CN102911568A - Aqueous fluorine carbon coating material and preparation technology thereof - Google Patents
Aqueous fluorine carbon coating material and preparation technology thereof Download PDFInfo
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Abstract
The invention discloses an aqueous fluorine carbon coating material and a preparation technology thereof. The preparation technology comprises the following steps of: firstly, respectively taking water, a dispersing agent, a wetting agent, a preservative, an antifoaming agent, a multifunctional additive, propylene glycol, pigment and filler, and dispersing at a high speed, sanding and filtering after mixing; (2) polymerizing a fluorine-containing olefin monomer and vinyl ether monomer emulsion to form seed polymer, adding acrylic ester into the seed polymer to copolymerize the seed emulsion to obtain a fluorine-containing acrylic copolymer, i.e., fluorine acrylic emulsion; and (3) adding the fluorine acrylic emulsion, a coalescing agent, a thickening agent, a flatting agent and a coating surface hydrophilc agent into filtered sizing agent for paint mixing, and stirring and mixing at a low speed to obtain a finished aqueous fluorine carbon coating material. According to the invention, the acrylic resin is guided into the fluororesin, so that the performances of the coating layer, i.e., the washability, the corrosion resistance and the flexibility can be obviously improved, and the cost of the fluorine coating material can be reduced; the hydrophilic monomer is induced, so that the crystallinity of the fluororesin and the glass-transition temperature can be reduced; and the fluorine content of the fluorine acrylic emulsion is controlled, so that the low construction difficulty can be guaranteed, and the construction method and the construction technology of the aqueous fluorine carbon coating material are as the same as those of the common emulsion paint, so that the coating material is an aqueous fluorine carbon coating material which is suitable for large-scale popularization and application.
Description
Technical field
The present invention relates to a kind of aqueous fluorocarbon coating and preparation technology thereof.
Background technology
Fluorocarbon coating has high-insulation, and the paint film molecular structure is fine and close, demonstrates good not adhesivity, low surface tension, low friction property and scolds water, scolds oil, scolds the performance such as dirt.Chemically then showing as preferably thermostability and unreactiveness, more be 20 years its outdoor work-ing life, considerably beyond general coating.Fluorocarbon coating obtains to use widely in various fields such as national defence, building, bridge, petrochemical compleies through the development of decades.The development experience of fluorocarbon coating solvent hot-melting type, solvent cross-linking type, three developmental stage of aqueous dispersion type.The solvent hot-melting type owing to need high bake, is mainly used in various precoating metal building materials take the PVDF polyvinylidene fluoride resin as representative; The solvent cross-linking type is take FEVE fluoroolefin-vinyl multi-copolymerization resin as representative, because normal temperature solidified, therefore can be widely used in various materials and various field, but the solvent-borne type normal temperature solidifying fluorine-carbon coating also has many shortcomings: a in application, two-component coating is strict to execution conditions and supplementary material in construction; B, solvent belong to inflammable, explosive hazardous substance, and store, transport inconvenience, and serious harm workmen's health; C, the densification of filming, ventilation property is poor, sometimes bubbles easily; D, solvent based coating contain a large amount of organic volatile (VOC), and environmental pollution is very serious, also waste resource simultaneously, waste energy.Along with the progress of science and technology, people improve constantly for the requirement of environmental protection, and aqueous fluorocarbon coating had become the trend and direction of fluorocarbon coating development already.Especially in building trade, aqueous fluorocarbon coating is a kind of desirable high-grade exterior wall decorating coating especially.Present domestic some aqueous fluorocarbon coatings of having developed, these products have solved the disadvantage that the solvent-borne type fluorocarbon coating exists, but aspect ageing resistance and contamination resistance, they generally also are unable to catch up with the solvent-borne type fluorocarbon coating.
Summary of the invention
The object of the invention is to propose a kind of weathering resistance and contamination resistance and solvent-borne type fluorocarbon coating quite or better, difficulty of construction is low, constructional method is the same with the generic latex lacquer with construction technology, is very suitable for the large-area aqueous fluorocarbon coating of applying and preparation technology thereof.
The technical solution used in the present invention is: a kind of aqueous fluorocarbon coating is characterized in that: comprise following component:
Water 10-30
Frostproofer 1-3
Wetting agent 0.1-1
Dispersion agent 0.1-1
Multifunctional assistant 0.1-1
Defoamer 0.1-1
Sanitas 0.1-1
Pigment 5-25
Filler 1-20
Fluorine acrylic emulsion 30-60
Film coalescence aid 1-5
Thickening material 0.1-2
Flow agent 0.1-1
Coatingsurface hydrophilizing agent 0.5-5
More than each component add up to 100;
The preparation method of wherein said fluorine carbon emulsion is for being in molar ratio fluorinated olefin monomers with fluorinated olefin monomers and vinyl ether monomers: vinyl ether monomers=(0.6～1.5): 1 carries out letex polymerization forms seed polymer, add again acrylate in the seed polymer and carry out seeded emulsion copolymerization, wherein the weight ratio of seed polymer and acrylate is 1:(0.1～0.5), getting the fluorine-containing propene acid copolymer is the fluorine acrylic emulsion.
Described frostproofer is propylene glycol or ethylene glycol, and pigment is titanium dioxide or pearlescence, and filler is process white, calcium carbonate or talcum powder.
The preparation technology who produces above-mentioned aqueous fluorocarbon coating is: 1. first respectively water intaking, dispersion agent, wetting agent, sanitas, defoamer, multifunctional assistant, frostproofer, pigment, filler, high speed dispersion, sand milling, filtration after mixing;
2. fluorinated olefin monomers and vinyl ether monomers are fluorinated olefin monomers in molar ratio: vinyl ether monomers=(0.6～1.5): 1 carries out letex polymerization forms seed polymer, add again acrylate in the seed polymer and carry out seeded emulsion copolymerization, wherein the weight ratio of seed polymer and acrylate is 1:(0.1～0.5), getting the fluorine-containing propene acid copolymer is the fluorine acrylic emulsion;
3. add fluorine acrylic emulsion, film coalescence aid, thickening material, flow agent, coatingsurface hydrophilizing agent in the slurry after filter and carry out paint, stirring at low speed is mixed to get the finished product aqueous fluorocarbon coating;
Wherein the weight percent of above-mentioned each component is:
Water 10-30
Frostproofer 1-3
Wetting agent 0.1-1
Dispersion agent 0.1-1
Multifunctional assistant 0.1-1
Defoamer 0.1-1
Sanitas 0.1-1
Pigment 5-25
Filler 1-20
Fluorine acrylic emulsion 30-60
Film coalescence aid 1-5
Thickening material 0.1-2
Flow agent 0.1-1
Coatingsurface hydrophilizing agent 0.5-5
More than each component add up to 100;
Wherein said frostproofer is propylene glycol or ethylene glycol, and pigment is titanium dioxide or pearlescence, and filler is process white, calcium carbonate or talcum powder.
The present invention improves its application performance by fluoro-resin is carried out modification, develops the fluorine carbon emulsion of excellent property, and produces on this basis high performance aqueous fluorocarbon coating.Concrete manifestation is as follows:
A. introduce the acrylic resin of excellent properties, preparation water-based fluorine acrylic emulsion
Because water-based fluorine acrylate dope property indices adapts to the requirement of construction industry, and price is placed in the middle, is easy to be accepted by the user, and can adapt to the requirement of environmental protection, so it has a good application prospect in construction industry.The water-based fluorine acrylic emulsion that the present invention adopts is introduced fluoro-containing group in the acrylic ester polymer, not only can keep the original excellent properties of acrylic ester polymer paint film, and weathering resistance and the didirtresistance of paint film have effectively been improved, the shortcomings such as the fluorine paint adhesion is poor, cost is high, solidification value is high have been remedied simultaneously, so fluorine the third resin application prospect after the modification is more extensive.Simultaneously in fluoropolymer, introduce esters of acrylic acid, can improve traditional fluoropolymer to the shortcomings such as low-temperature curing ability of base material poor adhesive force and coating, improve glossiness and the snappiness of fluorine coating, reduce simultaneously the cost of fluorine coating.
B. introduce hydrophilic monomer, reduce degree of crystallinity and the second-order transition temperature of fluoro-resin
Although water-based fluororesin has the characteristics such as good mechanical property and chemical-resistant, is subjected to the higher impact of homopolymer degree of crystallinity, the water-soluble and film forming sticking power of homopolymerization fluorine resin is relatively poor.For reducing the degree of crystallinity of homopolymerization fluorine resin, the present invention makes Fluorine containing olefine by adding some monomers that contain vinyl and its copolymerization, in the Fluorine containing olefine multipolymer, introduce simultaneously hydrophilic monomers such as ether, carboxyl, hydroxyl, but its degree of crystallinity of decrease, therefore formed crosslinked polymer temperature also can decrease, even can ambient cure.By in the Fluorine containing olefine multipolymer, introducing carboxyl, can promote the cross-linking and curing reaction of fluoro-resin and hydroxyl, hydrophilic oh group can also wetting pigment, prevent that fluorine coating from producing loose colour etc.; In the Fluorine containing olefine multipolymer, introduce hydroxyl, can with isocyanic ester-NCO reacts, and makes fluoro-resin crosslinked, shortens set time, can also increase the sticking power of paint film simultaneously, improves the snappiness of resin, reduces cost, improves resistance to acids and bases; By introduce cyclohexyl in the Fluorine containing olefine multipolymer, because the existence of the large ring of cyclohexyl in the side chain, resin degree of crystallinity reduces, and the rigidity of resin and the transparency improve; In the Fluorine containing olefine multipolymer, introduce alkyl, can increase the snappiness of fluoro-resin; In the Fluorine containing olefine multipolymer, introduce the ethylenically unsaturated monomers with the hydrolyzable siloxy, can effectively improve the sticking power of paint film and substrate etc.
C. be to improve resin property by the control to fluorine content
Fluorine content is the important indicator that fluorine coating is different from other kind coating, is the big event of distinguishing fluorine coating.The fluorine content of fluorine coating uses the content of fluorine element in the film forming base-material (resin and part of auxiliary etc.) to represent usually.China's watersoluble fluorine paint technology still is in the starting stage, and the reasonable control of fluorine content still is in the exploratory stage, and there is the construction temperature narrow range in fluorine content to 40% in the fluorine emulsion product, complicated construction technique; And fluorine content is when being lower than 10%, and the performances such as its weathering resistance, hydrophobic and lyophobic property are relatively poor again.Therefore, the present invention controls the fluorine content of fluorine acrylic emulsion between 15-30%, has both solved the construction temperature narrow limits, the deficiency of complicated construction technique, and the performances such as weathering resistance, hydrophobic and lyophobic property are all very high simultaneously.
In sum, the present invention introduces acrylic resin in the fluoro-resin, can significantly improve the performance such as abrasion resistance, erosion resistance, snappiness of coating, reduces simultaneously the cost of fluorine coating; By introducing hydrophilic monomer, reduce degree of crystallinity and the second-order transition temperature of fluoro-resin; By the fluorine content of control fluorine acrylic emulsion, guarantee that difficulty of construction is low, constructional method is the same with the generic latex lacquer with construction technology, is a kind of large-area aqueous fluorocarbon coating of applying that is very suitable for.
Embodiment
The present invention will be further described below in conjunction with embodiment, it should be understood that these embodiment only are used for the purpose of illustration, never limit protection scope of the present invention.
The technical scheme that the embodiment of the invention adopts is specific as follows: 1. first respectively water intaking, dispersion agent, wetting agent, sanitas, defoamer, multifunctional assistant, frostproofer, pigment, filler, high speed dispersion, sand milling, filtration after mixing;
2. fluorinated olefin monomers and vinyl ether monomers are fluorinated olefin monomers in molar ratio: vinyl ether monomers=(0.6～1.5): 1 carries out letex polymerization forms seed polymer, add again acrylate in the seed polymer and carry out seeded emulsion copolymerization, wherein the weight ratio of seed polymer and acrylate is 1:(0.1～0.5), getting the fluorine-containing propene acid copolymer is the fluorine acrylic emulsion;
3. add fluorine acrylic emulsion, film coalescence aid, thickening material, flow agent, coatingsurface hydrophilizing agent in the slurry after filter and carry out paint, stirring at low speed is mixed to get the finished product aqueous fluorocarbon coating;
Wherein the weight percent of above-mentioned each component is:
Water 10-30
Frostproofer 1-3
Wetting agent 0.1-1
Dispersion agent 0.1-1
Multifunctional assistant 0.1-1
Defoamer 0.1-1
Sanitas 0.1-1
Pigment 5-25
Filler 1-20
Fluorine acrylic emulsion 30-60
Film coalescence aid 1-5
Thickening material 0.1-2
Flow agent 0.1-1
Coatingsurface hydrophilizing agent 0.5-5
More than each component add up to 100;
Wherein frostproofer is propylene glycol or ethylene glycol, and pigment is titanium dioxide or pearlescence, and filler is process white, calcium carbonate or talcum powder.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention; the technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and the claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (3)
1. aqueous fluorocarbon coating is characterized in that: comprise following component:
Water 10-30
Frostproofer 1-3
Wetting agent 0.1-1
Dispersion agent 0.1-1
Multifunctional assistant 0.1-1
Defoamer 0.1-1
Sanitas 0.1-1
Pigment 5-25
Filler 1-20
Fluorine acrylic emulsion 30-60
Film coalescence aid 1-5
Thickening material 0.1-2
Flow agent 0.1-1
Coatingsurface hydrophilizing agent 0.5-5
More than each component add up to 100;
The preparation method of wherein said fluorine carbon emulsion is for being in molar ratio fluorinated olefin monomers with fluorinated olefin monomers and vinyl ether monomers: vinyl ether monomers=(0.6～1.5): 1 carries out letex polymerization forms seed polymer, add again acrylate in the seed polymer and carry out seeded emulsion copolymerization, wherein the weight ratio of seed polymer and acrylate is 1:(0.1～0.5), getting the fluorine-containing propene acid copolymer is the fluorine acrylic emulsion.
2. the preparation technology of described aqueous fluorocarbon coating according to claim 1, it is characterized in that: described frostproofer is propylene glycol or ethylene glycol, and pigment is titanium dioxide or pearlescence, and filler is process white, calcium carbonate or talcum powder.
3. preparation technology who prepares the described aqueous fluorocarbon coating of claim 1 is characterized in that: comprise following process:
1. first respectively water intaking, dispersion agent, wetting agent, sanitas, defoamer, multifunctional assistant, frostproofer, pigment, filler, high speed dispersion, sand milling, filtration after mixing;
2. fluorinated olefin monomers and vinyl ether monomers are fluorinated olefin monomers in molar ratio: vinyl ether monomers=(0.6～1.5): 1 carries out letex polymerization forms seed polymer, add again acrylate in the seed polymer and carry out seeded emulsion copolymerization, wherein the weight ratio of seed polymer and acrylate is 1:(0.1～0.5), getting the fluorine-containing propene acid copolymer is the fluorine acrylic emulsion;
3. add fluorine acrylic emulsion, film coalescence aid, thickening material, flow agent, coatingsurface hydrophilizing agent in the slurry after filter and carry out paint, stirring at low speed is mixed to get the finished product aqueous fluorocarbon coating;
Wherein the weight percent of above-mentioned each component is:
Water 10-30
Frostproofer 1-3
Wetting agent 0.1-1
Dispersion agent 0.1-1
Multifunctional assistant 0.1-1
Defoamer 0.1-1
Sanitas 0.1-1
Pigment 5-25
Filler 1-20
Fluorine acrylic emulsion 30-60
Film coalescence aid 1-5
Thickening material 0.1-2
Flow agent 0.1-1
Coatingsurface hydrophilizing agent 0.5-5
More than each component add up to 100;
Wherein said frostproofer is propylene glycol or ethylene glycol, and pigment is titanium dioxide or pearlescence, and filler is process white, calcium carbonate or talcum powder.
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| CN2012104417698A CN102911568A (en) | 2012-11-08 | 2012-11-08 | Aqueous fluorine carbon coating material and preparation technology thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360874A (en) * | 2013-07-22 | 2013-10-23 | 天长市开林化工有限公司 | Waterborne exterior-wall paint and its preparation method |
| CN103865213A (en) * | 2014-03-14 | 2014-06-18 | 福州皇家地坪有限公司 | Weather-proof fouling resisting floor cover optical material and preparation method thereof |
| CN103923539A (en) * | 2014-05-01 | 2014-07-16 | 湖州中辰建设有限公司 | Novel highly weather-proof water-based fluorocarbon exterior emulsion coating |
| CN105440871A (en) * | 2015-12-31 | 2016-03-30 | 南京福臻再生资源科技股份有限公司 | Fluorocarbon paint with excellent colorability and preparation method thereof |
| CN105462425A (en) * | 2015-12-31 | 2016-04-06 | 祁守岗 | Fluorocarbon paint high in fluorine content and preparation method thereof |
| CN106349830A (en) * | 2016-08-26 | 2017-01-25 | 江苏格桑花涂料有限公司 | Modified waterborne fluorine coating and preparation method thereof |
| CN108610864A (en) * | 2016-11-29 | 2018-10-02 | 宝山钢铁股份有限公司 | It is a kind of to prevent process of coking from generating coating and its application method that burnt plate is dropped down in tar adherency |
| CN111410859A (en) * | 2020-01-16 | 2020-07-14 | 佛山市大幸新材料有限公司 | Perfluoro antifouling protective material for ceramic tile |
| CN113136129A (en) * | 2021-03-18 | 2021-07-20 | 广东至诚紫光新材料有限公司 | Water-based high-weather-resistance fluorocarbon coating composition and preparation method thereof |
| WO2022041195A1 (en) * | 2020-08-31 | 2022-03-03 | Dow Global Technologies Llc | Aqueous composition |
| CN114292560A (en) * | 2022-01-12 | 2022-04-08 | 上海船舶工艺研究所(中国船舶工业集团公司第十一研究所) | High-durability water-based fluorocarbon paint and preparation method thereof |
| CN114316768A (en) * | 2021-12-29 | 2022-04-12 | 亚士创能科技(上海)股份有限公司 | Water-based fluorocarbon coating and preparation method and application thereof |
| CN115433493A (en) * | 2022-06-14 | 2022-12-06 | 上海衡峰厚千水性氟碳涂料有限公司 | Solid color finish paint and application thereof |
| CN116285553A (en) * | 2023-03-30 | 2023-06-23 | 广东鑫皇冠新材料有限公司 | Preparation method of water-based protective paint for household PVC film |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360874A (en) * | 2013-07-22 | 2013-10-23 | 天长市开林化工有限公司 | Waterborne exterior-wall paint and its preparation method |
| CN103865213A (en) * | 2014-03-14 | 2014-06-18 | 福州皇家地坪有限公司 | Weather-proof fouling resisting floor cover optical material and preparation method thereof |
| CN103865213B (en) * | 2014-03-14 | 2016-08-17 | 福州皇家地坪有限公司 | A kind of weather-proof, stain resistant terrace Lacquer finish material and preparation method thereof |
| CN103923539A (en) * | 2014-05-01 | 2014-07-16 | 湖州中辰建设有限公司 | Novel highly weather-proof water-based fluorocarbon exterior emulsion coating |
| CN105440871A (en) * | 2015-12-31 | 2016-03-30 | 南京福臻再生资源科技股份有限公司 | Fluorocarbon paint with excellent colorability and preparation method thereof |
| CN105462425A (en) * | 2015-12-31 | 2016-04-06 | 祁守岗 | Fluorocarbon paint high in fluorine content and preparation method thereof |
| CN106349830A (en) * | 2016-08-26 | 2017-01-25 | 江苏格桑花涂料有限公司 | Modified waterborne fluorine coating and preparation method thereof |
| CN108610864B (en) * | 2016-11-29 | 2020-10-27 | 宝山钢铁股份有限公司 | Coating for preventing tar generated in coking process from adhering to coke dripping plate and using method thereof |
| CN108610864A (en) * | 2016-11-29 | 2018-10-02 | 宝山钢铁股份有限公司 | It is a kind of to prevent process of coking from generating coating and its application method that burnt plate is dropped down in tar adherency |
| CN111410859A (en) * | 2020-01-16 | 2020-07-14 | 佛山市大幸新材料有限公司 | Perfluoro antifouling protective material for ceramic tile |
| WO2022041195A1 (en) * | 2020-08-31 | 2022-03-03 | Dow Global Technologies Llc | Aqueous composition |
| CN113136129A (en) * | 2021-03-18 | 2021-07-20 | 广东至诚紫光新材料有限公司 | Water-based high-weather-resistance fluorocarbon coating composition and preparation method thereof |
| CN114316768A (en) * | 2021-12-29 | 2022-04-12 | 亚士创能科技(上海)股份有限公司 | Water-based fluorocarbon coating and preparation method and application thereof |
| CN114316768B (en) * | 2021-12-29 | 2023-03-14 | 亚士创能科技(上海)股份有限公司 | Water-based fluorocarbon coating and preparation method and application thereof |
| CN114292560A (en) * | 2022-01-12 | 2022-04-08 | 上海船舶工艺研究所(中国船舶工业集团公司第十一研究所) | High-durability water-based fluorocarbon paint and preparation method thereof |
| CN114292560B (en) * | 2022-01-12 | 2024-01-05 | 上海船舶工艺研究所(中国船舶集团有限公司第十一研究所) | High-durability water-based fluorocarbon paint and preparation method thereof |
| CN115433493A (en) * | 2022-06-14 | 2022-12-06 | 上海衡峰厚千水性氟碳涂料有限公司 | Solid color finish paint and application thereof |
| CN116285553A (en) * | 2023-03-30 | 2023-06-23 | 广东鑫皇冠新材料有限公司 | Preparation method of water-based protective paint for household PVC film |
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Application publication date: 20130206 |