CN108822668A - A kind of UV resistance hydrophobic coating agent and its preparation method and application - Google Patents
A kind of UV resistance hydrophobic coating agent and its preparation method and application Download PDFInfo
- Publication number
- CN108822668A CN108822668A CN201810566206.9A CN201810566206A CN108822668A CN 108822668 A CN108822668 A CN 108822668A CN 201810566206 A CN201810566206 A CN 201810566206A CN 108822668 A CN108822668 A CN 108822668A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- coupling agent
- acid
- hydrophobic coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
-
- 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
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of UV resistance hydrophobic coating agent, it includes acid-organosilicon crylic acid polymer emulsion 20-30 parts by weight, low molecular weight hydroxy-terminated dimethyl silicone polymer 2-10 parts by weight, modified array carbon nano tube 2-5 parts by weight, hydrophobicity titanium dioxide 3-8 parts by weight, dispersing agent 1-3 parts by weight, defoaming agent 0-2 parts by weight, distilled water 100-300 parts by weight；Modified array carbon nano tube and hydrophobicity titanium dioxide are using amino silicane coupling agent, fluorine containing silane coupling agent and to be handled to obtain, and finally realize that adhesive force is appropriate, hydrophobicity excellent effect.
Description
Technical field
The present invention relates to hydrophobic coating agent fields, and in particular to the stronger UV resistance hydrophobic coating agent field of adhesive force, also
It is related to the preparation method and application field of coating agent.
Background technique
Universal with automobile in recent years, the owning amount of automobile, which is presented, quickly to be increased, and bring peripheral vehicle produces therewith
Product become popular direction.In automobile in use, it is found that vehicle outer side is removed in humidity, the biggish situation of temperature spread
It will form mist layer with rearview mirror surface layer, or when rainy, rearview mirror is not seen or side glass is fuzzy, and fuzzy glass surface is tight
The sight of the influence driver of weight influences traveling vehicle safety.
In view of the above-mentioned problems, glass is generally taken to heat or the mode of mirror heater, but it is usually present certain stagnant
Property afterwards, and most of vehicle is also without above-mentioned configuration.As supplement, the hydrophilicity-imparting treatment or silicic acid anhydride of outside glass become
A kind of common mode.The hydrophilicity-imparting treatment of outside glass can play higher effect to fog, to bigger than normal for rainfall
In the case of, difficulties in dispersion selects silicic acid anhydride to become an important means.
For the demand of the silicic acid anhydride agent of glass, technical staff has carried out long-term system research, silicic acid anhydride
There are contradictions with its adhesive force, this also becomes the research hotspot and difficult point in the field.
Summary of the invention
Goal of the invention：For the problem in background technique, the present invention passes through matrix resin structure choice and dewatering filling
Preparation and compounding selection, obtain that a kind of adhesive force is appropriate, hydrophobicity is excellent while having the hydrophobic painting of the UV resistance of UV resistance characteristic
Layer agent.
The present invention also provides a kind of preparation methods of UV resistance hydrophobic coating agent.
The present invention furthermore provides a kind of application of UV resistance hydrophobic coating agent.
In order to which the technical solution for reaching said effect is as follows：
Summary of the invention
The present invention provides a kind of UV resistance hydrophobic coating agent comprising acid-organosilicon crylic acid polymer emulsion 20-30 weight
Part, low molecular weight hydroxy-terminated dimethyl silicone polymer 2-10 parts by weight, modified array carbon nano tube 2-5 parts by weight, hydrophobicity two
Titanium oxide 3-8 parts by weight, dispersing agent 1-3 parts by weight, defoaming agent 0-2 parts by weight, distilled water 100-300 parts by weight.
As further preferred technical solution, the preparation method of the modified array carbon nano tube includes：
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes as particle；
(2) hydrofluoric acid solution is added in particle obtained by step (1), stirred 10-20 minutes, it is dry；
(3) product of step (2) is added in the alcohol solution containing amino silicane coupling agent, is stirred 1 hour or so, water
It washes；
(4) product of step (3) is used fluorine containing silane coupling agent treatment 2 hours or so, is drying to obtain modified array carbon
Nanotube.
As further preferred technical solution, the hydrophobicity titanium dioxide is to be added in titanium dioxide containing amino silane idol
It in the alcohol solution for joining agent, stirs 30 minutes or so, washing；It further uses fluorine containing silane coupling agent treatment 2 hours or so, does
Dry hydrophobicity titanium dioxide to obtain the final product.
As further preferred technical solution, the acid-organosilicon crylic acid polymer emulsion using methyl methacrylate,
Methacrylic acid, butyl acrylate, methacrylic acid -2- hydroxy methacrylate and vinyltriethoxysilane obtain, volume ratio
Preferably 1-1.5：0.1-0.2：1-1.5：0.1-0.2：0.15-0.25.
As further preferred technical solution, the low molecular weight hydroxy-terminated preferred end group of dimethyl silicone polymer also contains
Alkoxy.
As further preferred technical solution, the low molecular weight hydroxy-terminated dimethyl silicone polymer molecular weight is preferably
500-3000。
As further preferred technical solution, it is described containing amino silicane coupling agent can choose A-1100, A-1120 or
One or more kinds of mixtures of Y5691.
As further preferred technical solution, the fluorine containing silane coupling agent is 17 fluorine ruthenium trimethoxysilanes.
The present invention also provides a kind of preparation methods of UV resistance hydrophobic coating agent comprising:
One, the preparation of modified array carbon nano tube
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes as particle；
(2) hydrofluoric acid solution is added in particle obtained by step (1), stirred 10-20 minutes, it is dry；
(3) product of step (2) is added in the alcohol solution containing amino silicane coupling agent, is stirred 1 hour or so, water
It washes；
(4) product of step (3) is used fluorine containing silane coupling agent treatment 2 hours or so, is drying to obtain modified array carbon
Nanotube；
Two, the preparation method of hydrophobicity titanium dioxide
It will be added in the alcohol solution containing amino silicane coupling agent, stir 30 minutes or so, washing in titanium dioxide；Into one
Step uses fluorine containing silane coupling agent treatment 2 hours or so, is drying to obtain hydrophobicity titanium dioxide；
Three, the preparation method of acid-organosilicon crylic acid polymer emulsion
Acid-organosilicon crylic acid polymer emulsion uses methyl methacrylate, methacrylic acid, butyl acrylate, methyl-prop
Olefin(e) acid -2- hydroxy methacrylate and vinyltriethoxysilane obtain, and volume ratio is preferably 1-1.5：0.1-0.2：1-1.5：
0.1-0.2：0.15-0.25；
Four, the mixing of coating agent
By acid-organosilicon crylic acid polymer emulsion 20-30 parts by weight, low molecular weight hydroxy-terminated dimethyl silicone polymer 2-10
Parts by weight, modified array carbon nano tube 2-5 parts by weight, hydrophobicity titanium dioxide 3-8 parts by weight, dispersing agent 1-3 parts by weight, defoaming
Agent 0-2 parts by weight and distilled water 100-300 parts by weight high-speed stirred, froth in vacuum.
The present invention also provides a kind of UV resistance hydrophobic coating agent in side windshield of automobile, rear seat windscreen or rearview mirror
The application of glass silicic acid anhydride.
For the understanding technical solution of the present invention for keeping technical staff more detailed, introduction in detail below.
Detailed description of the invention
The present invention provides a kind of UV resistance hydrophobic coating agent comprising acid-organosilicon crylic acid polymer emulsion 20-30 weight
Part, low molecular weight hydroxy-terminated dimethyl silicone polymer 2-10 parts by weight, modified array carbon nano tube 2-5 parts by weight, hydrophobicity two
Titanium oxide 3-8 parts by weight, dispersing agent 1-3 parts by weight, defoaming agent 0-2 parts by weight, distilled water 100-300 parts by weight.
The program is evenly dispersed other components based on water-based emulsion, with acid-organosilicon crylic acid polymer emulsion and
Low molecular weight hydroxy-terminated dimethyl silicone polymer is basic polymer, and it is poly- that acid-organosilicon crylic acid polymer contains hydrophilic acrylic acid
It closes object and contains the higher organosilicon structures of hydrophobicity.
Low molecular weight hydroxy-terminated dimethyl silicone polymer contains hydrophobic structure, and hydroxy radical content should not be too large.Modified array
Carbon nanotube and hydrophobicity titanium dioxide belong to hydrophobic filler, and above-mentioned filler has all carried out special modification, guarantee adhesive force
While increase substantially hydrophobicity.Dosage of each component is also that special selection obtains.
(acid-organosilicon crylic acid polymer emulsion)
The acid-organosilicon crylic acid polymer that the present invention uses is a kind of polymer with multi-functional group, wherein methyl-prop
E pioic acid methyl ester is as basic monomer, the intensity after providing curing of coatings；Methacrylic acid and methacrylic acid -2- hydroxy methacrylate mention
For higher adhesive force, the cohesive force of polymer is larger；Meanwhile vinyltriethoxysilane belongs to polymerizable silane monomer,
Hydrophobicity element silicon can be provided, and the stability of subsequent filler can be improved after its its hydrolysis.
Specifically, the acid-organosilicon crylic acid polymer emulsion uses methyl methacrylate, methacrylic acid, propylene
Acid butyl ester, methacrylic acid -2- hydroxy methacrylate and vinyltriethoxysilane obtain, and volume ratio is preferably 1-1.5：0.1-
0.2：1-1.5：0.1-0.2：0.15-0.25.Wherein silane monomer should not be too large, the excessive removal for influencing follow-up coating, if
It is ineffective to cross few then stable filler, influences hydrophobicity.Meanwhile methacrylic acid and methacrylic acid -2- hydroxy methacrylate provide
Higher adhesive force can also improve the dispersibility of filler to a certain degree.
It, can be excellent with reference to the bibliography for preparing of acid-organosilicon crylic acid polymer emulsion for the preparation process of polymer
It is selected as " organic silicon-acrylate polymer emulsion synthesizes and granularmetric analysis ", Zhang Qingxuan etc., chemical research and application, volume 22
4th phase, the 1.2nd restraining are standby.
(low molecular weight hydroxy-terminated dimethyl silicone polymer)
There is no particular limitation for the low molecular weight hydroxy-terminated dimethyl silicone polymer of the present invention, common poly- two containing terminal hydroxy group
Methylsiloxane all matters use.For molecular weight, the low molecular weight hydroxy-terminated dimethyl silicone polymer molecular weight is preferably
500-3000, further preferred 1000-2000.
The preferred end group of low molecular weight hydroxy-terminated dimethyl silicone polymer also contains alkoxy, which can be improved
It is acted on the silane structure in acid-organosilicon crylic acid polymer, improves the compatibility of matrix resin, the stability with filler.
The structural formula of low molecular weight hydroxy-terminated dimethyl silicone polymer is preferably：
(RO) x (OH) ySiO (SiO) n (OH) y (RO) x, x >=1, y >=1, x+y=3, n=6-70, R=-CH3 ,-
CH2CH3；As optimal technical scheme, x=2, y=1, n=40 or so, R=-CH3；
(modified array carbon nano tube)
The present invention has been selected using special hydrophobic structure, and carried out special processing to improve hydrophobic property.But
Since carbon nanotube has black, additional amount be should not be too large, subsequent also to have cooperated hydrophobic titanium dioxide.
Array carbon nano tube is used in the present invention, the foundation of the array carbon nano tube is using in the prior art
Method preparation.(1) step uses document --- " Porous Aligned Carbon Nanotube Films for Ultrahydrophobic Surfaces " below, Li Huanjun etc., high
School chemistry journal, the 5th phase of volume 22, the 759-761 pages, experimental section is prepared.
The preparation method of the modified array carbon nano tube includes：
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes as particle；
(2) hydrofluoric acid solution is added in particle obtained by step (1), stirred 10-20 minutes, it is dry；
(3) product of step (2) is added in the alcohol solution containing amino silicane coupling agent, is stirred 1 hour or so, water
It washes；
(4) product of step (3) is used fluorine containing silane coupling agent treatment 2 hours or so, is drying to obtain modified array carbon
Nanotube.
The present invention uses the array carbon nano tube grown in quartz substrate, and by tentatively crushing, but degree of grinding is also not easy
It is excessive, using most preferably using for micron-scale；Meanwhile as the quartz of substrate there is hydrophily to adopt to reduce its influence
With corroding to above-mentioned particle for the hydrofluoric acid (0.01-0.1M) of low concentration, quartz portions are reduced, but handles and uses hydrofluoric acid
Concentration should not be too large and handle the time should not be too long, if overlong time or processing use hydrofluoric acid concentration excessive, stone
English substrate is largely corroded, and the structure of array carbon nano tube can be destroyed, and seriously affects later period hydrophobic effect.
Since list is unsatisfactory with regard to the hydrophobic effect of array carbon nano tube, the present invention is intended that with fluorine containing silane coupling agent
Further silicic acid anhydride is carried out, if it is only very excellent with fluorine containing silane coupling agent hydrophobic effect, but surface adhesion force is very
Difference, it is difficult to disperse well with matrix resin.
In order to solve this problem, the present invention devises a kind of processing mode, uses the alcohol containing amino silicane coupling agent first
Aqueous solution, the particle crushed in advance, the processing time is unsuitable too long, in order to avoid influence the grafting of subsequent fluorine containing silane coupling agent.
What is used can be improved filler in the dispersion and glass attachment power of water containing amino silicane coupling agent.
Amino silicane coupling agent dosage is the 1-2% of array carbon nano tube, and fluorine containing silane coupling agent dosage is that array carbon is received
The 5-10% of mitron.Dosage selection is meant to ensure that the hydrophobization performance of titanium dioxide surmounts hydrophilicity.
It is described to can choose any silane coupling agent type containing amino, preferably A- containing amino silicane coupling agent
1100, one or more kinds of mixtures of A-1120 or Y5691.
Fluorine containing silane coupling agent can choose arbitrary fluorine-containing silane coupling agent, and the fluorine containing silane coupling agent is preferably
17 fluorine ruthenium trimethoxysilanes.The step fluorine containing silane coupling agent can be handled under subacidity aqueous solution.
(hydrophobicity titanium dioxide)
Since modified array carbon nano tube has certain color, it is added that concentration is excessive to will affect translucency, if only made
With above-mentioned modified array carbon nano tube, hydrophobic effect is fine, but is not achieved excellent.In order to further increase hydrophobicity, at the same it is simultaneous
Care for ultraviolet-resistent property, the present invention has further used silicic acid anhydride, preparation method and array carbon nano tube it is almost the same.
Specific preparation method is as follows：
It will be added in the alcohol solution containing amino silicane coupling agent, stir 30 minutes or so, washing in titanium dioxide；Into one
Step uses fluorine containing silane coupling agent treatment 2 hours or so, is drying to obtain hydrophobicity titanium dioxide.The step fluorine containing silane coupling agent
It can be handled under subacidity aqueous solution.
Amino silicane coupling agent dosage is the 1-2% of titanium dioxide, and fluorine containing silane coupling agent dosage is the 5- of titanium dioxide
10%.Dosage selection is meant to ensure that the hydrophobization performance of titanium dioxide surmounts hydrophilicity.
It is described to can choose any silane coupling agent type containing amino, preferably A- containing amino silicane coupling agent
1100, one or more kinds of mixtures of A-1120 or Y5691.
Fluorine containing silane coupling agent can choose arbitrary fluorine-containing silane coupling agent, and the fluorine containing silane coupling agent is preferably
17 fluorine ruthenium trimethoxysilanes.
(preparation method)
The present invention provides a kind of preparation method of UV resistance hydrophobic coating agent comprising:
One, the preparation of modified array carbon nano tube
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes as particle；
(2) hydrofluoric acid solution is added in particle obtained by step (1), stirred 10-20 minutes, it is dry；
(3) product of step (2) is added in the alcohol solution containing amino silicane coupling agent, is stirred 1 hour or so, water
It washes；
(4) product of step (3) is used fluorine containing silane coupling agent treatment 2 hours or so, is drying to obtain modified array carbon
Nanotube；
Two, the preparation method of hydrophobicity titanium dioxide
It will be added in the alcohol solution containing amino silicane coupling agent, stir 30 minutes or so, washing in titanium dioxide；Into one
Step uses fluorine containing silane coupling agent treatment 2 hours or so, is drying to obtain hydrophobicity titanium dioxide；
Three, the preparation method of acid-organosilicon crylic acid polymer emulsion
Acid-organosilicon crylic acid polymer emulsion uses methyl methacrylate, methacrylic acid, butyl acrylate, methyl-prop
Olefin(e) acid -2- hydroxy methacrylate and vinyltriethoxysilane obtain, and volume ratio is preferably 1-1.5：0.1-0.2：1-1.5：
0.1-0.2：0.15-0.25；
Four, the mixing of coating agent
By acid-organosilicon crylic acid polymer emulsion 20-30 parts by weight, low molecular weight hydroxy-terminated dimethyl silicone polymer 2-10
Parts by weight, modified array carbon nano tube 2-5 parts by weight, hydrophobicity titanium dioxide 3-8 parts by weight, dispersing agent 1-3 parts by weight, defoaming
Agent 0-2 parts by weight and distilled water 100-300 parts by weight high-speed stirred, froth in vacuum.
(application)
The present invention also provides a kind of UV resistance hydrophobic coating agent in side windshield of automobile, rear seat windscreen or rearview mirror
The application of glass silicic acid anhydride, the glass preferably infrequently to rub are not suitable for before often having wiper friction
Windshield.
Beneficial technical effect
The present invention by matrix resin structure choice (silicone modified acrylic resin and hydroxyl dimethyl silicone polymer) and
The preparation and compounding selection (modified array carbon nano tube and hydrophobicity titanium dioxide) of dewatering filling, it is proper to obtain a kind of adhesive force
When, hydrophobicity is excellent while having the UV resistance hydrophobic coating agent of uvioresistant characteristic.
Specific embodiment
In order to make technical work personnel's more intuitive understanding claimed technical solution of the invention of this field.Under
Face provides several embodiment and comparative examples, but above-described embodiment and comparative example do not constitute the limit to claims
System, it is any to be fallen in the scope of the present invention without prejudice to design of the invention.
(preparation of modified array carbon nano tube)
Preparation example 1
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes the particle for 1 μm or so；
(2) 0.05M hydrofluoric acid solution is added in particle obtained by 100 parts by weight steps (1), stirred 15 minutes, it is dry；
(3) product of step (2) is added in the alcohol solution of 1.5 parts by weight A-1100 containing amino silicane coupling agent, is stirred
It mixes 1 hour or so, washes；
(4) at by the product of step (3) using the 17 fluorine ruthenium trimethoxysilane of fluorine containing silane coupling agent of 8 parts by weight
Reason 2 hours or so, is drying to obtain modified array carbon nano tube A1.
Preparation example 2
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes the particle for 1 μm or so；
(2) 0.5M hydrofluoric acid solution is added in particle obtained by 100 parts by weight steps (1), stirred 15 minutes, it is dry；
(3) product of step (2) is added in the alcohol solution of 1.5 parts by weight A-1100 containing amino silicane coupling agent, is stirred
It mixes 1 hour or so, washes；
(4) at by the product of step (3) using the 17 fluorine ruthenium trimethoxysilane of fluorine containing silane coupling agent of 8 parts by weight
Reason 2 hours or so, is drying to obtain modified array carbon nano tube A2.
Preparation example 3
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes the particle for 1 μm or so；
(2) particle obtained by 100 parts by weight steps (1) is added to the alcohol of 1.5 parts by weight A-1100 containing amino silicane coupling agent
It in aqueous solution, stirs 1 hour or so, washing；
(3) at by the product of step (2) using the 17 fluorine ruthenium trimethoxysilane of fluorine containing silane coupling agent of 8 parts by weight
Reason 2 hours or so, is drying to obtain modified array carbon nano tube A3.
Preparation example 4
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes the particle for 1 μm or so；
(2) 0.05M hydrofluoric acid solution is added in particle obtained by 100 parts by weight steps (1), stirred 15 minutes, it is dry；
(3) the fluorine-containing of 1.5 parts by weight A-1100 containing amino silicane coupling agent and 8 parts by weight is added in the product of step (2)
It in the alcohol solution of 17 fluorine ruthenium trimethoxysilane of silane coupling agent, stirs 2 hours or so, washing is drying to obtain modification
Array carbon nano tube A4.
Preparation example 5
(1) quartz substrate growth carbon nanotube forms array carbon nano tube, crushes the particle for 1 μm or so；
(2) 0.05M hydrofluoric acid solution is added in particle obtained by 100 parts by weight steps (1), stirred 15 minutes, it is dry；
(3) at by the product of step (2) using the 17 fluorine ruthenium trimethoxysilane of fluorine containing silane coupling agent of 8 parts by weight
Reason 2 hours or so, washing；
(4) product of step (3) is added in the alcohol solution of 1.5 parts by weight A-1100 containing amino silicane coupling agent, is stirred
It mixes 1 hour or so, is drying to obtain modified array carbon nano tube A5.
(hydrophobicity titanium dioxide)
Preparation example 6
The alcohol of 1.5 parts by weight A-1100 containing amino silicane coupling agent will be added in 1 μm or so of 100 parts by weight of titanium dioxide
It in aqueous solution, stirs 30 minutes or so, washing；Further use the 17 fluorine decyl front three of fluorine containing silane coupling agent of 8 parts by weight
Oxysilane is handled 2 hours or so, is drying to obtain hydrophobicity titanium dioxide B1.
Preparation example 7
1.5 parts by weight A-1100 containing amino silicane coupling agent and 8 will be added in 1 μm or so of 100 parts by weight of titanium dioxide
In the alcohol solution of the 17 fluorine ruthenium trimethoxysilane of fluorine containing silane coupling agent of parts by weight, handle 2 hours or so, drying is
Obtain hydrophobicity titanium dioxide B2.
Preparation example 8
17 fluorine of fluorine containing silane coupling agent for using 10 parts by weight will be added in 1 μm or so of 100 parts by weight of titanium dioxide
The alcohol solution of ruthenium trimethoxysilane is handled 2 hours or so, is drying to obtain hydrophobicity titanium dioxide B3.
(acid-organosilicon crylic acid polymer emulsion)
Preparation example 9
The formula of the acid-organosilicon crylic acid polymer emulsion is：Methyl methacrylate, methacrylic acid, acrylic acid fourth
Ester, methacrylic acid -2- hydroxy methacrylate and vinyltriethoxysilane, volume ratio are preferably 1-1.5：0.1-0.2：1-
1.5：0.1-0.2：0.15-0.25 obtains acid-organosilicon crylic acid polymer emulsion C1.
Preparation example 10
The formula of the acid-organosilicon crylic acid polymer emulsion is：Methyl methacrylate, methacrylic acid, acrylic acid fourth
Ester, methacrylic acid -2- hydroxy methacrylate, volume ratio is preferably 1-1.5：0.1-0.2：1-1.5：0.1-0.2 obtains organosilicon
Acrylate polymer emulsion C2.
Embodiment and comparative example
Following example and comparative example are all made of through preparation method, below dosage be 0 i.e. be added without the component, prepare
Step does not contain the component yet.
General preparation process is as follows：
By acid-organosilicon crylic acid polymer emulsion, low molecular weight hydroxy-terminated dimethyl silicone polymer, modified array carbon nanometer
Pipe, hydrophobicity titanium dioxide, dispersing agent, defoaming agent and distilled water high-speed stirred, froth in vacuum.
Dosage of each component is as follows：
It * is respectively molecular weight and dosage in table
& is using conventional untreated carbon nanotube
Test result method：
In the case of non-national standard, make hydrophobic coating agent being coated in glass surface in the antifog sample that the present invention measures, it is hydrophobic
The coated weight of coating agent is 12g/m2, natural drying.
1. contact angle determination using Germany KRUSS Ke Lvshi scientific instrument Shanghai Co., Ltd contact angle determination equipment into
Row test：
2. drawing 10 × 10 small nets of 1mm × 1mm on test sample surface with sharp cutter (knife edge angle is 30 ° or so)
The fragment of test zone is cleaned down with hairbrush, then firmly clings tested small grid with 3M600 gummed paper, grabbed with hand by lattice
Gummed paper is shut down in vertical direction (90 °) with faster speed in firmly adhesive tape one end, and same position carries out 2 same tests.It calculates and protects
The grid number stayed, retain grid number is indicated with percentage, and such as retaining grid number is 100, i.e., adhesiveness is 100%.
Test result
Above-mentioned test result data takes round mode to handle；The color of comparative example 3 is deep, is not available.
Claims (10)
1. a kind of UV resistance hydrophobic coating agent, it is characterised in that：Including acid-organosilicon crylic acid polymer emulsion 20-30 parts by weight,
Low molecular weight hydroxy-terminated dimethyl silicone polymer 2-10 parts by weight, modified array carbon nano tube 2-5 parts by weight, hydrophobicity titanium dioxide
Titanium 3-8 parts by weight, dispersing agent 1-3 parts by weight, defoaming agent 0-2 parts by weight, distilled water 100-300 parts by weight.
2. UV resistance hydrophobic coating agent according to claim 1, it is characterised in that：The system of the modified array carbon nano tube
Preparation Method includes：
（1）Quartz substrate grows carbon nanotube and forms array carbon nano tube, crushes as particle；
（2）By step（1）Hydrofluoric acid solution is added in gained particle, stirs 10-20 minutes, dry；
（3）By step（2）Product be added the alcohol solution containing amino silicane coupling agent in, stir 1 hour or so, washing；
（4）By step（3）Product use fluorine containing silane coupling agent treatment 2 hours or so, be drying to obtain modified array carbon nanometer
Pipe.
3. UV resistance hydrophobic coating agent according to claim 1, it is characterised in that：The hydrophobicity titanium dioxide is dioxy
Change in titanium and be added in the alcohol solution containing amino silicane coupling agent, stirs 30 minutes or so, washing；Further use fluorine containing silane
Coupling agent treatment 2 hours or so, it is drying to obtain hydrophobicity titanium dioxide.
4. UV resistance hydrophobic coating agent according to claim 1, it is characterised in that：The acid-organosilicon crylic acid polymer cream
Liquid uses methyl methacrylate, methacrylic acid, three second of butyl acrylate, methacrylic acid -2- hydroxy methacrylate and vinyl
Oxysilane obtains, and volume ratio is preferably 1-1.5：0.1-0.2：1-1.5：0.1-0.2： 0.15-0.25.
5. UV resistance hydrophobic coating agent according to claim 1, it is characterised in that：The low molecular weight hydroxy-terminated poly- diformazan
The preferred end group of radical siloxane also contains alkoxy.
6. UV resistance hydrophobic coating agent according to claim 1 or 5, it is characterised in that：It is described low molecular weight hydroxy-terminated poly-
Dimethyl siloxane molecular weight is preferably 500-3000.
7. UV resistance hydrophobic coating agent according to claim 2 or 3, it is characterised in that：It is described to contain amino silicane coupling agent
It can choose one or more kinds of mixtures of A-1100, A-1120 or Y5691.
8. UV resistance hydrophobic coating agent according to claim 2 or 3, it is characterised in that：The fluorine containing silane coupling agent is
17 fluorine ruthenium trimethoxysilanes.
9. the preparation method of UV resistance hydrophobic coating agent according to claim 1, which is characterized in that including:
One, the preparation of modified array carbon nano tube：
（1）Quartz substrate grows carbon nanotube and forms array carbon nano tube, crushes as particle；
（2）By step（1）Hydrofluoric acid solution is added in gained particle, stirs 10-20 minutes, dry；
（3）By step（2）Product be added the alcohol solution containing amino silicane coupling agent in, stir 1 hour or so, washing；
（4）By step（3）Product use fluorine containing silane coupling agent treatment 2 hours or so, be drying to obtain modified array carbon nanometer
Pipe；
Two, the preparation method of hydrophobicity titanium dioxide：
It will be added in the alcohol solution containing amino silicane coupling agent, stir 30 minutes or so, washing in titanium dioxide；Further make
With fluorine containing silane coupling agent treatment 2 hours or so, it is drying to obtain hydrophobicity titanium dioxide；
Three, the preparation method of acid-organosilicon crylic acid polymer emulsion：
Acid-organosilicon crylic acid polymer emulsion uses methyl methacrylate, methacrylic acid, butyl acrylate, metering system
Acid -2- hydroxy methacrylate and vinyltriethoxysilane obtain, and volume ratio is preferably 1-1.5：0.1-0.2：1-1.5：0.1-
0.2： 0.15-0.25；
Four, the mixing of coating agent：
By acid-organosilicon crylic acid polymer emulsion 20-30 parts by weight, low molecular weight hydroxy-terminated dimethyl silicone polymer 2-10 weight
Part, modified array carbon nano tube 2-5 parts by weight, hydrophobicity titanium dioxide 3-8 parts by weight, dispersing agent 1-3 parts by weight, defoaming agent 0-
2 parts by weight and distilled water 100-300 parts by weight high-speed stirred, froth in vacuum.
10. UV resistance hydrophobic coating agent of any of claims 1-8 in side windshield of automobile, rear seat windscreen
Or the application of back-mirror glass silicic acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810566206.9A CN108822668A (en) | 2018-06-04 | 2018-06-04 | A kind of UV resistance hydrophobic coating agent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810566206.9A CN108822668A (en) | 2018-06-04 | 2018-06-04 | A kind of UV resistance hydrophobic coating agent and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108822668A true CN108822668A (en) | 2018-11-16 |
Family
ID=64143655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810566206.9A Withdrawn CN108822668A (en) | 2018-06-04 | 2018-06-04 | A kind of UV resistance hydrophobic coating agent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108822668A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375414A (en) * | 2023-03-31 | 2023-07-04 | 深圳市龙岗大工业区混凝土有限公司 | Anti-cracking concrete and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585635A (en) * | 2012-01-12 | 2012-07-18 | 中山大桥化工集团有限公司 | Anti-icing paint and preparation method thereof |
| CN103408990A (en) * | 2013-08-14 | 2013-11-27 | 东莞市明天纳米科技有限公司 | Nanoparticle super-hydrophobic self-cleaning wall paint and preparation method thereof |
| CN104449024A (en) * | 2014-12-30 | 2015-03-25 | 马艳荣 | Preparing method for hydrophobicity nanometer titania |
| CN104946057A (en) * | 2015-07-20 | 2015-09-30 | 安吉祺隆新型建材有限公司 | Building exterior wall coating with high contamination resistance |
| CN106433364A (en) * | 2016-09-22 | 2017-02-22 | 南开大学 | Superhydrophobicity coating based on waterborne emulsion and preparing method and application thereof |
| CN106553414A (en) * | 2016-11-26 | 2017-04-05 | 马益元 | A kind of liquid crystal display surface protection film |
| CN106800885A (en) * | 2016-12-21 | 2017-06-06 | 中国科学院兰州化学物理研究所 | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating |
| CN107189609A (en) * | 2017-05-24 | 2017-09-22 | 广州大学 | A kind of emulsion comprising micro-nano hydrophobic material and preparation method and application |
-
2018
- 2018-06-04 CN CN201810566206.9A patent/CN108822668A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585635A (en) * | 2012-01-12 | 2012-07-18 | 中山大桥化工集团有限公司 | Anti-icing paint and preparation method thereof |
| CN103408990A (en) * | 2013-08-14 | 2013-11-27 | 东莞市明天纳米科技有限公司 | Nanoparticle super-hydrophobic self-cleaning wall paint and preparation method thereof |
| CN104449024A (en) * | 2014-12-30 | 2015-03-25 | 马艳荣 | Preparing method for hydrophobicity nanometer titania |
| CN104946057A (en) * | 2015-07-20 | 2015-09-30 | 安吉祺隆新型建材有限公司 | Building exterior wall coating with high contamination resistance |
| CN106433364A (en) * | 2016-09-22 | 2017-02-22 | 南开大学 | Superhydrophobicity coating based on waterborne emulsion and preparing method and application thereof |
| CN106553414A (en) * | 2016-11-26 | 2017-04-05 | 马益元 | A kind of liquid crystal display surface protection film |
| CN106800885A (en) * | 2016-12-21 | 2017-06-06 | 中国科学院兰州化学物理研究所 | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating |
| CN107189609A (en) * | 2017-05-24 | 2017-09-22 | 广州大学 | A kind of emulsion comprising micro-nano hydrophobic material and preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| 张庆轩等: "有机硅-丙烯酸酯聚合物乳液合成及粒径分析", 《化学研究与应用》 * |
| 李凤生等: "《微纳米粉体后处理技术及应用》", 30 September 2005, 国防工业出版社 * |
| 李欢军等: "超疏水多孔阵列碳纳米管薄膜", 《高等学校化学学报》 * |
| 翟锦等: "碳纳米管阵列超双疏性质的发现", 《物理》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375414A (en) * | 2023-03-31 | 2023-07-04 | 深圳市龙岗大工业区混凝土有限公司 | Anti-cracking concrete and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69720122T2 (en) | Water-repellent coating, process for its production, and its use in coatings and for coated objects | |
| CN100360401C (en) | Aqueous dispersion of hydrophobized silicon dioxide powder comprising a dispersing agent | |
| CN102408757B (en) | Solvent-based nano silicon oxide concentrated pulp and preparation method thereof | |
| DE10330020A1 (en) | Highly filled silane preparation | |
| CN107987675A (en) | A kind of wear-resisting super hydrophobic coating composition and its preparation method and application | |
| CN101346435A (en) | Silanization polymer emulsion and preparation method and application thereof | |
| DE60301001T2 (en) | Aqueous silica dispersion | |
| WO2010006837A2 (en) | Process for preparing redispersible surface-modified silicon dioxide particles | |
| CN104177951B (en) | Anti-dazzle coating composition and its preparation and use | |
| CN106479245B (en) | Aqueous dispersions of hydrophobically modified pigment particles | |
| CN105793195B (en) | Hydrophobic particulate wet silicon dioxide, its manufacturing method and antifoaming agent | |
| JP7238975B2 (en) | Silica-coated particles and method for producing the same | |
| WO2011006684A1 (en) | Dispersion and method for modifying a surface with hydrophobized silica | |
| CN106519741B (en) | The compound super hydrophilic wear-resistant paint of silicon zirconium | |
| CN108822712A (en) | A kind of super-hydrophilic coating agent and preparation method thereof | |
| JP5553297B2 (en) | Coating composition | |
| JP4409169B2 (en) | Paint containing colored pigment particles, substrate with visible light shielding film | |
| CN108822668A (en) | A kind of UV resistance hydrophobic coating agent and its preparation method and application | |
| CN114854243B (en) | Preparation method and application of modified silicon dioxide for environment-friendly water-repellent and oil-repellent coating | |
| JP2002348538A (en) | Curing composition for coating containing scaly silica particle and cured coating film | |
| CN109971361A (en) | A kind of automobile finish polishing agent and preparation method thereof | |
| CN106398512B (en) | Super hydrophilic antifog nanometer phosphoric acid hydrogen zirconium hybridization coating | |
| WO2010006839A2 (en) | Dispersion of hydrophobicized silicon dioxide particles and granules thereof | |
| Ullah et al. | Fabrication and characterization of functionalized nano-silica based transparent superhydrophobic surface | |
| WO2017107184A1 (en) | Composition, method of making composition, and article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20181116 |
|
| WW01 | Invention patent application withdrawn after publication |