CN1384165A - Titania nano-paint for forming photocatalytic transparent hydrophilic coating and its prepn - Google Patents
Titania nano-paint for forming photocatalytic transparent hydrophilic coating and its prepn Download PDFInfo
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- CN1384165A CN1384165A CN 01115626 CN01115626A CN1384165A CN 1384165 A CN1384165 A CN 1384165A CN 01115626 CN01115626 CN 01115626 CN 01115626 A CN01115626 A CN 01115626A CN 1384165 A CN1384165 A CN 1384165A
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Abstract
The present invention relates to a paint. At normal temperature, nano-titania sol, organosilicon adhesive and solvent are mixed homogeneously to form the titania paint capable of forming photocatalytic transparent hydrophilic coating. The nano-titania content in the paint system is 0.5-30 g/L, and the organosilicon adhesive content is 0.2-1 times that of titania. The coating formed by the paint can form transparent superhydrophilic surface with contact angle smaller than 3 deg under photocatalysis.
Description
The invention belongs to paint field, particularly a kind of titania nano-paint that is used to form photocatalytic transparent hydrophilic coating and preparation method thereof.
As everyone knows, the booty degree of the body surface amphipathic property surperficial with it is closely related, if body surface is hydrophilic, then adheres to inorganic minerals such as sand and dust easily, otherwise, if body surface is lipophilic, then adhere to organism such as oil smoke easily.Along with Motor vehicles such as automobile are on the increase, airborne organic dirt sharply increases, exterior walls etc. are exposed to airborne body surface and are easy to dirty, the adhesivity of the inorganics that organic dirt compares is stronger, be difficult to remove, so be necessary body surface is made hydrophilic, to improve its anti-dirty ability.
Occurring in nature seldom has other Superhydrophilic material except mica, people can use tensio-active agent to realize the wetting ability of body surface, but tensio-active agent is easy to volatilization or washed away, can only keep the hydrophilic effect of a few hours to a couple of days.Since the nineties, it is found that titanium dioxide can realize super hydrophilic effect under the rayed effect, and this effect is a kind of photocatalysis, titanium dioxide itself can't be consumed, thereby is a kind of persistent effect.
Titanium dioxide is as a kind of important mineral dye, and the preparation method is a lot, and two kinds of sulfuric acid process and chlorination processs are wherein arranged.Sulfuric acid process is the titanium sulfate solution heating hydrolysis, after the metatitanic acid precipitation that obtains is purified, calcines under the high temperature more than 800 ℃, pulverizes then and makes finished product; Chlorination process is that the gas phase titanium tetrachloride is at high temperature used dioxygen oxidation, the preparation TiO 2 particles.
Have above-mentioned hydrophilic nmature in order to form at body surface, need be titanium dioxide or titanium dioxide nano-particle appendix to body surface.One of method is that the pure titanium plate of atmospheric oxidation or anodic oxidation forms titanium dioxide film, but pure titanizing stable in properties is difficult to oxidation, and hydrophilicity can not get guaranteeing.Another kind method is with CVD method evaporation titanium dioxide, forms film at substrate surface, and this method is the price height not only, and can only be used for specific base material.Also having a kind of method is that titanium dioxide nano-particle is distributed in water or the organic solvent, make coating, be sprayed onto on the base material, water or organic solvent volatilization back form the titanium dioxide nano-particle film, but titanium dioxide nano-particle is difficult to disperse, the film tack is poor, and smoothness is not enough, and hydrophilicity is bad.The method that solves is that the titanic acid ester hydrolysis is prepared titanium dioxide nano sol at present, then it is coated on and forms film on the matrix, but the shortcoming of this method is that the titanic acid ester raw material is expensive, titanium dioxide nano-particle is a undefined structure in the film, do not have the photochemical catalysis hydrophilic active, must be after the pyroprocessing more than 400 ℃ possess hydrophilic property energy, can not be used for the base material of non-refractory, as plastics etc., be not suitable for preparation big area coating yet.
The objective of the invention is to overcome preparation during titania nano-paint used titanic acid ester raw material expensive, titanium dioxide nano-particle does not have crystalline structure in the film of making, need defectives such as pyroprocessing ability possess hydrophilic property energy, a kind of titania nano-paint that is used to form photocatalytic transparent hydrophilic coating is provided.
A further object of the present invention provides the preparation method of the titania nano-paint that is used to form photocatalytic transparent hydrophilic coating, and this method is simple to operate, easy to implement.
The object of the present invention is achieved like this: the titania nano-paint that is used to form photocatalytic transparent hydrophilic coating comprises titanium dioxide nano-particle, organosilicon caking agent and solvent, and wherein titanium dioxide nano-particle content is 0.5～30 grams per liter of coating total amount; With SiO
2Meter, organosilicon caking agent content are 0.2～1 times of content of titanium dioxide in the coating.
The content of described titanium dioxide nano-particle in coating, preferably 2～10g/l.
Described solvent is water, alcohol or their mixture.Described alcohol is methyl alcohol, ethanol, Virahol or their mixture.
The median size of described titanium dioxide nano-particle is between the 3-100 nanometer; Between preferred 10～20 nanometers.
Described titanium dioxide nano-particle crystal formation is sharp titanium structure, rutile structure or their mixing crystal formation.
Described organosilicon caking agent is that silicone resin or structural formula are R
1 pSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof, wherein: R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, p+q+t=4,4 〉=q+t 〉=1, q+t is between 2～4, between preferred 3～4.
Further contain the known dispersion agent of those skilled in the art, coupling agent, perfume compound in the described coating.
Titanium dioxide nano-particle in the coating of the present invention, the preferred 3--100 nanometer of its particle diameter.When particle diameter is higher than 100 nanometers, cause the visible light scattering easily, make the coating of final formation opaque, influence the color and luster effect of coated article body itself, range of application is restricted; On the other hand, particle is more little, and the photochemical catalysis effect is good more, and the time that forms super hydrophily is short more.
The crystal formation of the titanium dioxide nano-particle in the coating of the present invention can be sharp titanium structure, it also can be rutile structure, can also be the mixing of sharp titanium and rutile crystal type structure, but the titanium dioxide nano-particle photocatalytic activity of anatase crystal type is better, price be also more cheap.
With the titanium sulfate thermal hydrolysis, the preparation metatitanic acid, purification, dry, low temperature calcination are used the monoprotic acid dispergation then, obtain titanium dioxide nano-particle colloidal sol.This colloidal sol transparent clear, wherein titanium dioxide nano-particle is in monodisperse status, and the median size of particle is between the 3-100 nanometer; Between preferred 10～20 nanometers, and crystal formation is sharp titanium or rutile structure, is specially adapted to the photocatalyst among the present invention.
The content of titanium dioxide nano-particle is 0.5～30 grams per liter of coating total amount among the present invention, and the too high then coat-thickness of titanium dioxide nano-particle content increases, and the transparency descends; The too low coatingsurface titanium dioxide nano-particle quantity not sufficient that then forms of titanium dioxide nano-particle content has reduced the photocatalytic surfaces hydrophilicity.Preferred content is 2～10g/l.
Caking agent is as a kind of important industrial raw materials and small stores, of a great variety, but most of organic adhesives all can be decomposed by the photocatalytic oxidation properties of titanium dioxide nano-particle, and the bonding strength of general inorganic adhesive and transparency all have problem.
Caking agent of the present invention is an available silicone resin on the market, also can prepare with hydrolyzable silicon compound and derivative (as silicon tetrachloride, silicon ester etc.) thereof.The preparation method of organosilicon caking agent is a lot, is R as adopting structural formula
1 pSiX
q(OR
2)
tThe hydrolyzable silicate of (p+q+t=4,4 〉=q+t 〉=1), under acidity or basic catalyst effect, hydrolysis prepares silanol, the crosslinked effect that can play caking agent of silanol.In the said structure formula, R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, they are collectively referred to as functional group.The q+t of functional group for a long time, coating hardness is good; The q+t of functional group after a little while, then the coating pliability is good.Functional group's q+t quantity is between 2～4, between preferred 3～4 in the silicoorganic compound of selecting for use among the present invention.Be used for rigid objects surfaces such as glass, ceramic tile, exterior wall, preferably selecting the q+t of functional group quantity for use is 4 silicon ester; When being used for plastics film, fibre product, preferably selecting the q+t of functional group quantity for use is 2～3 silicon ester.
Organosilicon caking agent in the coating of the present invention is with SiO
2Meter, its content is 0.2～1 times (weight ratio) of titanium dioxide nano-particle content in the system.If caking agent surpasses the content of titanium dioxide nano-particle, then the hydrophilic speed of photochemical catalysis is very slow, and final hydrophily also is difficult to reach perfect condition; If caking agent is less than 0.2 times (weight ratio) of titanium dioxide nano-particle content, then with body surface adhesion strength variation.
Solvent in the coating of the present invention preferably makes the mixed system of water and alcohol in order to obtain appearance of coat preferably, and the part by weight of alcohol is not less than 50%.If less demanding to transparency, then Chun ratio can reduce.
The preparation of coating of the present invention, under the normal temperature, that titanium dioxide nano-particle colloidal sol, organosilicon binding agent and solvent is even; Wherein titanium dioxide nano-particle content is 0.5～30 grams per liter of coating system total amount, with SiO
2Meter, organosilicon caking agent content is 0.2～1 times (weight ratio) of content of titanium dioxide in the coating system, makes the titania nano-paint that is used to form photocatalytic transparent hydrophilic coating.
The coating construction of coating of the present invention can be adopted common process such as dip-coating, brushing, spraying, some difference of appearance of coat possibility that different coating processes form, will be between economy and aesthetic property balance, the coating that forms can be dry at normal temperatures, if talk about easily, can be 50～150 ℃ of oven dry down, to bring into play organosilyl bonding strength to greatest extent, but being higher than 150 ℃ can cause the photochemical catalysis hydrophilic active to descend, if in outdoor big area coating, consider the influence of atmospheric moisture, high humidity is then dry slow, causes visual appearance to descend.
The coating that coating of the present invention forms, be preferably in solar radiation 1～2 day, to form hydrophilic surface, promptly the contact angle with water can reach below 3 °, even can be 0 °, under this super hydrophily, not only organism can not adhere to, even if inorganics dust etc. also just contact with body surface by water, thereby be very easy to clean; Even if after this a few days does not have the sunlight direct irradiation, super hydrophily still can be kept in its surface, if the longer time does not have solar radiation, hydrophily variation gradually then, and later in case solar radiation is arranged, its super hydrophily again can very fast recovery, and various can emitting contained the following ultraviolet source of artificial light of 380 nanometers and can both be played the effect same with solar radiation, wavelength is short more, the easy more realization of photochemical catalysis hydrophily.
Further describe technical scheme of the present invention below in conjunction with embodiment.
Embodiment 1. by weight percentage.
The preparation of nano titanic oxide sol: adjust titanium sulfate solution TiO
2Concentration 120g/l gets titanium sulfate solution 1000ml, with TiO
2Meter, add 1% crystal seed, be heated to boiling and keep boiling 3 hours, cooled and filtered is washed in the metatitanic acid iron level less than 100ppm with 5% aqueous sulfuric acid, under 200 ℃, be dried to water-content less than 1%, measuring the particle crystal formation with X-ray diffraction method is anatase titanium dioxide, stirs down and slowly joins 5% salpeter solution, and making concentration is the 200g/l TiO 2 sol, this colloidal sol is as clear as crystal, and measuring the TiO 2 particles mean diameter with laser method is 20 nanometers.
The preparation of organosilicon caking agent: in 250ml methyl alcohol, add 30ml silicic acid tetraethyl ester, stir, drip the mixed solution of deionized water 50ml and 60wt% nitric acid 2ml, add fashionable maintaining the temperature under 30 ℃, hydrolysis 5 hours, caking agent content is with SiO in the hydrolyzed solution that makes
2Be calculated as 40g/l.
The preparation of coating: under the normal temperature, get methyl alcohol 60ml, add the above-mentioned organosilicon caking agent 20ml that makes, stir, add the above-mentioned TiO 2 sol 4ml that makes then, adding methyl alcohol is 100ml to final volume, stirs promptly to make in 1 hour, wherein TiO
2/ SiO
2Weight ratio=1, titanium dioxide nano-particle content are 8g/l.
The preparation of coating and photocatalytic hydrophilic are measured: on the experiment print, seasoning forms Clear coating, scrapes resitant coatings with fingernail, cut do not occur with the above-mentioned coating dip coating that makes.With the medical sterilizing viltalight lamp irradiation of 15w, measure water contact angle after 4 hours less than 3 °; Sample is put in the container of complete light tight line, measuring water contact angle after 1 month is 5 °.
Embodiment 2.
With the coating that embodiment 1 prepares, dip-coating is placed on irradiation under the sunlight on the experiment print, measure water contact angle after 8 hours less than 3 °.
Example executes 3.
Organosilicon caking agent content and titanium dioxide nano-particle content ratio one are regularly investigated titanium dioxide nano-particle content to hydrophilic influence.
Press embodiment 1 described method, preparation titanium dioxide nano-particle content is respectively the coating of 0.3g/l, 1g/l, 3g/l, 5g/l, 8g/l, 10g/l, method by embodiment 1 prepares coating again, with the medical sterilizing viltalight lamp irradiation of 15w, except the coating of titanium dioxide nano-particle content 0.3g/l, other coating was measured water contact angle all less than 3 ° after 4 hours.Titanium dioxide nano-particle content is that the coating of the coating preparation of 0.3g/l, 1g/l is wiped easily with finger.
Embodiment 4.
Organosilicon caking agent content one is regularly investigated titanium dioxide nano-particle content to hydrophilic influence.
Press the same method of embodiment 1, preparation organosilicon caking agent content is 3g/l, and titanium dioxide nano-particle content is respectively the coating of 3g/l, 6g/l, 9g/l, 12g/l, 15g/l, 18g/l.Method by embodiment 1 prepares coating, and with the medical sterilizing viltalight lamp irradiation of 15w, time and coating hardness that water contact angle arrival is 0 ° see Table 1.
Table 1: organosilicon caking agent content one is nano titania regularly
Particle content is to hydrophilic influence
| TiO 2Content | 3g/l | ?6g/l | ?9g/l | ?12 ?g/l | ?15 ?g/l | ?18 ?g/l |
| Water contact angle arrives 0 ° of time | ＞12h | ?4h | ?3h | ?2.5h | ?2h | ?2h |
| Hardness | ◎ | ?◎ | ?◎ | ?○ | ?○ | ?× |
The measurement of hardness explanation
*. just can make breakdown of coating with the finger wiping
Zero. stayed cut with the finger wiping
◎. there is not cut with pointing to wipe to stay
Claims (10)
1. titania nano-paint that is used to form photocatalytic transparent hydrophilic coating, it is characterized in that: this coating comprises titanium dioxide nano-particle, organosilicon caking agent and solvent, and wherein titanium dioxide nano-particle content is 0.5～30 grams per liter of coating total amount; With SiO
2Meter, organosilicon caking agent content are 0.2～1 times of content of titanium dioxide in the coating.
2. coating as claimed in claim 1 is characterized in that: the content of described titanium dioxide nano-particle in coating is 2～10g/l.
3. coating as claimed in claim 1 is characterized in that: described solvent is water, alcohol or their mixture.
4. coating as claimed in claim 3 is characterized in that: described alcohol is methyl alcohol, ethanol, Virahol or their mixture.
5. coating as claimed in claim 1 is characterized in that: the median size of described titanium dioxide nano-particle is between 3～100 nanometers.
6. as claim 1 or 5 described coating, it is characterized in that: described titanium dioxide nano-particle particle diameter is between 10～20 nanometers.
7. coating as claimed in claim 1 is characterized in that: described titanium dioxide nano-particle crystal formation is sharp titanium structure, rutile structure or their mixing crystal formation.
8. coating as claimed in claim 1 is characterized in that described organosilicon caking agent is that silicone resin or structural formula are R
1 pSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof, wherein: R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, p+q+t=4,4 〉=q+t 〉=1, q+t is between 2～4.
9. coating as claimed in claim 8 is characterized in that: described structural formula is R
1 pSiX
q(OR
2)
tQ+t between 3～4.
10. the preparation method of the described coating of claim 1-9, it is characterized in that: under the normal temperature, titanium dioxide nano-particle colloidal sol, organosilicon binding agent and solvent is even, wherein titanium dioxide nano-particle content is 0.5～30 grams per liter of coating system total amount, organosilicon caking agent content is 0.2～1 times of content of titanium dioxide in the coating system, makes the titania coating that is used to form photocatalytic transparent hydrophilic coating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011156260A CN1167760C (en) | 2001-04-28 | 2001-04-28 | Titania nano-paint for forming photocatalytic transparent hydrophilic coating and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011156260A CN1167760C (en) | 2001-04-28 | 2001-04-28 | Titania nano-paint for forming photocatalytic transparent hydrophilic coating and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1384165A true CN1384165A (en) | 2002-12-11 |
| CN1167760C CN1167760C (en) | 2004-09-22 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911846B (en) * | 2006-08-15 | 2010-05-12 | 福耀玻璃工业集团股份有限公司 | Nanometer self-cleaning composition |
| CN102459086A (en) * | 2009-05-07 | 2012-05-16 | 南欧派克有限公司 | Aqueous titanium dioxide paste composition and method for preparing same |
| CN105273443A (en) * | 2014-06-05 | 2016-01-27 | 北京中科东亚纳米材料科技有限公司 | Nanometer self-cleaning, anti-fog and sterilization glass coating and preparation method thereof |
| CN105733324A (en) * | 2016-04-05 | 2016-07-06 | 四川理工学院 | Transparent super-hydrophilic coating emulsion and preparation method thereof |
| CN109913073A (en) * | 2019-03-01 | 2019-06-21 | 浙江大学 | A kind of super-hydrophilic coating and preparation method for medical endoscope camera lens |
| CN112920707A (en) * | 2021-04-08 | 2021-06-08 | 广东邦固化学科技有限公司 | Super-hydrophilic silicon nano coating and preparation method thereof |
-
2001
- 2001-04-28 CN CNB011156260A patent/CN1167760C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911846B (en) * | 2006-08-15 | 2010-05-12 | 福耀玻璃工业集团股份有限公司 | Nanometer self-cleaning composition |
| CN102459086A (en) * | 2009-05-07 | 2012-05-16 | 南欧派克有限公司 | Aqueous titanium dioxide paste composition and method for preparing same |
| CN105273443A (en) * | 2014-06-05 | 2016-01-27 | 北京中科东亚纳米材料科技有限公司 | Nanometer self-cleaning, anti-fog and sterilization glass coating and preparation method thereof |
| CN105733324A (en) * | 2016-04-05 | 2016-07-06 | 四川理工学院 | Transparent super-hydrophilic coating emulsion and preparation method thereof |
| CN105733324B (en) * | 2016-04-05 | 2017-12-26 | 四川理工学院 | A kind of transparent super-hydrophilic coating emulsion and preparation method thereof |
| CN109913073A (en) * | 2019-03-01 | 2019-06-21 | 浙江大学 | A kind of super-hydrophilic coating and preparation method for medical endoscope camera lens |
| CN109913073B (en) * | 2019-03-01 | 2020-08-21 | 浙江大学 | Super-hydrophilic coating for medical endoscope lens and preparation method thereof |
| CN112920707A (en) * | 2021-04-08 | 2021-06-08 | 广东邦固化学科技有限公司 | Super-hydrophilic silicon nano coating and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1167760C (en) | 2004-09-22 |
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Owner name: ZHONGKE NANO TECH ENGINEERING CENTER CO., LTD. Free format text: FORMER OWNER: CHEMISTRY INSTITUTE, CHINESE ACADEMY OF SCIENCES Effective date: 20031222 |
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Effective date of registration: 20031222 Address after: 100080 No. 52 Haidian Road, Beijing, 1508, Pacific Science and technology center, Zhongguancun Applicant after: Zhongke Nanometer Technology Engineering Center Co., Ltd. Address before: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Applicant before: Institute of Chemistry, Chinese Academy of Sciences |
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