CN101220231A - Bi-component titanium dioxide film forming liquid - Google Patents
Bi-component titanium dioxide film forming liquid Download PDFInfo
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- CN101220231A CN101220231A CNA2007101730571A CN200710173057A CN101220231A CN 101220231 A CN101220231 A CN 101220231A CN A2007101730571 A CNA2007101730571 A CN A2007101730571A CN 200710173057 A CN200710173057 A CN 200710173057A CN 101220231 A CN101220231 A CN 101220231A
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Abstract
The invention relates to a film forming reagent which is used for preparing super hydrophilic film with the function of catalytic active nanometer titanium dioxide under low temperature. The film forming reagent mainly consists of A component which contains titania sol in type of anatase crystal, an adhesive and a plasticizer and B component which contains a cross linker; wherein, the adhesive is polyacrylic ester (molecular weight: 10<5> to 2 multiplied by 10<5>), water soda ash glass (Na2O nSO2, wherein, n(modulus equals to 1 to 3) or polyvinyl alcohol (1,750 plus or minus 50); the plasticizer is glycol; the cross linker is oxalic acid, oxalic aldehyde, glutaric dialdehyde, sodium pyroborate or boracic acid. The titanium dioxide thin film prepared by film-forming reagent has permeability, photo-catalytic activity, super-hydrophilicity and antibiotic activity in visible light; beside, the titanium dioxide thin film made by the method has good mechanical property.
Description
Technical field
The present invention relates to a kind of film forming liquid that the low temperature preparation has Superhydrophilic and photocatalytic activity nano titanium oxide functional film that is used for.
Background technology
Because nano titanium oxide (TiO
2) function film has good optical property and dielectric properties, thereby be subjected to extensive concern in optics, photoelectronics and person in electronics.What is more important, it possesses photocatalytic activity and photic Superhydrophilic, makes TiO
2Function film becomes a kind of very practical Multifunction material.
TiO
2In the function film to TiO
2Crystalline structure certain requirement is arranged, normally the mode by high-temperature calcination realizes TiO
2The commentaries on classics crystalline substance of film.Yet the carrier in the practical application at present mostly is plastics, resin and color steel etc., and the organic polymer thermotolerance on surface is relatively poor, and surface energy is less, with TiO
2Poor Deng the interface compatibility between the inorganic coating.Therefore, how can be under cold condition, prepare at heat labile surface of polymer material and to have photic active nano-TiO
2Film, thus expand TiO
2The range of application of film is one of focus of research at present, also is the technical issues that need to address of the present invention.
Summary of the invention
The objective of the invention is to, a kind of film forming liquid that the low temperature preparation has Superhydrophilic and photocatalytic activity nano titanium oxide functional film that is used for is provided.
The said titanium dioxide film forming liquid of the present invention is a two-pack film forming liquid, and it is mainly by the titanium dioxide (TiO of anatase crystal
2) colloidal sol, binding agent and softening agent (A component), and linking agent (B component) is formed;
Wherein said binding agent is that (molecular weight is 10 to polyacrylic ester
5～2 * 10
5), sodium silicate (Na
2OnSO
2N (modulus)=1～3 wherein) or polyvinyl alcohol (PVA, molecular weight are 1750 ± 50), its consumption is every liter of anatase crystal TiO
2Colloidal sol adds 0.5 gram～2 grams; Said softening agent is an ethylene glycol, and its consumption is that ethylene glycol and concentration are that the volume ratio of the adhesive solution of 1wt%～3wt% is (0.05～0.8): 1, be preferably (0.1～0.2): 1
Said linking agent be oxalic acid, oxalic dialdehyde, glutaraldehyde, sodium tetraborate (borax) or boric acid.
In an optimal technical scheme of the present invention, in said A component, also comprise the water-based flow agent, as polyether-modified dimethyl siloxane water-based flow agent (JS-3018 Shanghai Jinshan Chemical Co., Ltd.) etc.
Description of drawings
Fig. 1 is the TiO with anatase crystal of embodiment 1 preparation
2The X-ray diffraction of powder (XRD) figure,
Fig. 2 is the TiO of embodiment 2 steps (a) preparation
2The visible light transmissivity figure of film,
Wherein a is a sample, and b is substrate.
Fig. 3 is the TiO of embodiment 2 steps (b) preparation
2The photocatalytic activity test pattern of film,
Fig. 4 is the TiO of embodiment 2 steps (b) preparation
2The Superhydrophilic test pattern of film.
Embodiment
Prepare the method for the said titanium dioxide film forming liquid of the present invention, comprise the steps:
(1) titanium dioxide (TiO of anatase crystal
2) preparation of colloidal sol:
With C
1-C
6It is in 0.5v/v%～2v/v% aqueous nitric acid that the mixed solution of alkyl titanate (preferred tetrabutyl titanate) and dehydrated alcohol is added drop-wise to concentration, stir, generate white suspension, obtaining blue opalescent translucent colloidal sol in 60 ℃～100 ℃ these white suspension of stirring (is the TiO of anatase crystal
2Colloidal sol);
Wherein: C
1-C
6The volume ratio of alkyl titanate and dehydrated alcohol is 20: 2.5.
(2) preparation of target compound:
By aforementioned ratio binding agent and softening agent are added TiO by the prepared anatase crystal of step (1)
2Promptly get the A component of titanium dioxide film forming liquid of the present invention after mixing in the colloidal sol.In addition, in prepared A component, also an amount of flow agent can be added, more smooth slick film can be obtained with this.The A component of gained and linking agent (B component) " compatibility " promptly constitute the said titanium dioxide film forming liquid of the present invention.
Be that base material (or claiming carrier) is example below with glass, the using method of the said titanium dioxide film forming liquid of the present invention be described:
Adopt the A component of the titanium dioxide film forming liquid that spraying method or crystal pulling method say the present invention to coat that (when adopting spraying method, spout is 5cm～10cm apart from the distance of glass baseplate on the simple glass; When adopting crystal pulling method, putting forward the film speed control is 2 millimeters～5 mm/second), at 15 ℃～30 ℃, humidity is under 40%～80% condition, at least 24 hours film forming (wet film) of drying, film gets product then its immersion to be contained in the supersaturated solution of linking agent (carrying out crosslinked) 5～30 minutes (preferred 20～25 minutes).
Utilize the made titanium deoxid film of film forming liquid provided by the invention that excellent perviousness is arranged in visible-range, the particle diameter of the Titanium particles in the film is 5nm～15nm, and by the anatase octahedrite phase composite single, that crystallization degree is good.Thereby it can show very strong photocatalytic activity, Superhydrophilic and anti-microbial activity under uv irradiating.In addition, made titanium deoxid film possesses excellent mechanical property.
The invention will be further elaborated by the following examples.Protection scope of the present invention is not limited by the cases cited.
Embodiment 1
The preparation of titanium dioxide film forming liquid (A component):
(a) mixed solution of 20ml tetrabutyl titanate and 2.5ml dehydrated alcohol being added drop-wise to volumetric concentration is that vigorous stirring 1h obtains white suspension in 1% the aqueous nitric acid.80 ℃ of heating 5 hours, vigorous stirring obtained blue opalescent translucent colloidal sol simultaneously with this suspension.
The colloidal sol that obtains 50 ℃ of 0.1MPa rotary evaporations 1 hour, and is diluted with water to 80ml, makes the titania hydrosol of 0.67M.Get small portion colloidal sol and be scattered in the big furnace pot, it is obtained corresponding powder in drying at room temperature, be used to do X-ray diffraction (XRD) test, characterize the prepared TiO of the present invention
2The crystal formation of colloidal sol.Test result is seen Fig. 1, shows the prepared TiO of the present invention
2Colloidal sol is single anatase crystal.
(b) take by weighing 2g polyvinyl alcohol (PVA) and join in the 100ml ionized water, swelling 2 hours heats to 100 ℃, and stirring and refluxing 1 hour obtains the water white transparency PVA aqueous solution.Get the colloidal sol that 25ml makes by step (a) and dilute 4 times, stir, refrigeration in the ice bath adds the made PVA aqueous solution of 6ml under ultransonic effect, and vigorous stirring, obtains the oyster white homogeneous solution, is original film forming liquid.On the basis of original film forming liquid, add ethylene glycol 1ml, polyether-modified dimethyl siloxane water-based flow agent 0.1ml, the A component of final film forming liquid.
Glass baseplate surface transparent TiO
2The preparation of film:
(a) will not make the vertical A component of inserting by the prepared final film forming liquid of embodiment 1 of the sheet glass of any processing, and form a wet film with crystal pulling method on the glass baseplate surface, pull rate is 1.6mm/s, and with the wet film drying at room temperature, promptly getting surface-coated has transparent TiO
2The glass baseplate of film.Perhaps, sheet glass placed be equipped with by 5cm place before the spraying plant nozzle of the A component of the prepared final film forming liquid of embodiment 1, evenly spraying forms a wet film on the glass baseplate surface, and with the wet film drying at room temperature, promptly getting surface-coated has transparent TiO
2The glass of film.
Tested the blank glass substrate and the surface scribbles TiO with the ultra-violet absorption spectrum instrument
2The UV, visible light light transmission rate of the glass baseplate of film.Test result is seen Fig. 2, shows to scribble TiO
2The glass baseplate of film is almost consistent with the blank glass base material in the transmitance at visible light place, and good transparency is arranged.
(b) will be coated with transparent TiO by what step (a) made
2The glass of film places oversaturated borax solution, keeps 20～30 minutes, takes out, and washes out a small amount of borax solid that separate out on the surface with deionized water, and drying at room temperature promptly gets crosslinked TiO
2Film.Adhesive force after crosslinked is significantly improved, and by the situation that comes off with the sand paper friction, and the sticking power that cross-hatching records all is greatly improved than before uncrosslinked.Wherein, the detected result of cross-hatching reaches 0 grade standard fully, and the cut edge is level and smooth fully, does not have at all to come off, and the netted three-dimensional structure that forms PVA is described, makes TiO
2Film is made the as a whole very excellent sticking power that has.
The TiO that the present invention is prepared
2The photocatalytic activity test of film:
Will be by the embodiment 2 prepared TiO that are covered with
2The glass of film vertically places 5mgL is housed
-1In the silica tube of rhodamine B solution, and be 25cm apart from light source center.Illumination 0-180min carries out the photocatalytic degradation reaction to rhodamine B solution under the high voltage mercury lamp of employing 300W, get part rhodamine B solution at set intervals, measure its absorbancy with Cary100 ultra-violet absorption spectrum instrument then and change, characterize surface of the present invention with this and scribble TiO in the maximum absorption wave strong point
2The photocatalytic activity of the glass of film, measurement result is seen Fig. 3.As shown in Figure 3, the prepared TiO of the present invention
2Film has good photocatalytic activity.
Embodiment 4
The TiO that the present invention is prepared
2The Superhydrophilic test of film:
Will be by the embodiment 2 prepared TiO that are covered with
2The glass of film is placed 5 days in air after, the black lamp that is placed on 125W shines different time down, measures the size of water contact angle.The centre wavelength of this black lamp is 365nm, and sample places on the flat board apart from the about 25cm of black lamp place, and it is the JC98A contact angle measurement that contact angle is measured used instrument, and test result is seen Fig. 4.As shown in Figure 4, illumination is after 10 minutes, and water is at the TiO that is tested
2Contact angle on the film has reached 2 degree, sprawls fully at substrate surface.The TiO that the present invention is prepared is described
2Film has good photic Superhydrophilic, can be used as materials such as anti-droplet, automatically cleaning.
Claims (6)
1. one kind is used for the film forming liquid that the low temperature preparation has Superhydrophilic and photocatalytic activity nano titanium oxide functional film, it is characterized in that, said film forming liquid is two-pack film forming liquid, and it is by the A component: the TiO 2 sol, binding agent and the softening agent that comprise anatase crystal; With the B component: linking agent is formed;
Wherein said binding agent is that molecular weight is 10
5～2 * 10
5Polyacrylic ester, modulus be that 1～3 sodium silicate or molecular weight are 1750 ± 50 polyvinyl alcohol; Said softening agent is an ethylene glycol; Said linking agent be oxalic acid, oxalic dialdehyde, glutaraldehyde, sodium tetraborate or boric acid.
2. film forming liquid as claimed in claim 1 is characterized in that, wherein the consumption of binding agent is every liter of anatase crystal TiO
2The binding agent that adds 0.5 gram～2 grams in the colloidal sol.
3. film forming liquid as claimed in claim 1 is characterized in that, wherein softening agent and concentration are that the volume ratio of the adhesive solution of 1wt%～3wt% is (0.05～0.8): 1.
4. film forming liquid as claimed in claim 3 is characterized in that, wherein softening agent and concentration are that the volume ratio of the adhesive solution of 1wt%～3wt% is (0.1～0.2): 1.
5. film forming liquid as claimed in claim 1 is characterized in that, also comprises the water-based flow agent in the A component.
6. film forming liquid as claimed in claim 5 is characterized in that, wherein said water-based flow agent is polyether-modified dimethyl siloxane water-based flow agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101730571A CN101220231B (en) | 2007-12-26 | 2007-12-26 | Bi-component titanium dioxide film forming liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101730571A CN101220231B (en) | 2007-12-26 | 2007-12-26 | Bi-component titanium dioxide film forming liquid |
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| CN101220231A true CN101220231A (en) | 2008-07-16 |
| CN101220231B CN101220231B (en) | 2010-06-16 |
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ID=39630320
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648148B (en) * | 2009-09-23 | 2011-01-12 | 合肥工业大学 | Preparation method of nanometer photocatalyst film for degrading organic matter in waste water |
| CN102205253A (en) * | 2011-04-18 | 2011-10-05 | 四川大学 | Supported photocatalyst with high activity under visible light and preparation method thereof |
| CN103031026A (en) * | 2011-10-08 | 2013-04-10 | 常熟市屹浩食品包装材料有限公司 | Polyvinyl alcohol radical composite coating fresh keeping packaging material nano TiO2 functional modification method |
| CN105107488A (en) * | 2015-08-04 | 2015-12-02 | 苏州聚康新材料科技有限公司 | Preparation method for TiO2 thin film available for photocatalytic degradation of organic pollutants |
| CN105423714A (en) * | 2015-12-30 | 2016-03-23 | 唐伟 | Medical instrument drying and storing device |
| CN105860597A (en) * | 2016-03-25 | 2016-08-17 | 南京工业大学 | Preparation method of low-cost titanium dioxide film forming liquid |
| CN107029691A (en) * | 2017-04-28 | 2017-08-11 | 华中科技大学 | A kind of preparation method and applications of air type light-catalyzed reaction film |
| CN111138893A (en) * | 2020-01-19 | 2020-05-12 | 广州市建桥音响配件有限公司 | Self-cleaning horn paint |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334143C (en) * | 2005-11-30 | 2007-08-29 | 华东理工大学 | Method for preparing titanium dioxide functional film from poly ethylene glycol terephthalate substrate surface |
-
2007
- 2007-12-26 CN CN2007101730571A patent/CN101220231B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648148B (en) * | 2009-09-23 | 2011-01-12 | 合肥工业大学 | Preparation method of nanometer photocatalyst film for degrading organic matter in waste water |
| CN102205253A (en) * | 2011-04-18 | 2011-10-05 | 四川大学 | Supported photocatalyst with high activity under visible light and preparation method thereof |
| CN103031026A (en) * | 2011-10-08 | 2013-04-10 | 常熟市屹浩食品包装材料有限公司 | Polyvinyl alcohol radical composite coating fresh keeping packaging material nano TiO2 functional modification method |
| CN103031026B (en) * | 2011-10-08 | 2015-08-12 | 常熟市屹浩食品包装材料科技有限公司 | A kind of PVA-based compelx coating fresh-keeping packaging material nano-TiO 2function modified method |
| CN105107488A (en) * | 2015-08-04 | 2015-12-02 | 苏州聚康新材料科技有限公司 | Preparation method for TiO2 thin film available for photocatalytic degradation of organic pollutants |
| CN105423714A (en) * | 2015-12-30 | 2016-03-23 | 唐伟 | Medical instrument drying and storing device |
| CN105860597A (en) * | 2016-03-25 | 2016-08-17 | 南京工业大学 | Preparation method of low-cost titanium dioxide film forming liquid |
| CN107029691A (en) * | 2017-04-28 | 2017-08-11 | 华中科技大学 | A kind of preparation method and applications of air type light-catalyzed reaction film |
| CN107029691B (en) * | 2017-04-28 | 2020-02-21 | 华中科技大学 | Preparation method and application of air type photocatalytic reaction film |
| CN111138893A (en) * | 2020-01-19 | 2020-05-12 | 广州市建桥音响配件有限公司 | Self-cleaning horn paint |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN113083040B (en) * | 2021-04-23 | 2022-03-01 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
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|---|---|
| CN101220231B (en) | 2010-06-16 |
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