder coatings and dispersion polymerization preparation method thereof |
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| CN104946063A (en) * | 2015-06-15 | 2015-09-30 | 蚌埠市阳光粉沫涂料有限责任公司 | Nano calcium carbonate-modified acrylic resin type powder coating |
| CN105273558A (en) * | 2015-11-06 | 2016-01-27 | 广州擎天材料科技有限公司 | Low-temperature curing type epoxy group acrylic acid transparent powder coating and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102443330B (en) * | 2011-10-17 | 2013-06-19 | 重庆文理学院 | Coating material and its preparation method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478836A (en) * | 2003-07-10 | 2004-03-03 | 广州电器科学研究院 | Thermo setting low temperature solidify whether resistant low light powder paint |
| CN101358097A (en) * | 2008-09-19 | 2009-02-04 | 河北科技大学 | Nano composite powder coatings and dispersion polymerization preparation method thereof |
| CN104130676A (en) * | 2014-07-25 | 2014-11-05 | 安徽华辉塑业科技股份有限公司 | Low-temperature curing powder coating and preparation method thereof |
| CN104946063A (en) * | 2015-06-15 | 2015-09-30 | 蚌埠市阳光粉沫涂料有限责任公司 | Nano calcium carbonate-modified acrylic resin type powder coating |
| CN105273558A (en) * | 2015-11-06 | 2016-01-27 | 广州擎天材料科技有限公司 | Low-temperature curing type epoxy group acrylic acid transparent powder coating and preparation method thereof |
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