CN112322185A - Super-hydrophobic antifouling ceramic tile - Google Patents
Super-hydrophobic antifouling ceramic tile Download PDFInfo
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- CN112322185A CN112322185A CN202011447524.7A CN202011447524A CN112322185A CN 112322185 A CN112322185 A CN 112322185A CN 202011447524 A CN202011447524 A CN 202011447524A CN 112322185 A CN112322185 A CN 112322185A
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/34—Filling pastes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention relates to a super-hydrophobic antifouling ceramic tile which is characterized in that a super-hydrophobic fluorosilicone resin ceramic antifouling agent is coated on the surface of the ceramic tile, wherein the weight of the super-hydrophobic fluorosilicone resin ceramic antifouling agent is about 1-2 g/cm2Obtaining the super-hydrophobic antifouling ceramic tile; the super-hydrophobic fluorosilicone resin ceramic antifouling agent is prepared by using perfluoro-hydrogenous polymethylhydrosiloxane as matrix resin, amino-substituted cage polysilsesquioxane and polyisocyanate as cross-linking catalysts and nano-alumina as reinforcing fillers. The invention is super-hydrophobicThe antifouling ceramic tile has the advantages of small influence on glossiness, excellent hydrophobicity and good antifouling effect.
Description
Technical Field
The invention relates to a ceramic tile, in particular to a super-hydrophobic antifouling tile, and belongs to the technical field of hydrophobic antifouling tiles.
Technical Field
The residual air holes and micro cracks of the green brick or the glaze surface can adsorb pollutants in the firing process of the ceramic tile, and the existing ultra-clean bright ceramic tile is added with an antifouling agent to fill the holes during polishing to solve the problems. At present, the super-clean bright ceramic tile at home and abroad adopts better antifouling property, namely nano antifouling property, namely a layer with a special protection function is formed on the edge surface of a polished tile or a glazed tile, and a nano protective layer with a stable structure is mainly used for improving the antifouling property of the ceramic polished tile, is praised as a revolutionary breakthrough of the antifouling technology of the ceramic building industry, and simultaneously greatly enhances the glossiness of the surface of the tile body. With the improvement of living standard of people, the ink-jet pattern-penetrating matte bricks and the full-glazed matte bricks are paid attention in recent years.
However, the matte brick also has the problem that pollutants can be adsorbed due to residual air holes and micro cracks of a green brick or a glaze surface in the firing process, the luminosity of the ceramic tile can be greatly increased in the polishing process of the matte brick by adopting the traditional nano material, and the matte brick does not meet the matte standard, so that the matte antifouling pore-filling material without increasing the luminosity is urgently needed in the production of the matte brick. At present, an organic silicon antifouling agent is used in the market, under a specific condition, a silanol group on the surface of a ceramic and an organic silicon molecular group of a ceramic product treated by the organic silicon antifouling agent undergo a condensation dehydration reaction, so that the organic silicon molecular bond is connected to the surface of the ceramic product and is tightly combined together to form an organic siloxane hydrophobic film, and the hydrophobic film is in a directional arrangement structure.
Chinese patent CN201510026840.X relates to a ceramic tile antifouling agent and a preparation method thereof, wherein the antifouling agent comprises the following raw materials in percentage by mass: 6-16% of methyl high hydrogen silicone oil, 2-12% of low hydrogen silicone oil, 4-12% of 107 silicone rubber, 0.1-1% of silane coupling agent and 65-85% of No. 120 solvent oil; the invention is specially developed for the ceramic tile, is nontoxic and non-corrosive, can effectively protect the ceramic tile by simply coating the surface of the ceramic tile, has a glossy and beautiful film layer of the antifouling agent, well resists the infiltration of pollutants such as oily pens, ink, coffee, tea and the like while not influencing the glossiness of the surface of the ceramic tile, and has no risk of sticking the ceramic tile after the ceramic tile is packed. But for the matte brick with more pores on the brick surface, the antifouling effect of the organic silicon antifouling agent is relatively poor.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a super-hydrophobic fluorosilicone resin ceramic antifouling agent and a preparation method thereof.
The invention relates to a super-hydrophobic fluorosilicone resin ceramic antifouling agent, which is a normal-temperature cured super-hydrophobic fluorosilicone resin generated by taking perfluoro hydrogen-containing polymethylhydrosiloxane as matrix resin, amino-substituted cage polysilsesquioxane and polyisocyanate as crosslinking catalysts and nano aluminum oxide as reinforcing filler. The concrete formula comprises the following components in percentage by mass: 15.0 to 20.0 percent of perfluoro hydrogen-containing polymethylhydrosiloxane, 3.0 to 6.0 percent of amino substituted cage polysilsesquioxane, 1.0 to 2.0 percent of polyisocyanate, 3.0 to 6.0 percent of nano alumina, 4.0 to 8.0 percent of polyhydroxy polysiloxane, 1.0 to 3.0 percent of boric acid derivative and 60.0 to 72.0 percent of diluent.
The viscosity of the perfluoro hydrogen-containing polymethylhydrosiloxane is 20-60 mPa & s, and the hydrogen content is 1.0-1.7%.
The amino-substituted cage polysilsesquioxane is at least one of octaaminophenyl POSS and octa-3-aminopropyl POSS.
The polyisocyanate is an aliphatic polyisocyanate, and preferably at least one of hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, and methylcyclohexyl diisocyanate.
The nano-alumina has a particle size of 8-20 nm and a specific surface area of 150-300 m2/g。
The viscosity of the polyhydroxy polysiloxane is 80-200 mPa.s, and the hydroxyl content is 2-4%.
The boric acid derivative is at least one of phenylboronic acid, 3-fluorophenyl boric acid, sec-butyl boric acid, 4-fluorophenyl boric acid, 3-methoxyphenyl boric acid, n-butyl boric acid, 2-methoxyphenyl boric acid, p-ethylphenylboronic acid, 2-fluoropyridine-3-boric acid, n-propylboronic acid, 4-n-propylphenylboronic acid and p-carboxyphenylboronic acid.
The diluent is at least one of petroleum ether (with a boiling range of 60-120 ℃), a D40 solvent, kerosene, diesel oil and n-heptane.
The preparation method of the super-hydrophobic fluorosilicone resin ceramic antifouling agent comprises the following steps:
at normal temperature, adding perfluoro hydrogen-containing polymethylhydrosiloxane, nano alumina, boric acid derivative and diluent of 4/5-5/6 into a reactor, uniformly stirring, then dropwise adding a mixed solution of amino-substituted cage polysilsesquioxane and diluent of 1/6-1/5, after 0.5-1 h of dropwise addition, and continuing to react for 2-4 h; and respectively dripping polyisocyanate and polyhydroxy polysiloxane into the reactor simultaneously, continuing to react for 2-4 hours after dripping is finished for 0.5-1 hour, and taking out liquid to obtain the super-hydrophobic fluorosilicone resin ceramic antifouling agent.
The application method of the super-hydrophobic fluorosilicone resin ceramic antifouling agent comprises the following steps: in the final step of polishing the matte brick on a ceramic tile polishing production line, the matte ceramic antifouling agent is applied to the surface of the matte brick by a nylon wheel or a sponge wheel under certain pressure, and the weight is about 3-5 g/m2And the conventional antifouling and wear-resistant detection of the ceramic production line can be carried out after 5-10 min.
Compared with the prior art, the invention has the following advantages: (1) the main component of the antifouling agent is fluorosilicone resin with excellent hydrophobicity and good antifouling effect; (2) the cage-type polysilsesquioxane and polyisocyanate substituted by amino with eight functionalities are used as a crosslinking catalyst for the first time, and are synthesized by adopting a twice dripping process, so that the antifouling agent is higher in crosslinking density and uniform in crosslinking; (3) the nano alumina is used as a filler, and the boric acid derivative is used for chemical modification, so that the antifouling agent has higher hardness and better filling property; (4) the antifouling agent has small influence on the glossiness of the ceramic, and the experiment tests show that the glossiness change of the ceramic is less than 3 degrees on the premise of ensuring the antifouling effect.
Detailed Description
The super-hydrophobic fluorosilicone resin ceramic antifouling agent and the preparation method thereof according to the present invention are further described below with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A super-hydrophobic fluorosilicone resin ceramic antifouling agent is prepared by taking perfluoro hydrogen-containing polymethylhydrosiloxane as matrix resin, amino-substituted cage polysilsesquioxane and polyisocyanate as crosslinking catalysts, and nano aluminum oxide as reinforcing filler, and curing at normal temperature to obtain super-hydrophobic fluorosiliconeThe resin comprises the following specific formula components in mass: perfluoro hydrogen-containing polymethylhydrosiloxane (with hydrogen content of 1.2% and viscosity of 60 mPa.s) 15.0%, octaaminophenyl POSS 6.0%, 4' -dicyclohexylmethane diisocyanate 1.0%, and nano alumina 6.0% (with particle size of 13nm and specific surface area of 200 +/-20 m)2The coating comprises the following components of per gram), 4.0 percent of polyhydroxy polysiloxane (the viscosity is 100mPa & s, the hydroxyl content is 3.6 percent), 3.0 percent of 3-fluorophenyl boric acid and petroleum ether (the boiling range is 90-120 ℃).
The preparation method of the super-hydrophobic fluorosilicone resin ceramic antifouling agent comprises the following steps:
at normal temperature, adding a diluent of perfluoro-hydrogen-containing polymethylhydrosiloxane, nano-alumina, boric acid derivative and 5/6 into a reactor, uniformly stirring, then dropwise adding a mixed solution of amino-substituted cage polysilsesquioxane and 1/6 diluent, after 1h of dropwise addition, continuing to react for 4 h; and respectively dripping polyisocyanate and polyhydroxy polysiloxane into the reactor simultaneously, continuing to react for 3 hours after dripping is finished for 0.5 hour, and taking out liquid to obtain the super-hydrophobic fluorosilicone resin ceramic antifouling agent.
Example 2
A super-hydrophobic fluorosilicone resin ceramic antifouling agent is prepared by taking perfluoro hydrogen-containing polymethylhydrosiloxane as matrix resin, amino-substituted cage polysilsesquioxane and polyisocyanate as crosslinking catalysts, and nano aluminum oxide as reinforcing filler, wherein the normal-temperature cured super-hydrophobic fluorosilicone resin comprises the following specific formula components in mass: perfluoro hydrogen-containing polymethylhydrosiloxane (viscosity 20 mPa.s, hydrogen content 1.63%), octa-3-aminopropyl POSS 3.0%, hexamethylene diisocyanate 2.0%, nano alumina (particle size 10nm, specific surface area 230 +/-20 m)2(g) 3.0%, polyhydroxy polysiloxane (viscosity 200 mPas, hydroxyl content 2.1%), 4-n-propylphenylboronic acid 1.0%, D40 solvent 63.0%.
The preparation method of the super-hydrophobic fluorosilicone resin ceramic antifouling agent comprises the following steps:
at normal temperature, adding a diluent of perfluoro-hydrogen-containing polymethylhydrosiloxane, nano-alumina, boric acid derivative and 4/5 into a reactor, uniformly stirring, then dropwise adding a mixed solution of amino-substituted cage polysilsesquioxane and 1/5 diluent, continuously reacting for 3 hours after dropwise adding is finished for 0.8 hour; and respectively dripping polyisocyanate and polyhydroxy polysiloxane into the reactor simultaneously, continuously reacting for 4 hours after dripping is finished for 0.8 hour, and taking out liquid to obtain the super-hydrophobic fluorosilicone resin ceramic antifouling agent.
Example 3
A super-hydrophobic fluorosilicone resin ceramic antifouling agent is prepared by taking perfluoro hydrogen-containing polymethylhydrosiloxane as matrix resin, amino-substituted cage polysilsesquioxane and polyisocyanate as crosslinking catalysts, and nano aluminum oxide as reinforcing filler, wherein the normal-temperature cured super-hydrophobic fluorosilicone resin comprises the following specific formula components in mass: 17.0 percent of perfluoro hydrogen-containing polymethylhydrosiloxane (viscosity is 30mPa & s, hydrogen content is 1.48 percent), 4.0 percent of octa-3-aminopropyl POSS, 1.5 percent of isophorone diisocyanate, and nano alumina (18nm, specific surface area is 170 +/-20 m)2/g) 3.5%, polyhydroxy polysiloxane (viscosity 80 mPas, hydroxyl content 3.9%), 2.0% 3-methoxyphenylboronic acid, 36.0% D40 solvent, 15.0% kerosene, 15.0% n-heptane.
The preparation method of the super-hydrophobic fluorosilicone resin ceramic antifouling agent comprises the following steps:
at normal temperature, adding a diluent of perfluoro-hydrogen-containing polymethylhydrosiloxane, nano-alumina, boric acid derivative and 9/11 into a reactor, uniformly stirring, then dropwise adding a mixed solution of amino-substituted cage polysilsesquioxane and 2/11 diluent, after 0.5h of dropwise addition, continuing to react for 2 h; and respectively dripping polyisocyanate and polyhydroxy polysiloxane into the reactor simultaneously, continuing to react for 2 hours after dripping is finished for 0.5 hour, and taking out liquid to obtain the super-hydrophobic fluorosilicone resin ceramic antifouling agent.
Testing the film forming property: the super-hydrophobic fluorosilicone resin ceramic antifouling agent prepared in the embodiments 1, 2 and 3 is coated on the surface of a ceramic tile, and the weight of the antifouling agent is about 1-2 g/cm2The coating film performance is shown in the attached table as follows:
| example 1 | Example 2 | Example 3 | |
| Hardness of pencil | 3H | 3H | 3H |
| Contact angle of water and film | 156 | 152 | 154 |
| Light transmittance | 81％ | 82％ | 81％ |
And (3) application performance testing: the super-hydrophobic fluorosilicone resin ceramic antifouling agent in the embodiments 1, 2 and 3 is used on a ceramic tile polishing production line, in the final step of polishing the matte brick, the nylon wheel or the sponge wheel applies the matte ceramic antifouling agent on the surface of the matte brick under certain pressure, and the weight is about 5-10 g/m2And after 5-10 min, the conventional antifouling detection of the ceramic production line can be carried out, and the detection data are as follows:
| example 1 | Example 2 | Example 3 | Commercial silicone antifouling wax | |
| Gloss before polishing /) | 31±2 | 33±2 | 35±2 | 33±2 |
| Gloss after polishing/%) | 32±2 | 34±2 | 36±2 | 45±2 |
| Olive oil resistant grade | 5 | 5 | 5 | 4 |
| Blue ink/grade resistance | 5 | 5 | 5 | 3 |
| Iron oxide red resistant aqueous solution/grade | 5 | 5 | 5 | 3 |
| Chromium-resistant green aqueous solution/grade | 5 | 5 | 5 | 3 |
| Tea stain/grade resistance | 5 | 5 | 5 | 4 |
| Soy sauce resistant grade | 5 | 5 | 5 | 4 |
Claims (9)
1. The super-hydrophobic antifouling ceramic tile is characterized in that the super-hydrophobic fluorosilicone resin ceramic antifouling agent is coated on the surface of the ceramic tile and accounts for 1-2 g/cm2Obtaining the super-hydrophobic antifouling ceramic tile; the super-hydrophobic fluorosilicone resin ceramic antifouling agent is prepared by using perfluoro-hydrogenous polymethylhydrosiloxane as matrix resin, amino-substituted cage polysilsesquioxane and polyisocyanate as cross-linking catalysts and nano-alumina as reinforcing fillers.
2. The super-hydrophobic antifouling tile according to claim 1, wherein the specific formula comprises the following components in percentage by mass: 15.0 to 20.0 percent of perfluoro hydrogen-containing polymethylhydrosiloxane, 3.0 to 6.0 percent of amino substituted cage polysilsesquioxane, 1.0 to 2.0 percent of polyisocyanate, 3.0 to 6.0 percent of nano alumina, 4.0 to 8.0 percent of polyhydroxy polysiloxane, 1.0 to 3.0 percent of boric acid derivative and 60.0 to 72.0 percent of diluent.
3. A superhydrophobic, soil resistant tile according to claim 1 or 2 wherein: the viscosity of the perfluoro hydrogen-containing polymethylhydrosiloxane is 20-60 mPa & s, and the hydrogen content is 1.0-1.7%.
4. A superhydrophobic, soil resistant tile according to claim 1 or 2 wherein: the amino-substituted cage polysilsesquioxane is at least one of octaaminophenyl POSS and octa-3-aminopropyl POSS.
5. A superhydrophobic, soil resistant tile according to claim 1 or 2 wherein: the polyisocyanate is aliphatic polyisocyanate, preferably at least one of hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate and methylcyclohexyl diisocyanate.
6. A superhydrophobic, soil resistant tile according to claim 1 or 2 wherein: the nano-alumina has a particle size of 8-20 nm and a specific surface area of 150-300 m2(ii)/g; the viscosity of the polyhydroxy polysiloxane is 80-200 mPa.s, and the hydroxyl content is 2-4%.
7. The super-hydrophobic antifouling tile according to claim 2, wherein: the boric acid derivative is at least one of phenylboronic acid, 3-fluorophenyl boric acid, sec-butyl boric acid, 4-fluorophenyl boric acid, 3-methoxyphenyl boric acid, n-butyl boric acid, 2-methoxyphenyl boric acid, p-ethylphenylboronic acid, 2-fluoropyridine-3-boric acid, n-propylboronic acid, 4-n-propylphenylboronic acid and p-carboxyphenylboronic acid.
8. The super-hydrophobic antifouling tile according to claim 2, wherein: the diluent is at least one of petroleum ether, D40 solvent, kerosene, diesel oil and n-heptane.
9. The superhydrophobic antifouling tile according to any one of claims 1 to 8, wherein the superhydrophobic fluorosilicone ceramic antifouling agent of the dots comprises the steps of: at normal temperature, adding perfluoro hydrogen-containing polymethylhydrosiloxane, nano alumina, boric acid derivative and diluent of 4/5-5/6 into a reactor, uniformly stirring, then dropwise adding a mixed solution of amino-substituted cage polysilsesquioxane and diluent of 1/6-1/5, after 0.5-1 h of dropwise addition, and continuing to react for 2-4 h; and respectively dripping polyisocyanate and polyhydroxy polysiloxane into the reactor simultaneously, continuing to react for 2-4 hours after dripping is finished for 0.5-1 hour, and taking out liquid to obtain the super-hydrophobic fluorosilicone resin ceramic antifouling agent.
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| CN202011447524.7A CN112322185A (en) | 2017-11-10 | 2017-11-10 | Super-hydrophobic antifouling ceramic tile |
| CN201711102363.6A CN107858097A (en) | 2017-11-10 | 2017-11-10 | A kind of super-hydrophobic fluorine silicon resin ceramic stain control agent and preparation method thereof |
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| CN202011447524.7A Withdrawn CN112322185A (en) | 2017-11-10 | 2017-11-10 | Super-hydrophobic antifouling ceramic tile |
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| CN106750308A (en) * | 2017-02-09 | 2017-05-31 | 南京大学 | A kind of multi-hydroxy alkyl phenyl sesquisiloxane and its preparation method and purposes |
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2017
- 2017-11-10 CN CN202011447507.3A patent/CN112500793A/en not_active Withdrawn
- 2017-11-10 CN CN201711102363.6A patent/CN107858097A/en not_active Withdrawn
- 2017-11-10 CN CN202011447524.7A patent/CN112322185A/en not_active Withdrawn
- 2017-11-10 CN CN202011447517.7A patent/CN112409923A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249609A (en) * | 2021-12-06 | 2022-03-29 | 清远市简一陶瓷有限公司 | Preparation method of low-gloss antifouling brick |
| CN117229686A (en) * | 2023-11-13 | 2023-12-15 | 福建宏华集团有限公司 | Anti-slip wear-resistant glazed paint for ceramic tiles and preparation method and application thereof |
| CN117229686B (en) * | 2023-11-13 | 2024-02-23 | 福建宏华集团有限公司 | Anti-slip wear-resistant glazed paint for ceramic tiles and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107858097A (en) | 2018-03-30 |
| CN112500793A (en) | 2021-03-16 |
| CN112409923A (en) | 2021-02-26 |
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