CN109749619B - Super-hydrophobic and stain-resistant water-based UV coating and preparation method thereof - Google Patents
Super-hydrophobic and stain-resistant water-based UV coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a super-hydrophobic and stain-resistant water-based UV coating and a preparation method thereof, wherein the coating comprises the following components in percentage by mass: 25-35% of polyurethane acrylate, 20-30% of epoxy acrylate, 5-10% of hyperbranched polyurethane, 1-10% of water-soluble reactive diluent, 5-15% of organic silicon hydrophobic agent, 1-10% of photoinitiator, 2-10% of dispersant, 2-10% of assistant and 5-20% of water. Compared with the prior art, the invention has the advantages of simple preparation, good adhesion performance, low cost and excellent hydrophobic effect and contamination resistance of the formed coating.
Description
Technical Field
The invention relates to the field of water-based UV (ultraviolet) coatings and 3C (carbon dioxide) products or automotive interior coatings, in particular to a super-hydrophobic and stain-resistant water-based UV coating and a preparation method thereof.
Background
The 3C products (a general name of electronic products such as communication and the like) and the automotive interior products have attracted attention in hand sweat resistance, stain resistance, self-cleaning and other properties.
Generally, the surface material of the electronic product is basically plastic material, so that most of the surface coating is carried out by adopting low-temperature curing modes such as UV curing and the like, and in addition, the UV curing coating has the advantages of high curing speed, less residual volatile components, less energy consumption and the like, so that the UV curing coating becomes the first choice for coating the product. Therefore, the UV curing coating which can form a coating with the functions of stain resistance, hand sweat resistance, self-cleaning and the like is certainly favored by the market.
The general way to achieve such functions is to incorporate fluorocarbon-based materials, such as fluorocarbon resins, fluorocarbon auxiliaries, etc., into the coating system, but such materials are expensive to prepare and expensive.
Furthermore, the general UV curing coating in the market is still mainly oily, and the formula of the coating contains volatile reactive diluent before curing, so that the coating has strong irritation, is harmful to the health of people and pollutes the environment. The water-based paint has the imperative for high solid content.
Patent CN105111912B discloses a UV aqueous photocurable coating, which is composed of a urethane acrylate dispersion and a photoinitiator, wherein the urethane acrylate is prepared from an acrylic polymer and isocyanate, the acrylic polymer is prepared by copolymerization of an acrylic monomer, and the acrylic monomer at least comprises a polyoxyalkylene acrylate monomer and a hydroxy acrylic monomer. The invention still can not meet the requirements of super hydrophobicity and stain resistance of the UV coating.
Disclosure of Invention
The invention aims to solve the problems and provide a super-hydrophobic and stain-resistant water-based UV coating with low cost and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a super-hydrophobic and stain-resistant water-based UV coating comprises the following components in percentage by mass:
preferably, the polyurethane acrylate is chain-extended bifunctional polyurethane acrylate synthesized by using toluene diisocyanate as a hard segment, using polyethylene glycol as a soft segment, using hydroxyethyl acrylate as a blocking agent, and using ethylene glycol or 1, 4-butanediol as a chain extender.
Preferably, the polyurethane acrylate is prepared by the following method: at the temperature of 35-45 ℃, mixing excessive Toluene Diisocyanate (TDI) and polyethylene glycol (PEG, hydroxyl value is 50-400 mg (KOH)/g), heating to 70-80 ℃ by using dibutyltin dilaurate as a catalyst, reacting for two hours, cooling to 35-45 ℃, adding excessive hydroxyethyl acrylate and a small amount of polymerization inhibitor p-methoxyphenol, uniformly mixing, heating to 60-70 ℃ again, reacting for 4 hours, cooling, and discharging to obtain the polyurethane acrylate. Wherein the ratio of TDI to PEG and the hydroxyl value of PEG are adjusted according to the hardness and hardness requirements.
Preferably, the epoxy acrylate is bisphenol A epoxy acrylate with the epoxy value of more than or equal to 0.3
mol/100g of epoxy resin and acrylic acid.
Preferably, the epoxy acrylate is prepared by the following method: uniformly mixing epoxy resin and acrylic acid according to a molar ratio of 1:1 at normal temperature, adding a small amount of hydroquinone as a polymerization inhibitor and triethylamine as a catalyst, stirring, reacting for 2 hours at 90-110 ℃, measuring an acid value, adding maleic anhydride with an equal molar quantity to the residual hydroxyl, heating to 50-70 ℃ to completely esterify the residual hydroxyl, adding triethanolamine to neutralize the residual carboxyl, cooling and discharging to obtain the epoxy acrylate.
Preferably, the hyperbranched polyurethane is prepared by the following method:
(1) pentaerythritol and dimethylolpropionic acid form a primary polyester polyol (OH-8) containing eight hydroxyl groups;
(2) then toluene diisocyanate and hydroxyethyl acrylate react according to the molar ratio of 1:1 to form an acrylate intermediate (ACR-NCO) containing isocyanate;
(3) and (3) reacting the acrylate intermediate (ACR-NCO) with polyester polyol (OH-8) according to the molar ratio of isocyanate to hydroxyl of 1:1 to form the hyperbranched polyurethane.
Preferably, the organosilicon hydrophobic agent is a dispersed emulsion of a reaction product of hydrogen-containing silicone oil and a vinyl silane coupling agent, and the preparation method of the organosilicon hydrophobic agent comprises the following steps: the silicone oil containing hydrogen and vinyl silane coupling agent (A171 and the like) react at 80-100 ℃ according to the molar ratio of hydrogen content to vinyl of 1:1 to prepare (platinum gold water is used as a catalyst), and then emulsifying by using an emulsifying agent (nonionic and anionic matched for use) to obtain the organic silicon hydrophobic agent.
Preferably, the dispersant is a polymeric hyperdispersant selected from polyether esters of styrene-maleic anhydride copolymer resins. The preparation process comprises the following steps: dissolving the benzene-maleic resin in acetone, adding the polyether (polyethylene glycol monomethyl ether) with the end capped by the monomethyl group into a reaction system, reacting at 60-90 ℃ under the action of an esterifying agent (p-toluenesulfonic acid), and adding a neutralizing agent (tertiary amine substance, such as triethylamine) to neutralize maleic anhydride to obtain the required dispersing agent.
Preferably, the water-soluble reactive diluent is a water-soluble monomer selected from acrylic acid, maleic acid, hydroxyethyl acrylate or acrylamide; the photoinitiator is an aqueous photoinitiator and is selected from one of 2959 (supplied by Pasteur, Germany), 819DW (supplied by Pasteur, Germany) and KIPEM (stable aqueous emulsion for KIP150, supplied by Pasteur, Germany); the auxiliary agent is one or a mixture of more of a flatting agent, a defoaming agent, a thickening agent, an adhesion promoter, a pigment, a filler or an amine neutralizing agent.
A preparation method of super-hydrophobic and stain-resistant water-based UV coating comprises the following steps:
(1) preparing materials according to the mass percent of each component;
(2) sequentially adding polyurethane acrylate, epoxy acrylate and hyperbranched polyurethane into an aqueous solution in which a dispersing agent and a water-soluble active diluent are dissolved, and uniformly stirring and dispersing;
(3) adding an organic silicon hydrophobic agent into the aqueous system, and then stirring and uniformly dispersing;
(4) adding the auxiliary agent according to the requirement under the stirring state, and standing for a period of time to obtain the product.
Further, the stirring speed in the step (4) is 500-.
The super-hydrophobic and stain-resistant water-based UV coating adopts three kinds of oligomer resins, and the three kinds of oligomer resins are terminated by double bonds of acrylate, so that the coating has good photocuring activity.
The assistant with the hydrophobic effect and the stain resistance effect is mainly an organic silicon hydrophobic agent, alkoxy is introduced to the surface of the organic silicon hydrophobic agent through hydrosilation reaction, hydrolysis is carried out in the film forming process of the coating to form hydroxyl with strong adhesive force, the hydroxyl is uniformly and downwards attached to the surface of the coating, and meanwhile, a silane chain with strong hydrophobicity is upwards attached to the surface of the coating to form a hydrophobic layer and a stain resistance layer.
In order to uniformly disperse the UV curing resins in water, the function of the dispersing agent is particularly important, the addition of the hyper-dispersing agent is the key for realizing the water-based curing, one end of the hyper-dispersing agent is the styrene-maleic anhydride resin with oleophylic property, the styrene-maleic anhydride resin has good compatibility with structures such as TDI, bisphenol A and the like, and the other end of the hyper-dispersing agent is provided with a longer polyethylene glycol chain, so that the hyper-dispersing agent has good compatibility with polyether in polyurethane on one hand, and the hyper-dispersing agent is used as a solvating group to realize the function of a hydrophilic end on the.
Compared with the prior art, the invention has the following characteristics:
1) the coating is pollution-free, and has the advantages of no pollution of a water-based coating besides the advantages of a common UV curing coating;
2) the coating prepared by the coating has good surface hydrophobicity and stain resistance, and is widely applied.
3) The invention changes the traditional method of introducing fluorocarbon resin and introduces the organosilicon with low price into the coating system by a simple emulsification method.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the present invention is not limited thereto in any way.
Example 1
The super-hydrophobic and stain-resistant water-based UV coating comprises the components with the percentage content shown in the table 1. The preparation method comprises the following steps:
(1) preparing the components according to the weight parts;
(2) sequentially adding polyurethane acrylate, epoxy acrylate and water-based hyperbranched polyurethane into an aqueous solution in which a dispersing agent and a water-soluble active diluent are dissolved according to the dosage, and uniformly stirring and dispersing;
(3) adding the organosilicon hydrophobic agent into the aqueous system, and then stirring and uniformly dispersing.
(4) Sequentially adding other required additives in a stirring state, stirring for 15-20min at the rotating speed of 500 plus 2500rpm, and standing for a period of time to obtain the super-hydrophobic and stain-resistant water-based UV coating.
The results of the tests on the coatings produced after spray curing are detailed in table 2, wherein:
contact angle: reference GB/T30693-;
static contact angle: 153.02 degrees; rolling contact angle: 9.55 degrees;
and (3) stain resistance test: refer to GB/T9780 and 2013.
Example 2
The components and percentage contents of the super-hydrophobic and stain-resistant water-based UV coating are detailed in table 1. The preparation method is described in example 1.
The results of the tests on the coatings produced after spray curing are detailed in table 2, wherein:
contact angle: reference GB/T30693-;
static contact angle: 150.02 degrees; rolling contact angle: 10.01 degrees;
and (3) stain resistance test: refer to GB/T9780 and 2013.
Example 3
The components and percentage contents of the super-hydrophobic and stain-resistant water-based UV coating are detailed in table 1. The preparation method is described in example 1.
The results of the tests on the coatings produced after spray curing are detailed in table 2, wherein:
contact angle: reference GB/T30693-;
static contact angle: 154.11 degrees; rolling contact angle: 8.31 degrees;
and (3) stain resistance test: refer to GB/T9780 and 2013.
Example 4
The components and percentage contents of the super-hydrophobic and stain-resistant water-based UV coating are detailed in table 1. The preparation method is described in example 1.
Example 5
The components and percentage contents of the super-hydrophobic and stain-resistant water-based UV coating are detailed in table 1. The preparation method is described in example 1.
Example 6
The components and percentage contents of the super-hydrophobic and stain-resistant water-based UV coating are detailed in table 1. The preparation method is described in example 1.
TABLE 1 Components and percent amounts of the coatings of the various examples
Table 2 test results for coatings of examples 1, 2 and 3
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-mentioned embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention according to the teaching of the present invention.
Claims (8)
1. The super-hydrophobic and stain-resistant water-based UV coating is characterized by comprising the following components in percentage by mass:
25-35% of polyurethane acrylate
20-30% of epoxy acrylate
5-10% of hyperbranched polyurethane
1-10% of water-soluble active diluent
5-15% of organic silicon hydrophobing agent
1 to 10 percent of photoinitiator
2 to 10 percent of dispersant
2 to 10 percent of auxiliary agent
5-20% of water;
the organosilicon hydrophobic agent is a dispersed emulsion of a reaction product of hydrogen-containing silicone oil and a vinyl silane coupling agent; the dispersing agent is a high-molecular hyper-dispersing agent and is selected from polyether ester of styrene-maleic anhydride copolymer resin.
2. The super-hydrophobic and stain-resistant waterborne UV coating as claimed in claim 1, wherein the urethane acrylate is a chain-extended bifunctional urethane acrylate synthesized by using toluene diisocyanate as a hard segment, polyethylene glycol as a soft segment, hydroxyethyl acrylate as a capping agent, and ethylene glycol or 1, 4-butanediol as a chain extender.
3. The super-hydrophobic and contamination-resistant waterborne UV coating of claim 2, wherein the urethane acrylate is prepared by the following steps: at the temperature of 35-45 ℃, mixing excessive toluene diisocyanate with polyethylene glycol, heating to 70-80 ℃ by using dibutyltin dilaurate as a catalyst, reacting for two hours, cooling to 35-45 ℃, adding excessive hydroxyethyl acrylate and a small amount of polymerization inhibitor p-methoxyphenol, uniformly mixing, heating to 60-70 ℃ again, reacting for 4 hours, cooling, and discharging to obtain the polyurethane acrylate.
4. The super-hydrophobic and contamination-resistant waterborne UV coating of claim 1, wherein the epoxy acrylate is bisphenol A epoxy acrylate prepared by reacting an epoxy resin having an epoxy value of 0.3 mol/100g or more with acrylic acid.
5. The super-hydrophobic and stain-resistant waterborne UV coating according to claim 4, wherein the epoxy acrylate is prepared by the following method: uniformly mixing epoxy resin and acrylic acid according to a molar ratio of 1:1 at normal temperature, adding a small amount of hydroquinone as a polymerization inhibitor and triethylamine as a catalyst, stirring, reacting for 2 hours at 90-110 ℃, measuring an acid value, adding maleic anhydride with an equal molar quantity to the residual hydroxyl, heating to 50-70 ℃ to completely esterify the residual hydroxyl, adding triethanolamine to neutralize the residual carboxyl, cooling and discharging to obtain the epoxy acrylate.
6. The super-hydrophobic and stain-resistant waterborne UV coating according to claim 1, wherein the super-branched polyurethane is prepared by the following steps:
(1) pentaerythritol and dimethylolpropionic acid form a primary polyester polyol containing eight hydroxyl groups;
(2) then toluene diisocyanate and hydroxyethyl acrylate react according to the molar ratio of 1:1 to form an acrylate intermediate containing isocyanate;
(3) and reacting the acrylate intermediate with polyester polyol according to the molar ratio of isocyanate to hydroxyl of 1:1 to form the hyperbranched polyurethane.
7. The super-hydrophobic and contamination-resistant waterborne UV coating of claim 1, wherein the water-soluble reactive diluent is a water-soluble monomer selected from acrylic acid, maleic acid, hydroxyethyl acrylate or acrylamide; the photoinitiator is an aqueous photoinitiator and is selected from one of 2959, 819DW and KIPEM; the auxiliary agent is one or a mixture of more of a flatting agent, a defoaming agent, a thickening agent, an adhesion promoter, a pigment, a filler or an amine neutralizing agent.
8. The method of preparing a superhydrophobic and stain resistant aqueous UV coating of any one of claims 1-7, comprising the steps of:
(1) preparing materials according to the mass percent of each component;
(2) sequentially adding polyurethane acrylate, epoxy acrylate and hyperbranched polyurethane into an aqueous solution in which a dispersing agent and a water-soluble active diluent are dissolved, and uniformly stirring and dispersing;
(3) adding an organic silicon hydrophobic agent into the aqueous system, and then stirring and uniformly dispersing;
(4) adding the auxiliary agent according to the requirement under the stirring state, and standing for a period of time to obtain the product.
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| CN112126341A (en) * | 2020-09-29 | 2020-12-25 | 杭州吉邦综合服务有限公司 | Green environment-friendly water-based paint and preparation method thereof |
| CN114953687A (en) * | 2022-05-11 | 2022-08-30 | 江苏邦宇薄膜技术有限公司 | Online coated uvioresistant polyester film and preparation method thereof |
| CN116283151B (en) * | 2023-03-24 | 2023-08-11 | 佛山市维配可建材有限公司 | Waterproof, antibacterial and mildew-proof ceramic tile joint mixture and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146298A (en) * | 2013-02-26 | 2013-06-12 | 刘宁晔 | Ultraviolet coating and application thereof |
| WO2015109466A1 (en) * | 2014-01-22 | 2015-07-30 | 中国科学院化学研究所 | Methods for preparing aqueous ice-covering resistant mono-component hybrid coating and coating layer thereof, and use thereof |
| CN105131581A (en) * | 2015-09-30 | 2015-12-09 | 深圳市安品有机硅材料有限公司 | Light-cured liquid resin composite for three-dimensional forming and formative object obtained through light-curing of light-cured liquid resin composite |
| CN105331279A (en) * | 2015-12-16 | 2016-02-17 | 沈阳顺风新城建筑材料有限公司 | Water-borne UV paint and preparation method thereof |
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| CN104231918B (en) * | 2014-09-19 | 2016-06-29 | 中科院广州化学有限公司 | The quick-dry type oiliness infiltration nano combined protective agent of film-forming type and preparation method and application |
| CN106317285B (en) * | 2016-08-17 | 2019-02-12 | 苏州世名科技股份有限公司 | A kind of waterborne pigment dispersant |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146298A (en) * | 2013-02-26 | 2013-06-12 | 刘宁晔 | Ultraviolet coating and application thereof |
| WO2015109466A1 (en) * | 2014-01-22 | 2015-07-30 | 中国科学院化学研究所 | Methods for preparing aqueous ice-covering resistant mono-component hybrid coating and coating layer thereof, and use thereof |
| CN105131581A (en) * | 2015-09-30 | 2015-12-09 | 深圳市安品有机硅材料有限公司 | Light-cured liquid resin composite for three-dimensional forming and formative object obtained through light-curing of light-cured liquid resin composite |
| CN105331279A (en) * | 2015-12-16 | 2016-02-17 | 沈阳顺风新城建筑材料有限公司 | Water-borne UV paint and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《电晕处理技术在水性油墨印刷中的应用》;蒋欣;《塑料包装》;20170831;第27卷(第4期);45-46 * |
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