CN108822603A - A kind of preparation method of coating composition - Google Patents
A kind of preparation method of coating composition Download PDFInfo
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- CN108822603A CN108822603A CN201810780642.6A CN201810780642A CN108822603A CN 108822603 A CN108822603 A CN 108822603A CN 201810780642 A CN201810780642 A CN 201810780642A CN 108822603 A CN108822603 A CN 108822603A
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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
- C09D5/08—Anti-corrosive paints
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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
- 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
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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
- 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
- C08K7/00—Use of ingredients characterised by shape
Abstract
The present invention provides a kind of preparation method of coating composition, and coating composition contains：Nano-titanium dioxide class material 0.1-5 parts by weight；Nano silica class material 0.1-10 parts by weight；Aqueous hybrid resin 0.01-5 parts by weight；Auxiliary agent 0.1-5 parts by weight；And water 1-99 parts by weight, preparation method include the following steps：A) nano-titanium dioxide class material and nano silica class material are provided, at least one of nano-titanium dioxide class material and nano silica class material are aqueous sol；B) aqueous hybrid resin, auxiliary agent are provided；C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed, obtains coating composition.The coating composition that preparation method according to the present invention obtains, without containing the organic principle being harmful to the human body, safety and environmental protection improves the hardness of coating, has corrosion resistance, and scoring resistance energy enhances adhesive force, and self-cleaning effect is good.
Description
Technical field
The present invention relates to environment protection field, in particular to a kind of preparation method of coating composition.
Background technique
Building external paint can beautify the environment and room, but since traditional coating abrasion resistance is poor, coating easily occurs
Change colour, fall off, glass curtain wall or ceramic tile veneer can bring light pollution again, increase the problems such as building is self-possessed, there are security risks.
Currently, The Surroundings in Cities pollution is aggravating, wherein dust pollution, gaseous contamination are particularly acute, and external wall is especially high-rise
Building, by increasingly severe erosion, since performance difference is difficult to meet needs, automatic cleaning coating can make traditional coating
It obtains surface contaminant or dust granule voluntarily falls off under the external forces such as gravity, rainwater, wind-force, or pass through photocatalytic degradation
It removes, has the characteristics that water-saving, energy-saving and environmental protection, therefore, how to develop and have excellent performance, the coating with automatic cleaning action is
Problem to be solved.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of coating composition.
In order to solve the above technical problems, the present invention uses following technical scheme：
The preparation method of coating composition according to an embodiment of the present invention, coating composition contain：
Nano-titanium dioxide class material 0.1-5 parts by weight；
Nano silica class material 0.1-10 parts by weight；
Aqueous hybrid resin 0.01-5 parts by weight；
Auxiliary agent 0.1-5 parts by weight；And
Water 1-99 parts by weight,
Preparation method includes the following steps：
A) the nano-titanium dioxide class material and nano silica class material, the nano-titanium dioxide class material are provided
At least one of material and nano silica class material are aqueous sol；
B) the aqueous hybrid resin, auxiliary agent are provided；
C) the nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed
It closes, obtains the coating composition.
Further, the step a) includes：
A1-1 nano-titanium dioxide colloid) is provided, the partial size of the nano-titanium dioxide colloid is 1-99nm；And
A1-2) nanometer titanium dioxide colloidal silica is provided, first disperse ethyl orthosilicate in ethanol and be warming up to 120 DEG C, so
Hydrochloric acid solution is added dropwise in backward ethyl alcohol, the nanometer titanium dioxide colloidal silica is obtained after being stirred to react, wherein ethyl alcohol and positive silicic acid second
The volume ratio of ester is 4: 1, and the molar concentration of the hydrochloric acid solution is 1M, the volume of the hydrochloric acid solution and the ethyl orthosilicate
Than being 1: 4.
Further, the step a1-1) include：
It is added to the water after isopropanol and titanium isopropoxide are mixed, is stirred after titanium dioxide precipitation, filtering precipitate is used in combination
Deionized water washs to obtain wet cake, and by the wet cake, dispersion obtains dispersion liquid again in deionized water, into dispersion liquid
Add lactic acid and be cooled to room temperature after being sufficiently mixed, and pH value is adjusted to 7.0, obtains the nano-titanium dioxide colloid.
Further, the step c) includes：
First the aqueous hybrid resin, the auxiliary agent are separately added into the nanometer titanium dioxide colloidal silica and stirred, then plus
Enter the nano-titanium dioxide powder, obtains the coating composition.
Further, the step a) includes：
A2-1) nano-titanium dioxide colloid is provided；And
A2-2) nano silica powder is provided.
Further, the step a2-1) it specifically includes：
Titanium tetrachloride is added in 0-5 DEG C of water and is stirred, ammonium hydroxide stirring is then added dropwise, adjusting PH is 7.0, obtains described receive
Rice colloidal tio 2.
Further, the nano silica is long chain nano silica, and preparation method is as follows：
Silane-modified chain carbon dust is reacted to carbon in 400-700 DEG C of air and disappeared, the long chain can be obtained
Nano silica.
Further, the step c) includes：
The nano-titanium dioxide colloid is added to the water stirring, adds the aqueous hybrid resin, the auxiliary agent simultaneously
Then stirring adds the nano silica powder stirring, obtains the coating composition, wherein the nano-silica
The mass ratio for changing titanium colloid and the nano silica powder is 1: 5.
Further, the aqueous hybrid resin includes alkyd resin, epoxy resin, acrylate, polyurethane tree
Rouge, organic siliconresin, organic fluorine, amino resins, polyester resin, organosilicon-inorganic polysiloxane, polyester modification alkyd tree
Rouge, silicone alkyd, epoxy alkyd resin, bisphenol A epoxide resin, aliphatic glycidyl ether resin, hydrogen
Change bisphenol A epoxide resin, cycloaliphatic epoxy resin, styrene-acrylic resin, pure acrylate resin, organic-silicon-modified
It is acrylate, polyester modification acrylate, acrylate-polyurethane resin, acrylate-amino resins, wet solid
Change polyurethane resin, organic siliconresin-polyurethane resin, containing hydrogen silicone oil-organic siliconresin containing double bond, fluorocarbon resin, organosilicon
Fluorocarbon modified resin, unsaturated polyester resin, polyester-urethane resin, polysiloxane resin, polysilsesquioxane resins
One of or it is a variety of.
Further, the auxiliary agent includes surfactant, initiator, dispersing agent, wetting agent, thickener, levelling agent, disappears
One of infusion, anticrater agent, anti-sagging agent, anti-flash rusting agent, UV light absorber, antiager, heat stabilizer are a variety of.
Above-mentioned technical proposal of the invention one of at least has the advantages that：
The coating composition that the preparation method of coating composition according to the present invention obtains has without containing what is be harmful to the human body
Machine ingredient, formaldehydeless equal volatile organic matters release, safety and environmental protection, nano-titanium dioxide class material enable to surface contaminant
Or dust granule is removed by photocatalytic degradation, have obvious self-cleaning effect, nano silica class material with it is aqueous miscellaneous
Changing resin has stronger chemical cooperated effect, improves the hardness of coating, has corrosion resistance, and scoring resistance energy enhances attached
Put forth effort, coating composition is coated on coated article formation automatically cleaning water nano coating, and self-cleaning effect is good, coating performance compared with
It is good.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
The technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is of the invention one
Divide embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, those of ordinary skill in the art are obtained
The every other embodiment obtained, shall fall within the protection scope of the present invention.
The preparation method of coating composition according to an embodiment of the present invention is detailed below.
The preparation method of coating composition according to an embodiment of the present invention, coating composition contain：
Nano-titanium dioxide class material 0.1-5 parts by weight；
Nano silica class material 0.1-10 parts by weight；
Aqueous hybrid resin 0.01-5 parts by weight；
Auxiliary agent 0.1-5 parts by weight；And
Water 1-99 parts by weight,
Wherein, nano-titanium dioxide class material, nano silica class material can be contained in coating composition, wherein
The specific partial size and state of nano-titanium dioxide can according to need selection, and aqueous hybrid resin can be water-soluble resin, no
Organic solvent is needed to carry out dissolving resin, without containing the organic principle being harmful to the human body, formaldehydeless equal volatile organic matters release, peace
Loopful is protected.The content of each component can select according to actual needs in coating composition, and auxiliary agent may include dispersing agent, surface work
Property agent, levelling agent etc., enable nano-titanium dioxide class material, nano silica class material to be evenly dispersed in aqueous miscellaneous
Change in resin.
The preparation method of coating composition includes the following steps：
A) nano-titanium dioxide class material and nano silica class material, nano-titanium dioxide class material and nanometer are provided
At least one of silica based materials are aqueous sol；
B) aqueous hybrid resin, auxiliary agent are provided；
C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain coating composition.
That is, providing nano-titanium dioxide class material and nanometer two first during prepares coating composition
Silica type material provides aqueous hybrid resin, auxiliary agent, wherein nano-titanium dioxide class material and nano silica class material
At least one of material is aqueous sol, for example, nano-titanium dioxide class material is colloidal sol, nano silica class material is powder
Nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed, obtain coating by body
Composition.Can be by simple physical mixed method or situ aggregation method come prepares coating composition by each component raw material, it can be with
It is prepared after each component is mixed in 0-300 DEG C of reaction 10min-100h.
Nano-titanium dioxide class material can be nano-titanium dioxide, and nano-titanium dioxide is a kind of N semiconductor material,
There are a forbidden band between valence band full of electronics and the conduction band being made of hole, when being radiated at nano-titanium dioxide film surface
The energy of ultraviolet light be greater than forbidden bandwidth, the electronics in nano-titanium dioxide valence band is excited, and transits to conduction band, while in valence
Band forms hole；Electronics in conduction band is reacted with the oxygen in air generates superoxide anion (O2-)；Hole and surface in valence
The water of absorption forms hydroxyl radical free radical (OH), and hydroxyl radical free radical has strong oxidizing property, can will be adsorbed on nano-titanium dioxide painting
The various organic matter degradations of film surface are water and carbon dioxide, so that film has preferably automatic cleaning action.
The photic hydrophily of nano-titanium dioxide film is the electron-hole pair and superficial silicon dioxide that ultraviolet excitation generates
Titanium crystal effect, forms equally distributed hydrophilic microcell and hydrophobic microcell in plane of crystal, the width of each microcell only has more than ten
A nanometer, a water droplet is big more than hydrophilic microcell, therefore, can constantly sprawl on titanium deoxid film surface, ultraviolet light exists
Titanium deoxid film surface formed hydrophilic microcell be it is unstable, stop illumination after, enrichment of the oxygen in titanium dioxide surface
Film surface hydrophilic is set gradually to decay, the contact angle on water and surface is gradually increased, and has ultraviolet lighting reflective surface again, and have
New hydrophilic microcell is formed again, irradiates hydrophilic sound as a kind of ideal superhydrophilic self-cleaning coating it is necessary to shorten light as far as possible
Between seasonable, delay the speed of dark place hydrophily decaying.The coating composition contains nano-titanium dioxide, has automatic cleaning action.
Nano silica class material and aqueous hybrid resin have stronger chemical cooperated effect, can be improved the hardness of coating, have
There is corrosion resistance, scoring resistance energy enhances adhesive force, and coating composition, which is coated on coated article, forms the painting of automatically cleaning water nano
Layer, self-cleaning effect is good, and coating performance is preferable.
The coating composition that the preparation method of coating composition according to an embodiment of the present invention obtains as a result, without containing pair
The harmful organic principle of human body, formaldehydeless equal volatile organic matters release, safety and environmental protection, nano-titanium dioxide class material can make
It obtains surface contaminant or dust granule is removed by photocatalytic degradation, there is obvious self-cleaning effect, nano silica class
Material and aqueous hybrid resin have stronger chemical cooperated effect, improve the hardness of coating, have corrosion resistance, scratch resistant
Performance enhances adhesive force, and coating composition is coated on formation automatically cleaning water nano coating on coated article, and self-cleaning effect is good,
Coating performance is preferable.
In some embodiments of the invention, step a) may include：
A1-1 nano-titanium dioxide colloid) is provided, the partial size of the nano-titanium dioxide colloid is 1-99nm；And
A1-2) nanometer titanium dioxide colloidal silica is provided, first disperse ethyl orthosilicate in ethanol and be warming up to 120 DEG C, so
Hydrochloric acid solution is added dropwise in backward ethyl alcohol, the nanometer titanium dioxide colloidal silica is obtained after being stirred to react, wherein ethyl alcohol and positive silicic acid second
The volume ratio of ester is 4: 1, and the molar concentration of the hydrochloric acid solution is 1M, the volume of the hydrochloric acid solution and the ethyl orthosilicate
Than being 1: 4.
For example, 20ml ethyl orthosilicate is taken to be dispersed in 80ml ethyl alcohol, solution is placed in the twoport flask of 500ml, is added
Enter magneton stirring, stirring rate is 600 turns/min, and then flask is placed in heater and is heated to 120 DEG C, is stated then up molten
The hydrochloric acid solution 5ml of 1M is added in liquid to get nanometer titanium dioxide colloidal silica, the partial size of nanometer titanium dioxide colloidal silica is 5-99nm,
The partial size of nanometer titanium dioxide colloidal silica is smaller, and film self-cleaning effect is good.
According to some embodiments of the present invention, step a1-1) include：
It is added to the water after isopropanol and titanium isopropoxide are mixed, is stirred after titanium dioxide precipitation, filtering precipitate is used in combination
Deionized water washs to obtain wet cake, and by wet cake, dispersion obtains dispersion liquid again in deionized water, into dispersion liquid plus newborn
Acid is simultaneously cooled to room temperature after being sufficiently mixed, and pH value is adjusted to 7.0, obtains nano-titanium dioxide colloid, nano-silica
Under the partial size for changing titanium valve body, good evenness is easily dispersed, and film self-cleaning effect is good.
For example, the 50g titanium isopropoxide of 50g isopropanol is added slowly to 250g deionized water with vigorous stirring
In, after titanium dioxide precipitation, continues to stir 10min or more, sediment is filtered and is washed with 500g deionized water, wash
The wet cake crossed disperses again in deionized water, and being operated repeatedly to the total weight of dispersion is 250g.It is added into dispersion
6g lactic acid is simultaneously sufficiently mixed, then at 80 DEG C high-speed stirred for 24 hours, after colloidal sol is cooled to room temperature, pH value 2.6, to
Organic amine being added in colloidal sol, pH value being adjusted to 7.0 to get nano-titanium dioxide colloid is arrived, nano-titanium dioxide colloid is averaged
Partial size is 4.6nm.
Other embodiments according to the present invention, the step c) include：
First aqueous hybrid resin, auxiliary agent are separately added into nanometer titanium dioxide colloidal silica and stirred, nanometer titanium dioxide is added
Titanium valve body, obtains coating composition.Method is simple, and the coatings combine physical performance of preparation is good, and ageing-resistant, self-cleaning ability is strong.
In the implementation process of some embodiments of the invention, step a) may include：
A2-1) nano-titanium dioxide colloid is provided；And
A2-2) nano silica powder is provided.
According to some embodiments of the present invention, step a2-1) it can specifically include：
Titanium tetrachloride is added in 0-5 DEG C of water and is stirred, ammonium hydroxide stirring is then added dropwise, adjusting PH is 7.0, obtains nanometer two
Titanium oxide colloid, nano-titanium dioxide colloidal particle size is small, good evenness.
Other embodiments according to the present invention, nano silica are long chain nano silica, wherein long chain
Nano silica powder is easy to form rough micro nano structure in substrate surface, is conducive to improve water nano coating
Super-hydrophobic automatic cleaning effect.Long chain nano silica powder can be prepared by the following method：By silane-modified chain
Carbon dust reacts about 0.5-2 hours in 400-700 DEG C of air, and after handling in 400-700 DEG C of air, carbon finally disappears,
The long chain nano silica of stomach lining structure can be obtained, method is simple.
In some embodiments of the invention, the step c) includes：
Nano-titanium dioxide colloid is added to the water stirring, add aqueous hybrid resin, auxiliary agent and is stirred, is then added again
Enter nano silica powder stirring, high-speed stirred obtains coating composition after uniform stirring disperses, wherein nanometer two
The mass ratio of titanium oxide colloid and nano silica powder is 1: 5.It, can be in vacuum in order to avoid the generation of bubble in resin
It is stirred under environment.
In some embodiments of the invention, aqueous hybrid resin may include alkyd resin, epoxy resin, propylene
Acid ester resin, polyurethane resin, organic siliconresin, organic fluorine, amino resins, polyester resin, organosilicon-inorganic silicon tree
Rouge, polyester modification alkyd resin, silicone alkyd, epoxy alkyd resin, bisphenol A epoxide resin, aliphatic
Glycidyl ether resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin, styrene-acrylic resin, pure acrylic acid
Ester resin, Silicone-Modified Acrylate Resin, polyester modification acrylate, acrylate-polyurethane resin, acrylic acid
Ester-amino resins, moisture-cure polyurethane resin, organic siliconresin-polyurethane resin, containing hydrogen silicone oil-organic siliconresin containing double bond,
Fluorocarbon resin, organic-silicon-modified fluorocarbon resin, unsaturated polyester resin, polyester-urethane resin, polysiloxane resin,
One of polysilsesquioxane resins are a variety of, for example, aqueous hybrid resin may include alkyd resin, it may include poly- ammonia
Ester resin and organic siliconresin can also reasonably select according to the actual situation.
In other embodiments of the invention, auxiliary agent may include surfactant, initiator, dispersing agent, wetting agent,
Thickener, levelling agent, defoaming agent, anticrater agent, anti-sagging agent, anti-flash rusting agent, UV light absorber, antiager, heat stabilizer
One of or it is a variety of, for example, auxiliary agent may include surfactant, may include dispersing agent and levelling agent, be conducive to nanometer material
Material disperses in resin, is easy to levelling, can also include defoaming agent and antiager, avoid the generation of bubble in resin, prevent
Contain bubble, the performance of respective coatings in the coating of generation, antiager can enhance the ageing resistance of coating.
The coating composition that the preparation method of coating composition according to an embodiment of the present invention obtains, without containing having to human body
Harmful organic principle, formaldehydeless equal volatile organic matters release, safety and environmental protection, nano-titanium dioxide class material enable to surface
Pollutant or dust granule are removed by photocatalytic degradation, have obvious self-cleaning effect, nano silica class material with
Aqueous hybrid resin have stronger chemical cooperated effect, improve the hardness of coating, have corrosion resistance, scoring resistance energy,
Enhance adhesive force, coating composition is coated on formation automatically cleaning water nano coating on coated article, and self-cleaning effect is good, coating
It can be preferably.
In some embodiments of the invention, nano-titanium dioxide class material may include nano-titanium dioxide powder, receive
Rice colloidal tio 2 can also contain its mixture, can only include nano-titanium dioxide powder, also may include nanometer
Titanium dioxide powder and nano-titanium dioxide colloid, enable to nano-titanium dioxide by nano-titanium dioxide powder or colloid
It is mixed well with resin.
In other embodiments of the invention, the partial size of nano-titanium dioxide powder can be 3-20nm, nano-silica
The partial size for changing titanium colloid can be 1-99nm, and the nano-titanium dioxide in this particle size range can be evenly dispersed with resin, from
Cleaning effect is good.
According to some embodiments of the present invention, nano silica class material may include nano silica powder, receive
Or mixtures thereof rice silicon dioxide colloid, it may include nanometer titanium dioxide for example, nanometer titanium dioxide colloidal silica can be only included
Silicon powder and nanometer titanium dioxide colloidal silica, are easy to mix with resin, and uniformity is good.
Other embodiments according to the present invention, nano silica powder can be long-chain shape nano-silica powder
Body, partial size can be 50-2000nm；The partial size of nanometer titanium dioxide colloidal silica can be 5-99nm, wherein long chain nanometer two
Silica powder is easy to form rough micro nano structure in substrate surface, and it is super-hydrophobic to be conducive to raising water nano coating
Automatic cleaning action.Long chain nano silica powder can be prepared by the following method：Silane-modified chain can be used
Carbon dust, after handling in 400-700 DEG C of air, carbon finally disappears, and can be prepared by the long chain nanometer titanium dioxide of stomach lining structure
Silicon powder, method are simple.
The coating composition that the preparation method of coating composition according to an embodiment of the present invention obtains, without containing having to human body
Harmful organic principle, formaldehydeless equal volatile organic matters release, safety and environmental protection, nano-titanium dioxide class material enable to surface
Pollutant or dust granule are removed by photocatalytic degradation, have obvious self-cleaning effect, nano silica class material with
Aqueous hybrid resin have stronger chemical cooperated effect, improve the hardness of coating, have corrosion resistance, scoring resistance energy,
Enhance adhesive force, coating composition is coated on formation automatically cleaning water nano coating on coated article, and self-cleaning effect is good, coating
It can be preferably.
The coating composition that the preparation method of coating composition according to the present invention obtains is coated on coated article and is formed certainly
Aqueous nano coating is cleaned, the coating ageing-resistant performance is good, and self-cleaning performance is strong, not easily to fall off.Coating composition can pass through spray
It applies or roll coating model is applied directly on base material, coating composition can be widely used for calcium silicate board, cement fibrolite plate, artificial
And the natural marble space of a whole page, various insulation layer surfaces, glass concrete (GRC), fibre reinforced composites (FRP)
The assembled architectures such as moulding material enterprise can be used for the tables such as cement wall surface, cement flooring, FRP Columns, special-shaped deep cylinder, lines
Face coating is also used directly for the inner-outer wall of the high-grade building such as school, hospital, hotel, office building, government-works, villa
The surface of coating, effective protection coated article is not damaged, so that the surface of coated article has automatic cleaning action, removes surface contamination
Object.
In some structural bodies, structural body may include coated article and the coating that is formed on coated article, wherein coating
Can according to the embodiment of the present invention automatically cleaning water nano coating, be coated with the works of automatically cleaning water nano coating from clear
Clean performance is strong, can remove the pollutant on coated article surface.
Below with reference to some specific embodiments, coating composition according to the present invention is described further.
Embodiment 1
Coating composition contains：
0.1 parts by weight of nano-titanium dioxide class material；
10 parts by weight of nano silica class material；
5 parts by weight of aqueous hybrid resin；
0.1 parts by weight of auxiliary agent；And
99 parts by weight of water,
Preparation method includes the following steps：
A) nano-titanium dioxide class material and nano silica class material, nano-titanium dioxide class material and nanometer are provided
At least one of silica based materials are aqueous sol；
B) aqueous hybrid resin, auxiliary agent are provided；
C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain coating composition.
Wherein, step a) includes：
A1-1 nano-titanium dioxide colloid) is provided, the partial size of the nano-titanium dioxide colloid is 1-99nm；And
A1-2) nanometer titanium dioxide colloidal silica is provided, take 20ml ethyl orthosilicate to be dispersed in 80ml ethyl alcohol, solution is placed in
In the twoport flask of 500ml, magneton stirring is added, stirring rate is 600 turns/min, and then flask is placed in heater and is heated
To 120 DEG C, states the hydrochloric acid solution 5ml of 1M is added in solution to get nanometer titanium dioxide colloidal silica then up.
The preparation method of nano-titanium dioxide colloid includes：
The 50g titanium isopropoxide of 50g isopropanol is added slowly in 250g deionized water with vigorous stirring,
After titanium dioxide precipitation, continues to stir 10min or more, then filtering precipitate and be washed with 500g deionized water.It will washing
The wet cake crossed is 250g in the total weight that deionized water is dispersed to dispersion again.6g lactic acid is added into dispersion and is carried out
It is sufficiently mixed, then for 24 hours, after colloidal sol is cooled to room temperature, pH value 2.6 is added with high-speed stirred into colloidal sol at 80 DEG C
PH value is adjusted to 7.0 to get nano-titanium dioxide colloid is arrived by machine amine.
During the preparation process, first aqueous hybrid resin, auxiliary agent are separately added into nanometer titanium dioxide colloidal silica and are stirred, then plus
Enter nano-titanium dioxide powder, obtains coating composition.
Aqueous hybrid resin includes polyurethane resin, organic siliconresin, polyester resin, organosilicon-inorganic polysiloxane.
Auxiliary agent includes surfactant, dispersing agent, defoaming agent, antiager, heat stabilizer.
Embodiment 2
Coating composition contains：
5 parts by weight of nano-titanium dioxide class material；
10 parts by weight of nano silica class material；
0.01 parts by weight of aqueous hybrid resin；
5 parts by weight of auxiliary agent；And
1 parts by weight of water,
Preparation method includes the following steps：
A) nano-titanium dioxide class material and nano silica class material, nano-titanium dioxide class material and nanometer are provided
At least one of silica based materials are aqueous sol；
B) aqueous hybrid resin, auxiliary agent are provided；
C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain coating composition.
Step a) includes：
A2-1) nano-titanium dioxide colloid is provided；And
A2-2) nano silica powder is provided.
Step a2-1) it specifically includes：Titanium tetrachloride is added in 5 DEG C of water and is stirred, ammonium hydroxide is then added dropwise and stirs
It mixes, adjusting PH is 7.0, obtains nano-titanium dioxide colloid.
Nano silica is long chain nano silica, and preparation method is as follows：
Silane-modified chain carbon dust is reacted into 0.5h in 700 DEG C of air, long chain nano silica can be obtained.
The preparation method of coating composition is as follows：
Nano-titanium dioxide colloid is added to the water stirring, add aqueous hybrid resin, auxiliary agent and is stirred, is then added again
Enter nano silica powder stirring, obtains coating composition, wherein nano-titanium dioxide colloid and nano silica powder
Mass ratio be 1: 5.
Aqueous hybrid resin includes alkyd resin, acrylate, polyurethane resin, organic siliconresin, Organic fluoride tree
Rouge, amino resins, polyester resin, organosilicon-inorganic polysiloxane.
Auxiliary agent includes surfactant, dispersing agent, wetting agent, levelling agent, defoaming agent, antiager, heat stabilizer.
Embodiment 3
Coating composition contains：
5 parts by weight of nano-titanium dioxide class material；
10 parts by weight of nano silica class material；
0.01 parts by weight of aqueous hybrid resin；
5 parts by weight of auxiliary agent；And
1 parts by weight of water,
Preparation method includes the following steps：
A) nano-titanium dioxide class material and nano silica class material, nano-titanium dioxide class material and nanometer are provided
At least one of silica based materials are aqueous sol；
B) aqueous hybrid resin, auxiliary agent are provided；
C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain coating composition.
Step a) includes：
A2-1) nano-titanium dioxide colloid is provided；And
A2-2) nano silica powder is provided.
Step a2-1) it specifically includes：Titanium tetrachloride is added in 0 DEG C of water and is stirred, ammonium hydroxide is then added dropwise and stirs
It mixes, adjusting PH is 7.0, obtains nano-titanium dioxide colloid.
Nano silica is long chain nano silica, and preparation method is as follows：
Silane-modified chain carbon dust is reacted into 2h in 400 DEG C of air, long chain nano silica can be obtained.
The preparation method of coating composition is as follows：
Nano-titanium dioxide colloid is added to the water stirring, add aqueous hybrid resin, auxiliary agent and is stirred, is then added again
Enter nano silica powder stirring, obtains coating composition, wherein nano-titanium dioxide colloid and nano silica powder
Mass ratio be 1: 5.
Aqueous hybrid resin includes alkyd resin, acrylate, polyurethane resin, organic siliconresin, Organic fluoride tree
Rouge, amino resins, polyester resin, organosilicon-inorganic polysiloxane.
Auxiliary agent includes surfactant, dispersing agent, wetting agent, levelling agent, defoaming agent, antiager, heat stabilizer.
Embodiment 4
Coating composition contains：
0.1 parts by weight of nano-titanium dioxide class material；10 parts by weight of nano silica class material；Aqueous hybrid resin
0.01 parts by weight；0.1 parts by weight of auxiliary agent；And 99 parts by weight of water.
Preparation method includes the following steps：
A) nano-titanium dioxide class material and nano silica class material, nano-titanium dioxide class material and nanometer are provided
At least one of silica based materials are aqueous sol；
B) aqueous hybrid resin, auxiliary agent are provided；
C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain coating composition.
Aqueous hybrid resin include alkyd resin, epoxy resin, acrylate, polyurethane resin, organic siliconresin,
Organic fluorine, amino resins, polyester resin.
Auxiliary agent includes surfactant, dispersing agent, wetting agent, levelling agent, defoaming agent, anticrater agent, anti-sagging agent, UV light
Absorbent, antiager, heat stabilizer.
Embodiment 5
Coating composition contains：
5 parts by weight of nano-titanium dioxide class material；0.1 parts by weight of nano silica class material；5 weight of aqueous hybrid resin
Measure part；5 parts by weight of auxiliary agent；And 1 parts by weight of water.
Preparation method includes the following steps：
A) nano-titanium dioxide class material and nano silica class material, nano-titanium dioxide class material and nanometer are provided
At least one of silica based materials are aqueous sol；
B) aqueous hybrid resin, auxiliary agent are provided；
C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain coating composition.
Aqueous hybrid resin include alkyd resin, epoxy resin, acrylate, polyurethane resin, organic siliconresin,
Organic fluorine, amino resins, polyester resin.
Auxiliary agent includes surfactant, dispersing agent, wetting agent, levelling agent, defoaming agent, anticrater agent, anti-sagging agent, UV light
Absorbent, antiager, heat stabilizer.
Embodiment 6
Coating composition contains：
3 parts by weight of nano-titanium dioxide class material；5 parts by weight of nano silica class material；3 weight of aqueous hybrid resin
Part；3 parts by weight of auxiliary agent；And 50 parts by weight of water.
Preparation method includes the following steps：
A) nano-titanium dioxide class material and nano silica class material, nano-titanium dioxide class material and nanometer are provided
At least one of silica based materials are aqueous sol；
B) aqueous hybrid resin, auxiliary agent are provided；
C) nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain coating composition.
Aqueous hybrid resin include alkyd resin, epoxy resin, acrylate, polyurethane resin, organic siliconresin,
Organic fluorine, amino resins, polyester resin.
Auxiliary agent includes surfactant, dispersing agent, wetting agent, levelling agent, defoaming agent, anticrater agent, anti-sagging agent, UV light
Absorbent, antiager, heat stabilizer.
In order to further investigate the effect of coating composition, coating that the method using embodiment 1 to embodiment 6 is obtained
Composition, selects roll coating model to be coated in FPR plate surface, and test result is as shown in table 1：
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Environment-friendly type | Environmental protection | Environmental protection | Environmental protection | Environmental protection | Environmental protection | Environmental protection |
| Hardness | 5H | 6H | 6H | 6H | 6H | 5H |
| Automatically cleaning | It is good | It is good | It is good | It is good | It is good | It is good |
| Artificial ageing resistance | ≥3000h | ≥3000h | ≥3000h | ≥3000h | ≥3000h | ≥3000h |
| Abrasion resistance | >=3000 times | >=3000 times | >=3000 times | >=3000 times | >=3000 times | >=3000 times |
| Tensile property | It is good | It is good | It is good | It is good | It is good | It is good |
According to result in table it is found that coating is all environment-friendly type, for coating hardness between 5H-6H, automatically cleaning degree is good, resistance to artificial
Ageing time is both greater than 3000h, and abrasion resistance is both greater than 3000 times, and tensile property is good.
The coating composition prepared through the foregoing embodiment, it is formaldehydeless etc. to wave without containing the organic principle being harmful to the human body
The organic matter release of hair property, safety and environmental protection, nano-titanium dioxide class material enable to surface contaminant or dust granule to pass through light
Catalytic degradation and remove, there is obvious self-cleaning effect, nano silica class material and aqueous hybrid resin are with stronger
Chemical cooperated effect improves the hardness of coating, has corrosion resistance, and scoring resistance energy enhances adhesive force, and coating composition applies
Cloth forms automatically cleaning water nano coating on coated article, and self-cleaning effect is good, and coating performance is preferable.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of coating composition, which is characterized in that the coating composition contains：
Nano-titanium dioxide class material 0.1-5 parts by weight；
Nano silica class material 0.1-10 parts by weight；
Aqueous hybrid resin 0.01-5 parts by weight；
Auxiliary agent 0.1-5 parts by weight；And
Water 1-99 parts by weight,
The preparation method comprises the following steps：
A) the nano-titanium dioxide class material and nano silica class material be provided, the nano-titanium dioxide class material and
At least one of nano silica class material is aqueous sol；
B) the aqueous hybrid resin, auxiliary agent are provided；
C) the nano-titanium dioxide class material, nano silica class material, aqueous hybrid resin, auxiliary agent are mixed,
Obtain the coating composition.
2. preparation method according to claim 1, which is characterized in that the step a) includes：
A1-1 nano-titanium dioxide colloid) is provided, the partial size of nano-titanium dioxide colloid is 1-99nm；And
A1-2) nanometer titanium dioxide colloidal silica is provided, ethyl orthosilicate dispersion in ethanol and is first warming up to 120 DEG C, then to
Hydrochloric acid solution is added dropwise in ethyl alcohol, the nanometer titanium dioxide colloidal silica is obtained after being stirred to react, wherein ethyl alcohol and ethyl orthosilicate
Volume ratio is 4:1, the molar concentration of the hydrochloric acid solution is 1M, and the volume ratio of the hydrochloric acid solution and the ethyl orthosilicate is
1:4。
3. preparation method according to claim 2, which is characterized in that the step a1-1) include：
Will isopropanol and titanium isopropoxide mix after be added to the water, stirred after titanium dioxide precipitation, filtering precipitate and spend from
Sub- water washing obtains wet cake, and by the wet cake, dispersion obtains dispersion liquid again in deionized water, into dispersion liquid plus newborn
Acid is simultaneously cooled to room temperature after being sufficiently mixed, and pH value is adjusted to 7.0, obtains the nano-titanium dioxide colloid.
4. preparation method according to claim 3, which is characterized in that the step c) includes：
First the aqueous hybrid resin, the auxiliary agent are separately added into the nanometer titanium dioxide colloidal silica and stirred, institute is added
Nano-titanium dioxide powder is stated, the coating composition is obtained.
5. preparation method according to claim 1, which is characterized in that the step a) includes：
A2-1) nano-titanium dioxide colloid is provided；And
A2-2) nano silica powder is provided.
6. preparation method according to claim 5, which is characterized in that the step a2-1) it specifically includes：
Titanium tetrachloride is added in 0-5 DEG C of water and is stirred, ammonium hydroxide stirring is then added dropwise, adjusting PH is 7.0, obtains the nanometer two
Titanium oxide colloid.
7. preparation method according to claim 6, which is characterized in that the nano silica is long chain nano-silica
SiClx, preparation method are as follows：
Silane-modified chain carbon dust is reacted to carbon in 400-700 DEG C of air and disappeared, the long chain nanometer can be obtained
Silica.
8. preparation method according to claim 6, which is characterized in that the step c) includes：
The nano-titanium dioxide colloid is added to the water stirring, add the aqueous hybrid resin, the auxiliary agent and is stirred,
Then the nano silica powder stirring is added, obtains the coating composition, wherein the nano-titanium dioxide glue
The mass ratio of body and the nano silica powder is 1:5.
9. preparation method according to claim 1, which is characterized in that the aqueous hybrid resin includes alkyd resin, ring
It is oxygen resin, acrylate, polyurethane resin, organic siliconresin, organic fluorine, amino resins, polyester resin, organic
Silicon-inorganic polysiloxane, polyester modification alkyd resin, silicone alkyd, epoxy alkyd resin, bisphenol-A epoxy
Resin, aliphatic glycidyl ether resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin, cinnamic acrylic ester tree
Rouge, pure acrylate resin, Silicone-Modified Acrylate Resin, polyester modification acrylate, acrylate-polyurethane
Resin, acrylate-amino resins, moisture-cure polyurethane resin, organic siliconresin-polyurethane resin, containing hydrogen silicone oil-contain double bond
Organic siliconresin, fluorocarbon resin, organic-silicon-modified fluorocarbon resin, unsaturated polyester resin, polyester-urethane resin, gather it is organic
One of silicone resin, polysilsesquioxane resins are a variety of.
10. preparation method according to claim 1, which is characterized in that the auxiliary agent include surfactant, initiator,
It is dispersing agent, wetting agent, thickener, levelling agent, defoaming agent, anticrater agent, anti-sagging agent, anti-flash rusting agent, UV light absorber, resistance to old
One of agent, heat stabilizer are a variety of.
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