CN106905807A - Transparent hydrophobic oleophobic functional paint and its transparent hydrophobic oleophobic functional coating of formation - Google Patents
Transparent hydrophobic oleophobic functional paint and its transparent hydrophobic oleophobic functional coating of formation Download PDFInfo
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- CN106905807A CN106905807A CN201510969923.2A CN201510969923A CN106905807A CN 106905807 A CN106905807 A CN 106905807A CN 201510969923 A CN201510969923 A CN 201510969923A CN 106905807 A CN106905807 A CN 106905807A
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
The present invention provides a kind of transparent hydrophobic oleophobic functional paint, including fluorine resin, silica dioxide granule and solvent, and the mass concentration of the fluorine resin is 5-15%, and the silica dioxide granule quality is the 1-5% of fluorine resin quality；Fluorine resin includes at least one in fluoroacrylic resin, fluorocarbon resin, fluorine-containing modified polyurethane resin, fluorine-containing modified organic silicone resin, and the Oil repellent of fluorine resin is 10-50wt%；The particle diameter of silica dioxide granule is 10-40 nanometers, coupling agent modified by silicon fluoride in modified solvent；Solvent includes ethyl acetate, butyl acetate, isoamyl acetate, ethyl butyrate, acetone, butanone, cyclohexanone, toluene, dimethylbenzene or nine fluorine butyl ethers.The present invention also provides a kind of transparent hydrophobic oleophobic functional coating, is made up of above-mentioned transparent hydrophobic oleophobic functional paint.
Description
Technical field
The present invention relates to paint field, the transparent hydrophobic oleophobic functional coating of specially a kind of transparent hydrophobic oleophobic functional paint and its formation.
Background technology
Lotus effect is also called self_cleaning effect, may apply to many places, such as Water-proof and oil-proof, glass surface automatically cleaning etc..By the way that with its lotus leaf surface of the micro- sem observation of electronics surface sweeping, it finds that lotus leaf surface there are some small projections, this small projection is micron-sized, nano level projection is formed again on this micron-sized projection.The generation of lotus effect is main precisely due to the stacking of this micro-nano structure staggeredly imparts super-hydrophobic surface, therefore by the human simulation to this structure, can prepare the functional coating for being applied to waterproof and oilproof.
Preparing the method with this hydrophobic oleophobic functional coating has many kinds, common are Physical and chemical method.Including mechanical coining, vacuum coating etc., chemical method is mainly coating of fluorine material etc. to Physical.Mechanical coining is to extrude scraggly shape on required substrate surface using special installation to construct micro-nano structure, the hydrophobicity of the substrate surface being prepared is fine, surface is survivable, and will not occur the decline of performance because of the growth with use time.But many deficiencies are there is also, the requirement to equipment and precision are very high first, cost input is big, in addition the oleophobic poor performance on resulting surface.Vacuum coating is to use for plating coating materials to evaporate the surface for being re-depositing on base material under vacuum high-temperature environment, forms one layer of coating of even compact.Common plating coating materials has silica, silicon fluoride etc. for preparing hydrophobic coating.It is physical deposition yet with vacuum coating, interface binding power is weaker, easy to fall off, additionally, due to the condition of high temperature, limits the use scope of base material.Chemical method is with low cost due to simple to operate, and base material is applied widely, selection and flexible design additionally, due to filler grain and matrix resin, using more universal.
Common chemical method has the surface that such as Kynoar, polytetrafluoroethylene (PTFE) etc. are coated to base material, form hydrophobic coating, the hydrophobic oleophobic effect of the substrate surface that this mode is obtained is good, but contact angle is 120 degree to the maximum, simultaneously because the low surface of fluoropolymer can, adhesion and base material between is relatively weak, it is difficult to prepare relatively thin coating.A kind of preparation method of resistant to corrosion super-hydrophobic coat is disclosed in Chinese patent CN101992184A, ceramics, silicon compound, metal oxide or metal nitride coatings are formed on the surface of the small-bore tubing shape product such as sampling probe, probe using sol-gel process, the mechanical performance of film is improved.
The content of the invention
In view of above-mentioned deficiency, a kind of transparent hydrophobic oleophobic functional paint of present invention offer, can realize the hydrophobic oleophobicization treatment to material surface under gentle environment, cost is relatively low.The present invention additionally provides a kind of transparent hydrophobic oleophobic functional coating.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of transparent hydrophobic oleophobic functional paint, including fluorine resin, silica dioxide granule and solvent, the mass concentration of the fluorine resin is 5-15%, and the silica dioxide granule quality is the 1-5% of fluorine resin quality.
Further, the fluorine resin includes at least one in fluoroacrylic resin, fluorocarbon resin, fluorine-containing modified polyurethane resin, fluorine-containing modified organic silicone resin.
Further, the Oil repellent of the fluorine resin is 10-50wt%.
Further, the solvent includes ethyl acetate, butyl acetate, isoamyl acetate, ethyl butyrate, acetone, butanone, cyclohexanone, toluene, dimethylbenzene or nine fluorine butyl ethers.
Further, the particle diameter of the silica dioxide granule is 10-40 nanometers.
Further, the silica dioxide granule is coupling agent modified by silicon fluoride in modified solvent.
Further, the silicon fluoride coupling agent includes at least one in ten trifluoro octyl group trimethoxy silanes, tridecafluoro-n-octyltriethoxysilane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes.
Further, modified one or more included with solvent in methyl alcohol, ethanol, isopropanol, n-butanol.
A kind of transparent hydrophobic oleophobic functional coating, is made up of above-mentioned transparent hydrophobic oleophobic functional paint.
The beneficial effects of the invention are as follows, fluororesin provides film forming matter and oleophobic surface, the modified Nano particles of silicon dioxide of silicon fluoride provides micro-nano structure and hydrophobic surface, so that coating surface has super hydrophobic functional, additionally, due to easy to operate, the hydrophobic oleophobicization treatment to material surface can be realized under gentle environment, cost is relatively low.
Specific embodiment
To enable features described above of the invention and advantage to become apparent, special embodiment below is described in detail below.
The present invention provides a kind of transparent hydrophobic oleophobic functional paint, including fluorine resin, silica dioxide granule and solvent.
1. fluorine resin
Fluorine resin includes fluoroacrylic resin, fluorocarbon resin, fluorine-containing modified polyurethane resin, fluorine-containing modified organic silicone resin, and these two or more can be applied in combination individually or with its.Wherein, the Oil repellent of fluorine resin is 10-50wt%, preferably 20-50wt%, more preferably 20-40wt%.Relative to the gross mass of transparent hydrophobic oleophobic functional paint, the concentration of fluorine resin is 5-15wt%, preferably 5-12wt%, more preferably 7-12wt%.
2. silica dioxide granule
The particle diameter of silica dioxide granule is 10-40 nanometers, preferably 10-30 nanometers, more preferably 10-20 nanometers.Relative to the gross mass of fluorine resin, the content of silica dioxide granule is 1-5wt%.
Silica dioxide granule can be used by itself, or its surface can be coupling agent modified by silicon fluoride.Silicon fluoride coupling agent includes at least one in ten trifluoro octyl group trimethoxy silanes, tridecafluoro-n-octyltriethoxysilane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes, wherein preferably 17 fluorine decyl trimethoxy silanes and 17 fluorine decyl triethoxysilanes, these two or more can be applied in combination individually or with its.
The surface modification treatment of Nano particles of silicon dioxide can be carried out by following, by silica ultrasonic disperse in modified solvent, then silicon fluoride coupling agent is added in the solvent, and hydrolysis 2-6 hours is stirred at room temperature.Wherein, the solvent is selected from one or more in methyl alcohol, ethanol, isopropanol, n-butanol.
3. solvent
Solvent includes ethyl acetate, butyl acetate, isoamyl acetate, ethyl butyrate, acetone, butanone, cyclohexanone, toluene, dimethylbenzene, wherein nine fluorine butyl ethers, ethyl acetate, butyl acetate, isoamyl acetate, ethyl butyrate.
The present invention additionally provides a kind of transparent hydrophobic oleophobic functional coating, it is made up of above-mentioned transparent hydrophobic oleophobic functional paint.
Embodiment
Embodiment 1：
Fluoroacrylic resin (fluorinated volume 10%) is dissolved in butyl acetate, 5% mass concentration is configured to.By particle diameter for the silica of 10nm is processed with the ethanol solution of ten trifluoro octyl group trimethoxy silanes, hydrolysis time is centrifuged out silica, vacuum drying drying after 2 hours.The silica being modified is added in the resin solution of 5% concentration by the 1% of weight resin, by after ultrasonic 30min, obtaining the dispersion liquid of homogeneous transparent.Base material stainless steel substrates surface clean is clean, using dip coating by dispersion to stainless steel surfaces, treat that dry tack free, after 60 DEG C of drying, obtains hydrophobic oleophobic film.
Embodiment 2
Fluoroacrylic resin (fluorinated volume 30%) is dissolved in toluene, 10% mass concentration is configured to.By particle diameter for the silica of 25nm is processed with the aqueous isopropanol of tridecafluoro-n-octyltriethoxysilane, hydrolysis time is centrifuged out silica, vacuum drying drying after 2 hours.The silica being modified is added in the resin solution of 10% concentration by the 2% of weight resin, by after ultrasonic 40min, obtaining the dispersion liquid of homogeneous transparent.Base material stainless steel substrates surface clean is clean, using dip coating by dispersion to stainless steel surfaces, treat that dry tack free, after 60 DEG C of drying, obtains hydrophobic oleophobic film.
Embodiment 3
Fluorocarbon resin (fluorinated volume 50%) is dissolved in butanone, 5% mass concentration is configured to.By particle diameter for the silica of 40nm is processed with the butanol solution of 17 fluorine octyl group trimethoxy silanes, hydrolysis time is centrifuged out silica, vacuum drying drying after 2 hours.The silica being modified is added in the resin solution of 5% concentration by the 1% of weight resin, by after ultrasonic 30min, obtaining the dispersion liquid of homogeneous transparent.Base material polyimides (PI) frosting is cleaned up, using dip coating by dispersion to PI surfaces, treats that dry tack free, after 80 DEG C of drying, obtains hydrophobic oleophobic film.
Embodiment 4
Fluorocarbon resin (fluorinated volume 30%) is dissolved in nine fluorine butyl ethers, 15% mass concentration is configured to.By particle diameter for 20nm silica is processed with the methanol solution of 17 fluorine octyltri-ethoxysilanes, hydrolysis time is centrifuged out silica, vacuum drying drying after 2 hours.The silica being modified is added in the resin solution of 15% concentration by the 3% of weight resin, by after ultrasonic 40min, obtaining the dispersion liquid of homogeneous transparent.Base material stainless steel surfaces are cleaned up, using dip coating by dispersion to stainless steel surfaces, treats that dry tack free, after 80 DEG C of drying, obtains hydrophobic oleophobic film.
Embodiment 5
Fluorine-containing modified polyurethane (fluorinated volume 25%) resin is dissolved in butanone, 10% mass concentration is configured to.By particle diameter for 10nm silica is processed with the alcohol mixed solution of 17 fluorine octyl group trimethoxy silanes and ten trifluoro octyl group trimethoxy silanes, hydrolysis time is centrifuged out silica, vacuum drying drying after 2 hours.The silica being modified is added in the resin solution of 10% concentration by the 5% of weight resin, by after ultrasonic 50min, obtaining the dispersion liquid of homogeneous transparent.Base material polyimides (PI) frosting is cleaned up, using dip coating by dispersion to PI surfaces, treats that dry tack free, after 80 DEG C of drying, obtains hydrophobic oleophobic film.
Embodiment 6
Fluorine-containing modified organic silicone resin (fluorinated volume 10%) is dissolved in ethyl acetate, 15% mass concentration is configured to.By particle diameter for the silica of 40nm is processed with the aqueous isopropanol of 17 fluorine octyl group trimethoxy silanes, hydrolysis time is centrifuged out silica, vacuum drying drying after 2 hours.The silica being modified is added in the resin solution of 15% concentration by the 3% of weight resin, by after ultrasonic 50min, obtaining the dispersion liquid of homogeneous transparent.Substrate ceramic surface clean is clean, using dip coating by dispersion to ceramic surface, treat that dry tack free, after 60 DEG C of drying, obtains hydrophobic oleophobic film.
Embodiment 7 (comparative example)
Acryl-modified silicone resin resin is dissolved in ethyl acetate, 15% mass concentration is configured to.By particle diameter for the silica of 40nm is directly added in the resin solution of 15% concentration by the 3% of weight resin, by after ultrasonic 50min, obtaining the dispersion liquid of homogeneous transparent.Substrate ceramic surface clean is clean, using dip coating by dispersion to ceramic surface, treat that dry tack free, after 60 DEG C of drying, obtains film.
Surface hydrophobicity oleophobic is characterized using test water and octane in the contact angle on its surface.
From the results, it was seen that the resin in comparative example is not fluorine-containing acryl-modified silicone resin resin, also unused silicon fluoride coupling agent is surface-treated Nano particles of silicon dioxide；And the resin in embodiment 1-6 has all used fluorine resin, Nano particles of silicon dioxide has also carried out surface with silicon fluoride coupling agent and has been modified, the result for causing is that the water contact angle and oily contact angle of comparative example are smaller than other embodiment, reason is in resin, the introducing of fluorine atom enables resin to have relatively low surface, play a part of oleophobic, Nano particles of silicon dioxide surface silicon fluoride coupling agent treatment, one is to provide relatively low surface can, two are to provide micro-nano bulge-structure, both sides effect assigns the good hydrophobicity of film and oleophobic property, therefore there is more excellent hydrophobic oleophobic effect than comparative example.
Claims (9)
1. a kind of transparent hydrophobic oleophobic functional paint, including fluorine resin, silica dioxide granule and solvent, the quality of the fluorine resin
Concentration is 5-15%, and the silica dioxide granule quality is the 1-5% of fluorine resin quality.
2. transparent hydrophobic oleophobic functional paint according to claim 1, it is characterised in that the fluorine resin includes fluorine-containing propene
At least one in acid resin, fluorocarbon resin, fluorine-containing modified polyurethane resin, fluorine-containing modified organic silicone resin.
3. transparent hydrophobic oleophobic functional paint according to claim 1 and 2, it is characterised in that the Oil repellent of the fluorine resin
It is 10-50wt%.
4. transparent hydrophobic oleophobic functional paint according to claim 1, it is characterised in that the solvent includes ethyl acetate, second
Acid butyl ester, isoamyl acetate, ethyl butyrate, acetone, butanone, cyclohexanone, toluene, dimethylbenzene or nine fluorine butyl ethers.
5. transparent hydrophobic oleophobic functional paint according to claim 1, it is characterised in that the particle diameter of the silica dioxide granule is
10-40 nanometers.
6. transparent hydrophobic oleophobic functional paint according to claim 1, it is characterised in that the silica dioxide granule is in modified use
It is coupling agent modified by silicon fluoride in solvent.
7. transparent hydrophobic oleophobic functional paint according to claim 6, it is characterised in that the silicon fluoride coupling agent includes 13
Fluorine octyl group trimethoxy silane, tridecafluoro-n-octyltriethoxysilane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyls three
At least one in Ethoxysilane.
8. transparent hydrophobic oleophobic functional paint according to claim 6, it is characterised in that the modified solvent include methyl alcohol,
One or more in ethanol, isopropanol, n-butanol.
9. a kind of transparent hydrophobic oleophobic functional coating, the transparent hydrophobic oleophobic function as described in claim 1 to 8 any claim is applied
Material is made.
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| CN201510969923.2A CN106905807A (en) | 2015-12-22 | 2015-12-22 | Transparent hydrophobic oleophobic functional paint and its transparent hydrophobic oleophobic functional coating of formation |
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| CN108299880A (en) * | 2018-02-11 | 2018-07-20 | 东南大学 | A kind of aqueous super-amphiphobic coating and its preparation method and application |
| CN108384339A (en) * | 2018-01-08 | 2018-08-10 | 武汉疏能新材料有限公司 | A kind of super-hydrophobic composite coating of high durable and preparation method thereof and its porcelain insulator used |
| CN109021756A (en) * | 2018-07-02 | 2018-12-18 | 中山大学 | A kind of preparation method of the superoleophobic anti-pollution layer of resin lens |
| CN109054567A (en) * | 2018-09-03 | 2018-12-21 | 广州市绿森环保设备有限公司 | Superoleophobic spray of transparent hydrophobic and preparation method thereof |
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