CN102304326B - Coating and preparation method thereof - Google Patents
Coating and preparation method thereof Download PDFInfo
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- CN102304326B CN102304326B CN 201010254124 CN201010254124A CN102304326B CN 102304326 B CN102304326 B CN 102304326B CN 201010254124 CN201010254124 CN 201010254124 CN 201010254124 A CN201010254124 A CN 201010254124A CN 102304326 B CN102304326 B CN 102304326B
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Abstract
The invention relates to a coating, which comprises the following components: TiOx(OH)y(OR)z alcosol and a film forming component, wherein in the TiOx(OH)y(OR)z alcosol, x is not 0, z is not 0, x+(y+z)/2=2, and R refers to straight-chain or alkyl group with 2 to 9 carbon atoms, straight-chain or alkyl group with 3 to 6 carbon atoms preferably, and normal-butyl more preferably; TiOx(OH)y(OR)z fine particles of the alcosol have the particle size of 1-10nm; and a weight ratio of the TiOx(OH)y(OR)z alcosol based on titanium dioxide to the film forming component is 1:(15-85), 1:(20-65) preferably, and 1:(25-50) more preferably. The invention also relates to a method for preparing the coating. A coat prepared from the coating is smooth and flat, has formaldehyde purifying efficiency of about 82 percent and methylbenzene purifying efficiency of about 37 percent.
Description
Technical field
The present invention relates to a kind of coating, more specifically, relate to and contain TiO
x(OH)
y(OR)
zThe coating of alcosol.The invention further relates to the preparation method of described coating.
Background technology
Along with the raising of people's living standard, building coating is had higher requirement.Require building coating not only to have decoration functions, also have simultaneously radioprotective, degraded obnoxious flavour, purify air, the function such as sterilization and disinfection.
Nano titanium oxide safety non-toxic, stable, long service life.Under the condition that Guang Heshui exists, it has very strong Degradation and bacterium is had very strong killing action airborne obnoxious flavour such as oxynitride, formaldehyde, toluene etc.Simultaneously, nano titanium oxide has very strong ultraviolet absorption ability, can greatly reduce ultraviolet ray to the invasion and attack of macromolecular material, reduces the generation of living radical, and the protection macromolecular material is not degraded by ultraviolet ray.Therefore, nano titanium oxide can give coating good purify air, the performance such as antibacterium and radioprotective.Nano titanium oxide is applied to open up new approach for developing functional coating in the coating.
Nanoparticle in the nano paint often directly adds in the resin matrix with the form of auxiliary agent.Because the particle diameter of nano titanium oxide is little, specific surface energy is large, and it is very easy to reunite in coating or can be dispersed in the coating by pigment, filler embedding.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the paint field that contains nanoparticle, in the hope of obtaining a kind of titanium dioxide nano-particle Uniform Dispersion coating therein, the coating that is obtained by described coating has good appearance and shows the PARA FORMALDEHYDE PRILLS(91,95) of raising and the purification efficiency of toluene.Found that the TiO by being made by tetralkyl titanate
x(OH)
y(OR)
zAlcosol, film-forming components, optional pigment and filler and optional auxiliary agent mix the coating that can obtain to satisfy above-mentioned requirements in solvent.The present invention just is being based on above-mentioned discovery and is being accomplished.
The purpose of this invention is to provide a kind of TiO of containing
x(OH)
y(OR)
zThe coating of alcosol.
Another object of the present invention provides a kind of method for preparing above-mentioned coating.
One aspect of the present invention provides a kind of coating, and described coating comprises following component:
A) TiO
x(OH)
y(OR)
zAlcosol, wherein:
X is not 0;
Z is not 0;
X+ (y+z)/2=2; With
R represents to have the straight or branched alkyl of 2-9 carbon atom, preferably has the straight or branched alkyl of 3-6 carbon atom, more preferably normal-butyl;
The TiO of described alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 1-10nm;
With
B) film-forming components;
Wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 15-85 is preferably 1: 20-65, more preferably 1: 25-50.
The present invention provides a kind of method for preparing coating on the other hand, said method comprising the steps of:
1) stirring is lower is added drop-wise to tetralkyl titanate Ti (OR) with alcoholic solution
4Middle acquisition TiO
x(OH)
y(OR)
zAlcosol, wherein:
X is not 0;
Z is not 0;
X+ (y+z)/2=2; With
R represents to have the straight or branched alkyl of 2-9 carbon atom, preferably has the straight or branched alkyl of 3-6 carbon atom, more preferably normal-butyl;
The TiO of described alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 1-10nm;
Wherein:
Alcoholic solution is the aqueous solution of ethanol, propyl alcohol or butanols;
The mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.1-5 is preferably 1: 0.2-4, more preferably 1: 0.3-3; With
Rate of addition is 0.2-8ml/min, is preferably 0.3-6ml/min, more preferably 0.5-3ml/min; With
2) with TiO
x(OH)
y(OR)
zAlcosol, film-forming components, optional pigment and filler and optional auxiliary agent mix in solvent, wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 15-85 is preferably 1: 20-65, more preferably 1: 25-50.
In coating of the present invention, because the condensation TiO that do not have complete hydrolysis of titanium dioxide take particle diameter as about 1-10nm
x(OH)
y(OR)
zThe minuteness particle form exists, and its consistency with paint solvent is fine, so can be evenly dispersed in the coating.With described application of paints behind material surface to be coated, because TiO
x(OH)
y(OR)
zDuring minuteness particle substantially was fixed on and films, when making it further during hydrolysis, the condensation degree of hydrolysis gained titanium dioxide nano-particle can significantly not improve, and finally caused gained titanium dioxide nano-particle size homogeneous and was evenly distributed in the final coating.The purification efficiency that records its PARA FORMALDEHYDE PRILLS(91,95) according to JC/T1074-2008 " function of purifying indoor air coating material purifying property " is up to about 82%, to the purification efficiency of toluene up to about 37%.
These and other purposes, features and advantages of the present invention will be easy to be understood by those skilled after integral body is considered the present invention.
Embodiment
Coating of the present invention comprises following component: A) TiO
x(OH)
y(OR)
zAlcosol, wherein: x is not 0; Z is not 0; X+ (y+z)/2=2; Represent to have the straight or branched alkyl of 2-9 carbon atom with R, preferably have the straight or branched alkyl of 3-6 carbon atom, more preferably normal-butyl; And B) film-forming components; Wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 15-85 is preferably 1: 20-65, more preferably 1: 25-50.
TiO
x(OH)
y(OR)
zAlcosol makes in the tetralkyl titanate by stirring down alcoholic solution is added drop-wise to, and wherein the mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.1-5 is preferably 1: 0.2-4, more preferably 1: 0.3-3; Rate of addition is 0.2-8ml/min, is preferably 0.3-6ml/min, more preferably 0.5-3ml/min.Stirring velocity is generally 200-250rpm, for example 200rpm or 250rpm.Alcoholic solution is the aqueous solution of ethanol, propyl alcohol or butanols, and wherein the concentration of water is 0.2-0.3 volume %, for example can be 0.23 volume % or 0.25 volume %.Drip and usually carry out at normal temperatures.The TiO of described alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 1-10nm, for example 1-6nm or 3-9nm.
The film-forming components of in coating of the present invention, using can be known to those skilled in the art any film-forming components, the example is fluorocarbon resin, urethane resin, Synolac, thermosetting acrylic resin, resol, nitro-cotton, chlorinated rubber, pitch, modified rosin resin, thermoplastic acrylic resin etc.Being preferably membrane component is fluorocarbon resin.Be used for fluorocarbon resin of the present invention and be well known to those skilled in the art, the example is fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, tetrafluoroethylene propylene copolymer, tetrafluoroethylene-vinylidene-acrylic copolymer etc.The preferred used fluorocarbon resin of the present invention is selected from polyvinylidene difluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, tetrafluoroethylene-vinylidene-acrylic copolymer.
Coating of the present invention also comprises solvent.Solvent for use is common solvent or its mixture, includes but not limited to aromatic hydrocarbons such as dimethylbenzene, toluene etc.; Ester class such as ethyl acetate, butylacetate, Isoamyl Acetate FCC etc.; Alcohols such as butanols, isopropylcarbinol, phenylcarbinol etc.; Ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol diethyl ether etc.; Ketone such as methyl iso-butyl ketone (MIBK), methyl phenyl ketone, isophorone etc.Those skilled in the art can be according to the present invention the amount of definite solvent for use such as coating desired properties such as coating property.
Coating of the present invention also can comprise other component known to those skilled in the art, for example pigment; Filler, such as talcum powder, calcium carbonate, barium sulfate, silicon-dioxide etc.; Auxiliary agent, for example defoamer, wetting agent, dispersion agent, emulsifying agent, anti-settling agent, stablizer, antiskinning agent, flow agent, siccative, anti-sagging agent, softening agent, matting agent, fire retardant, mould inhibitor, sterilant, trapping agent etc.Those skilled in the art can be according to the present invention coating desired properties such as bactericidal property etc. determine concrete kind and the consumption thereof of used other component.
With the TiO that makes as mentioned above
x(OH)
y(OR)
zAlcosol, film-forming components, optional pigment and filler and optional auxiliary agent mix in solvent and obtain coating of the present invention, wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 15-85 is preferably 1: 20-65, more preferably 1: 25-50.
Used film forming component, solvent and optional pigment, filler and the auxiliary agent that uses are all as mentioned above.
The coating of the present invention that makes as mentioned above can be sealed, and in dry environment, preserve.Certainly, for coating of the present invention, preferred now-making-now-using.
Can be by any appropriate method known to those skilled in the art with application of paints of the present invention in material surface to be coated, such as roller coat, spraying, dip-coating, brushing, blade coating etc.With described application of paints after on the material surface to be coated, choose the TiO that in the presence of weak acid, makes in filming wantonly
x(OH)
y(OR)
zMinuteness particle further is hydrolyzed, and wherein weak acid can for example be formic acid, acetic acid, propionic acid or oxalic acid, and its concentration is the 0.1-10 % by weight, is preferably the 0.5-6 % by weight.In further hydrolytic process, because TiO
x(OH)
y(OR)
zMinuteness particle is during Uniform Dispersion and substantially being fixed on has been filmed, and the condensation degree that therefore is hydrolyzed the gained titanium dioxide nano-particle can not improve substantially, namely continues to remain about 1-10nm, obtains thus titanium dioxide nano-particle and is evenly distributed on wherein final coating.
Embodiment
Hereinafter by reference example the present invention is specifically described, but described embodiment does not consist of any restriction to the scope of the invention.
Embodiment 1
The 150g tetra-n-butyl titanate is added in the reactor, then, the aqueous ethanolic solution that with the 127ml water concentration is 0.25 volume % under the stirring velocity of 250rpm is added drop-wise in the reactor with the rate of addition of 3ml/min, dropwises rear continuation and stirs 1.5 hours, obtains water white TiO
x(OH)
y(OR)
zAlcosol.The particle size analyzer measuring result shows gained TiO
x(OH)
y(OR)
zThe TiO of alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 1-6nm.The volume ratio that the 0.71kg polyvinylidene difluoride (PVDF) is dispersed in dimethylbenzene, butylacetate and isophorone is to form the fluorocarbon resin dispersion system in 7: 2: 1 the mixed solvent, and its solid content is 40 % by weight.With gained TiO
x(OH)
y(OR)
zAlcosol adds in the fluorocarbon resin dispersion system and mixing obtains coating of the present invention.The gained paint spay-coating is obtained thickness on steel be about 30 microns filming, after the coating surface drying, with concentration be the acetic acid aqueous solution of 1.5 % by weight be sprayed at film on, and will film and be placed in the envrionment conditions, so that TiO wherein
x(OH)
y(OR)
zMinuteness particle further is hydrolyzed into titanium dioxide nano-particle.Final gained coating is tested, and acquired results sees Table 1.
Embodiment 2
The 150g titanium isopropylate is added in the reactor, then, the aqueous propanol solution that with the 124ml water concentration is 0.23 volume % under the stirring velocity of 200rpm is added drop-wise in the reactor with the rate of addition of 4ml/min, dropwises rear continuation and stirs 1.5 hours, obtains water white TiO
x(OH)
y(OR)
zAlcosol.The particle size analyzer measuring result shows gained TiO
x(OH)
y(OR)
zThe TiO of alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 2-8nm.The volume ratio that the 2.32kg vinylidene fluoride-hexafluoropropylene copolymer is dispersed in dimethylbenzene, butylacetate and isophorone is to form the fluorocarbon resin dispersion system in 7: 2: 1 the mixed solvent, and its solid content is 40 % by weight.With gained TiO
x(OH)
y(OR)
zAlcosol adds in the fluorocarbon resin dispersion system and mixing obtains coating of the present invention.The gained paint spay-coating is obtained thickness on steel be about 30 microns filming, after the coating surface drying, with concentration be the aqueous formic acid of 6 % by weight be sprayed at film on, and will film and be placed in the envrionment conditions, so that TiO wherein
x(OH)
y(OR)
zMinuteness particle further is hydrolyzed into titanium dioxide nano-particle.Final gained coating is tested, and acquired results sees Table 1.
Embodiment 3
The 150g tetra-n-butyl titanate is added in the reactor, then, the aqueous propanol solution that with the 17.3ml water concentration is 0.23 volume % under the stirring velocity of 250rpm is added drop-wise in the reactor with the rate of addition of 0.3ml/min, dropwises rear continuation and stirs 1.5 hours, obtains water white TiO
x(OH)
y(OR)
zAlcosol.The particle size analyzer measuring result shows gained TiO
x(OH)
y(OR)
zThe TiO of alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 1-10nm.The volume ratio that 1.41kg hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers is dispersed in dimethylbenzene, butylacetate and isophorone is to form the fluorocarbon resin dispersion system in 7: 2: 1 the mixed solvent, and its solid content is 40 % by weight.With gained TiO
x(OH)
y(OR)
zAlcosol adds in the fluorocarbon resin dispersion system and mixing obtains coating of the present invention.The gained paint spay-coating is obtained thickness on steel be about 30 microns filming, after the coating surface drying, with concentration be the oxalic acid aqueous solution of 0.6 % by weight be sprayed at film on, and will film and be placed in the envrionment conditions, so that TiO wherein
x(OH)
y(OR)
zMinuteness particle further is hydrolyzed into titanium dioxide nano-particle.Final gained coating is tested, and acquired results sees Table 1.
Embodiment 4
The 150g titanium isopropylate is added in the reactor, then, the aqueous ethanolic solution that with the 7.6ml water concentration is 0.25 volume % under the stirring velocity of 200rpm is added drop-wise in the reactor with the rate of addition of 0.8ml/min, dropwises rear continuation and stirs 1.5 hours, obtains water white TiO
x(OH)
y(OR)
zAlcosol.The particle size analyzer measuring result shows gained TiO
x(OH)
y(OR)
zThe TiO of alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 3-9nm.The volume ratio that 1.27kg tetrafluoroethylene-vinylidene-acrylic copolymer is dispersed in dimethylbenzene, butylacetate and isophorone is to form the fluorocarbon resin dispersion system in 7: 2: 1 the mixed solvent, and its solid content is 40 % by weight.With gained TiO
x(OH)
y(OR)
zAlcosol adds in the fluorocarbon resin dispersion system and mixing obtains coating of the present invention.The gained paint spay-coating is obtained thickness on steel be about 30 microns filming, after the coating surface drying, with concentration be the propionic acid aqueous solution of 2 % by weight be sprayed at film on, and will film and be placed in the envrionment conditions, so that TiO wherein
x(OH)
y(OR)
zMinuteness particle further is hydrolyzed into titanium dioxide nano-particle.Final gained coating is tested, and acquired results sees Table 1.
Performance test
Test foundation: JC/T1074-2008 " function of purifying indoor air coating material purifying property "
Test event: purifying formaldehyde efficient, toluene purification efficiency
Test condition: temperature (20 ± 2) ℃, relative humidity (50 ± 10) %, 48 hours test durations
Test result: as shown in table 1 below
Table 1
| The outward appearance of coating | The purification efficiency of PARA FORMALDEHYDE PRILLS(91,95) (%) | Purification efficiency (%) to toluene | |
| Embodiment 1 | Smooth smooth | 81.5 | 36.9 |
| Embodiment 2 | Smooth smooth | 80.5 | 36.3 |
| Embodiment 3 | Smooth smooth | 82.1 | 37.5 |
| Embodiment 4 | Smooth smooth | 80.1 | 36.1 |
Table 1 shows by coating gained coatingsurface of the present invention smooth smooth, and shows the purification efficiency of PARA FORMALDEHYDE PRILLS(91,95) of raising and the purification efficiency to toluene of raising.
Claims (28)
1. coating, described coating comprises following component:
A) TiO
x(OH)
y(OR)
zAlcosol, wherein:
X is not 0;
Z is not 0;
X+ (y+z)/2=2; With
R represents to have the straight or branched alkyl of 2-9 carbon atom;
The TiO of described alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 1-10nm; With
B) film-forming components;
Wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 15-85;
Wherein obtain TiO in the tetralkyl titanate by stirring down alcoholic solution is added drop-wise to
x(OH)
y(OR)
zAlcosol, wherein the mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.1-5; Rate of addition is 0.2-8ml/min.
2. the coating of claim 1, wherein R represents to have the straight or branched alkyl of 3-6 carbon atom.
3. the coating of claim 1, wherein R represents normal-butyl.
4. the coating of claim 1 is wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 20-65.
5. the coating of claim 1 is wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 25-50.
6. the coating of claim 1, wherein alcoholic solution is the aqueous solution of ethanol, propyl alcohol or butanols.
7. the coating of claim 1, wherein the mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.2-4.
8. the coating of claim 1, wherein the mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.3-3.
9. the coating of claim 1, wherein rate of addition is 0.3-6ml/min.
10. the coating of claim 1, wherein rate of addition is 0.5-3ml/min.
11. each coating among the claim 1-10, wherein film-forming components is fluorocarbon resin.
12. the coating of claim 11, wherein fluorocarbon resin is selected from fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, tetrafluoroethylene propylene copolymer, tetrafluoroethylene-vinylidene-acrylic copolymer.
13. the coating of claim 12, wherein fluorocarbon resin is selected from polyvinylidene difluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, tetrafluoroethylene-vinylidene-acrylic copolymer.
14. each coating among the claim 1-10, with described application of paints after on the material surface to be coated, choose the TiO that in the presence of weak acid, makes in filming wantonly
x(OH)
y(OR)
zMinuteness particle further is hydrolyzed.
15. the coating of claim 14, wherein weak acid is formic acid, acetic acid, propionic acid or oxalic acid, and its concentration is the 0.1-10 % by weight.
16. the coating of claim 14, wherein weak acid is formic acid, acetic acid, propionic acid or oxalic acid, and its concentration is the 0.5-6 % by weight.
17. a method for preparing coating said method comprising the steps of:
1) stirring is lower is added drop-wise to tetralkyl titanate Ti (OR) with alcoholic solution
4Middle acquisition TiO
x(OH)
y(OR)
zAlcosol, wherein:
X is not 0;
Z is not 0;
X+ (y+z)/2=2; With
R represents to have the straight or branched alkyl of 2-9 carbon atom;
The TiO of described alcosol
x(OH)
y(OR)
zThe particle diameter of minuteness particle is 1-10nm;
Wherein:
Alcoholic solution is the aqueous solution of ethanol, propyl alcohol or butanols;
The mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.1-5; With
Rate of addition is 0.2-8ml/min;
With
2) with TiO
x(OH)
y(OR)
zAlcosol, film-forming components, optional pigment and filler and optional auxiliary agent mix in solvent, wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 15-85.
18. the method for claim 17, wherein R represents to have the straight or branched alkyl of 3-6 carbon atom.
19. the method for claim 17, wherein R represents normal-butyl.
20. the method for claim 17, wherein the mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.2-4.
21. the method for claim 17, wherein the mol ratio of water is 1 in tetralkyl titanate and the alcoholic solution: 0.3-3.
22. the method for claim 17, wherein rate of addition is 0.3-6ml/min.
23. the method for claim 17, wherein rate of addition is 0.5-3ml/min.
24. the method for claim 17 is wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 20-65.
25. the method for claim 17 is wherein in the TiO of titanium dioxide
x(OH)
y(OR)
zThe weight ratio of alcosol and film-forming components is 1: 25-50.
26. each method among the claim 17-25, wherein film-forming components is fluorocarbon resin.
27. the method for claim 26, wherein fluorocarbon resin is selected from fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, tetrafluoroethylene propylene copolymer, tetrafluoroethylene-vinylidene-acrylic copolymer.
28. the method for claim 27, wherein fluorocarbon resin is selected from polyvinylidene difluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, tetrafluoroethylene-vinylidene-acrylic copolymer.
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|---|---|---|---|
| CN 201010254124 CN102304326B (en) | 2010-08-16 | 2010-08-16 | Coating and preparation method thereof |
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| CN102304326B true CN102304326B (en) | 2013-04-03 |
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| CN110195494B (en) * | 2019-06-28 | 2020-07-28 | 宁波瑞凌新能源科技有限公司 | Construction method of radiation refrigeration film on building outer layer and radiation refrigeration outer layer |
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| EP1281689A2 (en) * | 2001-07-31 | 2003-02-05 | Fuji Photo Film Co., Ltd. | Inorganic composition, film made therefrom, and method for producing such film |
| JP2003054950A (en) * | 2001-08-23 | 2003-02-26 | Ube Nitto Kasei Co Ltd | Method for producing metallic oxide thin film and method for producing organic-inorganic composite gradient material |
| CN1473884A (en) * | 2003-05-22 | 2004-02-11 | 福州大学 | Preparation of light purifying environment protection paint and coating technology |
| CN101184866A (en) * | 2005-05-31 | 2008-05-21 | 法国空中客车公司 | Sol for sol-gel process coating of a surface and coating method by sol-gel process using same |
| CN101318693A (en) * | 2007-06-04 | 2008-12-10 | 北京化工大学 | Method for preparing titanium dioxide nano -film in water solution |
-
2010
- 2010-08-16 CN CN 201010254124 patent/CN102304326B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000128645A (en) * | 1998-04-17 | 2000-05-09 | Ssi Technol Inc | Solgel binder solution and solution deposition therewith |
| EP1281689A2 (en) * | 2001-07-31 | 2003-02-05 | Fuji Photo Film Co., Ltd. | Inorganic composition, film made therefrom, and method for producing such film |
| JP2003054950A (en) * | 2001-08-23 | 2003-02-26 | Ube Nitto Kasei Co Ltd | Method for producing metallic oxide thin film and method for producing organic-inorganic composite gradient material |
| CN1473884A (en) * | 2003-05-22 | 2004-02-11 | 福州大学 | Preparation of light purifying environment protection paint and coating technology |
| CN101184866A (en) * | 2005-05-31 | 2008-05-21 | 法国空中客车公司 | Sol for sol-gel process coating of a surface and coating method by sol-gel process using same |
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